1254078 玖、發明說明 (發明說明應敘明:發明所屬之技術領域、先前技術、內容、實施方式及圖式簡 一、發明所屬之技術領域 5 ^別 本發明係關於一種電著塗裝上漆，尤指一種適用於 結合真空電鍍與水性電著塗裝上漆之方法。 一、先前技術 傳統的浸潰電鍍（Immersion plating)最大的缺點就 疋廢水中重金屬的污染問題，如果沒有完善的防治設 備’會對整個環境及生物造成極為嚴重的戕害，但防治 没備的投資不菲，如果曰常管理不善，空有設備也是枉 然。在環保觀念成為第一優先的時代，傳統電鍍已被渲 染為聞之色變的工藝。其次，大部分的電鍍金屬層活性 都很高，暴露在大氣中氧化的速度非常快，為了防止電 鍍金屬層的氧化及刮傷，通常都會在其上再噴一層透明 漆做為保護層之用。很不幸地，目前此塗裝工藝以溶劑 型的透明清漆（Solvent-based Lacquer)為主，又會造成大 量揮發性有機物質（V0C)的溢散問題。所以以傳統電鍍工 藝所製得之產品，如未能有效抑制改善在其生產過程中 所產生的廢水、重金屬及VOC問題，勢必會被日趨嚴苛 的％保法規所淘汰。 反觀，真空電鍍這項工藝，幾乎完全沒有廢水及衍 生的重金屬污染之問題，無疑是給電鍍工藝開了另外一 扇囪。雖然文限金屬氣化溫度的影響，現階段可以使用 此項工藝來蒸鍍之金屬種類不像浸潰電鑛來得變化多 !254〇78 端，但著科技的日新月異，此項瓶頸也在逐步打開之 中。 目前最普遍的金屬真空電鍍流程是，首先（a)在已處 理乾淨的工件表面先施塗佈一層平坦化的光亮底塗，然 後（b)進行金屬薄膜之真空電鍍作業，最後（c)再在此金屬 鍍膜之上塗佈另一層保護用的透明清漆。以上流程可得 到金屬原色的產品，但如果是希望得到其他的色系，就 必須應用染色工藝，此時在（b)步驟後，可用兩種途徑來 達成著色之目的：（(>1)在金屬薄膜上染色，之後，再塗 ^層透明保濩漆膜，或（c-2)直接在金屬薄膜上塗裝有 色透明漆。 在上述的塗裝流程中所使用之塗料，仍舊是以溶劑 型塗料的噴塗方式為主，此項作業無疑對於現場作業人 員及週遭環境造成嚴重的我害。纟其在法令對於VOC溢 散官制日趨嚴苛的同時，真空電鍍工藝的本身雖然解決 了傳統電鍍對於水污染的威脅，但其前後的溶劑型噴塗 塗裝作業，卻又引發另一層面的環保問題。 三、發明内容 本發明之主要目的係在提供一種電著塗裝上漆方 法，俾能用任何形式的水性電著塗料來取代金屬真空電 鍍流程中底漆之噴塗塗裝。 本發明之另一目的係在提供一種電著塗裝上漆方 法，俾此利用真空電鍍工藝在（丨）的表面上獲得金屬薄 膜’取代流程繁瑣且污染性大的傳統浸潰電鍍工藝。 1254078 、本發明之再一目的係在提供一種電著塗裝上漆方 法’俾能於金屬薄膜上，再利用任何形式的水性電著塗 裝’同時搭配染色系統，可得到類似仿金、青銅、紅銅 的電鍍效果，或是任何溶劑型浸染或喷塗色漆之塗膜效 果。 本發明之又一目的係在提供一種電著塗裝上漆方 T，俾能用水性電著塗裝線來取代喷塗作業線，達到更 環保且同時提升塗裝的品質及塗膜對於工件的保護效 果。 為達成上述目的，本發明之電著塗裝上漆 要包括：提供-金屬工件，其中該工件係經過至少一程 序選自包括·脫脂、酸洗、表面調整及皮膜化成；電著 塗裝底漆於該工件之表面；真空電鍍一金屬薄膜於該工 件之表面之底漆之上；提供一水性電著漆工作液，並將 。亥電著漆工作液置於一電著槽中，其中該水性電著漆工 作液係將一電著塗料原漆加入純水稀釋而得；將該工件 置於该電著槽中，電著塗裝表漆於該工件之表面之金屬 薄膜之上，以及取出該工件，水洗後烘乾，完成電著塗 裝上漆。 簡&之，本發明即針對金屬真空電鍍的前、後塗裝 作業做革命性的改良，利用電著塗裝的方式來塗佈上述 金屬真空電鍍流程（a)項中的底漆塗裝作業及流程（c)項 中的透明或有色透明表漆的塗裝作業，所使用之塗料是 水性的環保型電著塗料。 1254078 在本發明中所提及的金屬工件，彳包括所 吊用之金屬類，諸如··鐵、鋁、 系上 鐵鋁不鏽鋼、銅、鋁合金、 、，5金、鎮合金。工件先經 紫可田#、 、肌細作業去油脂，脫脂作 ._…脫脂、冷脫脂、電解脫脂、超音波脫脂等方式 :之後，如果必要，再經過酸洗作業及表調作業 乾淨的工件表面。有時，為了加強工件之耐钱效果， 也可在工件表面進行皮膜化成處理，可以生成磷酸鋅、 碌酸鐵、碟酸㈣'的皮膜，在以上步驟處理完畢，再經 過2〜3次的純水洗作業，基本上可以得到乾淨之工件， 即可進行第一次的底塗電著作業。 底塗所用之電著塗料，可為陽離子型的電著塗料， 如環氧樹脂型電著塗料、丙烯酸（壓克力）樹脂型電著塗料 或聚胺酯（PU)樹脂型電著塗料，也可以為陰離子型電著 塗料，如陰離子壓克力樹脂電著塗料、陰離子聚胺酯樹 脂型電著塗料，這些電著塗料可以直接在市面上購得或 自行合成之。市售之電著塗料固成份都在25 wt%以上， 甚至高達60 wt%，所以使用前必須先經過加純水稀釋之 步驟。 電者塗料的插作固成分約在5〜20wt%之間，最佳範 圍在8〜15wt%之間。操作電壓可從30〜300V之間，最佳 範圍在50〜200V之間。電著時間在20〜180秒之間，最佳 電著時間在30〜120秒之間。其他的控制參數依品牌、種 類不同而不同。電著完成的濕膜，經2〜3道的純水洗之 後，進入烤爐中進行交鏈硬化。烘烤溫度及時間，依所 使用電著塗料而不同，一般烤溫約在90〜220°C之間，最 1254078 佳fe圍在130〜180C之間；烘烤時間在1〇〜5〇分鐘，最 佳範圍在20〜35分鐘之間。 除了以上只使用透明電著塗料外，也可以使用已添 加色：之電著塗料來作為底塗用漆，所添加之色料，可 為目前市面上廣泛認知的電著塗料用色料，諸如碳黑色 系、二氧化鈦色系、或其他無機色系之顏料系統。亦可 =使用其他添加劑的色料系統，利用添加消光粉、消光 霄或消光樹脂之類的消光型電著塗料。以此消光系統作 為底塗時，可以得到霧面的真空金屬薄膜。 、已完成平坦化底塗之工件，在保持絕對乾淨之下， 進入真工爸中進行金屬薄膜之蒸鑛。在本發明中，此項 真空電鍍流程’並無任何之限制’只要真空設備能達到 之條件下’任何可進行真空電鍍之金屬、合金類都可適 用。真空電鑛最大的優點是：⑴工作環境乾淨、安全， 無傳統浸潰電鍍的劇毒電鑛液（2)節省水資源⑺無重 金屬污染之虞（4)節省工時，可在1〇〜4〇分鐘内完成整個 金屬薄膜之蒸鍍作業。金屬鏟膜會因底漆性能的不同及 被蒸鑛金屬種類不同，得到效果、色澤不同之金屬鑛膜， 如鏡面銘膜、霧面銘膜、鈦膜、錫膜等。 —在真空電鍍作業完成之後，緊接著立刻進行表漆的 電者塗製作業’此作業最重要的目的即在保護性及 之變化。 作為表塗之電著樹脂，由於考慮到光澤、耐候、硬 度等，能，所以使用之樹脂多所限制。雖_氧樹脂型 之電著塗料有優良的耐㈣力，但耐候性卻不佳，而且 !254〇78 有黃變（yellowing)及透明度不夠的缺陷，並不適用於表漆 之電著塗裝，所以應用在表漆之電著塗料以市售的陽離 子型壓克力樹脂及聚胺酯樹脂，或陰離子型壓克力樹脂 為主。 表塗用電者漆的槽漆固成分維持在5〜15 wt%，最佳 範圍在8〜12wt%。操作電壓在3〇〜200V之間，最佳條件 在50〜150V之間。電著時間在10〜60秒，最適時間在2〇 〜45秒。塗膜之硬化溫度可在9〇〜17〇它之間，但為防止 咼/置硬化而造成塗膜之黃變（yeU〇wing)，硬化溫度最好在 150°C以下，而以i〇〇〜13(rc為最佳。烘烤的時間也不宜 過久，以40分鐘以内為佳，最好在2〇〜3〇分鐘。 除了上述熱硬化（thermosetting)的電著漆，紫外線硬 化（UV-curable)的電著漆也可以使用在本項發明中的底 塗及表塗作業上。 至於在塗膜顏色的變化上，本發明利用兩種途徑來 達到此目的。其一是直接在電著槽漆内添加染料（dye)或 顏料（pigment)，當進行電著時，染料或顏料會隨著樹脂 電沉積到金屬薄膜上，形成所需要之顏色。 對於染料系統而言，本發明中所使用之染料系統， 可為油性染料、水油兩用型染料、或水性染料，染料的 種類可為金屬錯化合物類、有機染料類或無機染料類， 染料添加到電著塗料的方式有三種： ()直接使用水可溶性的染料溶液添加到電著槽 漆之中。使用此種方法時，必須考慮到染料溶液與水性 電著塗料之相容性問題。由於槽漆之固成分約在ι〇%左 11 1254078 右’表不含有大於85%以上的水。所以最好使用水 兩用之染料種類’同時用來溶解染料粉末的溶劑也特 別加以選擇’適合的溶劑包括水、醇類；如乙醇、異丙 醇二正丁醇、異丁醇等’醇醚類如乙二醇單乙醚、2二 醇單丁醚。不同染料依對不同的溶劑的溶解度，先完全 溶解於該溶劑中製備成染料溶液，再依所要添加的槽二 系統來調整染料溶液之阳值’例如陽離子型電著槽漆， p^H值多為酸性’此時如果欲添加的染料溶液為驗性時， 最好用有機酸來調整染料溶液為酸性，使用的有機酸類 可為：醋酸、冰醋酸或乳酸等。反之，如果是陰離子型 電著漆則為驗性，染料溶液可用胺類或氨水來調整之。 常用之胺類有三乙胺、三乙醇胺等。 (二）染料粉末先用適合的溶劑完全溶解，再與高 ，份的電著樹脂充分混合，之後，再加純水稀釋成為電 著槽漆。使用此方法的染料是屬於油性染料，所以無法 直接加到水相的電著槽漆之中，所使用的程序是先將染 料粉末完全溶解於油性溶劑，例如：甲苯、二甲苯、= 基異丁酮、或親水性溶劑，例如：〔醇、異丙醇、乙二 醇單丁醚、乙一醇單己醚之中，再將此染料溶液與高固 份樹脂原漆（含水量最好低於1()%)充分混合之後，再 稀釋為電著槽漆。 (二）在上面第（二）項的方法中，染料粉末都需要高比 例的溶劑才能得到安定的染料溶液，㈣過量的溶劑也 進入到電著槽漆之中，會造成塗膜外觀的，，水痕，，缺陷。 為了改σ此缺’第（二）項的方法是先用溶劑把染料粉末 12 1254078 濕潤，染料與溶劑的比例約在1 : 1〜i: 5之間，最好在1 . 1〜1 : 3之間’所使用的溶劑種類可為第（二）項中所提及 的溶劑種類，但以醇醚類如乙二醇單乙醚、乙二醇單丁 j、乙二醇單己醚、或PPH(丙二醇單紛鍵）為佳。當染料 完全濕潤後，再加入高固份的電著樹脂原漆，使之完全 均勻，並加純水稀釋為電著槽漆。為了使染料與樹 脂能充分混合、溶解均勻’所添加之高固份電著樹脂原 漆之固成分應在40%以上，最好能維持在55%以上，對 染料才能得到較佳之溶解狀況。 有色電著槽漆的操作條件與透明電著槽漆大致相 同，基本上可依操作及管理透明電著槽漆之模式運作 之。唯一值得注意的是，塗膜的厚薄會直接影響到顏色 之深淺變化，所以在膜厚的控制上必須來得更精確一些< 另外一種塗膜著色的方式是用浸潰式（Dipping)的作 業方法，其流程是先利用電著的方式於金屬薄膜表面生 成一透明的樹脂塗膜，此透明塗膜經過水洗並吹乾之 後，直接浸入染料槽中進行著色作業。浸潰一定時間之 後，取出工件，再經水洗、一次性烘烤硬化後，即可得 到所需顏色之塗膜。在此作業方法中，透明電著漆可使 用上述提及的任何形式的表塗用電著樹脂。 至於浸潰式染料槽中所使用的染料系統，會因為前 面所使用的電著樹脂的帶電系統不同而改變。最簡單的 方式是用水、油兩用的染料，溶於強親水性溶劑之中， 例如·乙二醇單乙鱗、乙二醇單丙醚、乙二醇單丁醚等， 13 1254078 再用水稀釋成為染料水溶液，並用酸或胺類來調整溶液 之PH值，使之可與電著濕膜相容。 另一方法，是先將染料溶於溶劑之中，所用之溶劑 可為芳香族、酯類、酮類、醇類或醇醚類，但最好使用 醇類或醇醚類的親水性溶劑為佳。之後，再將此染料溶 液加到水溶性載體樹脂中，並加純水稀釋到可操作之黏 度範圍。在此所提及之水溶性載體樹脂，可為任何形式 的水可分散型樹脂，例如水性醇酸樹脂、水性環氧樹脂、 水性壓克力樹脂、水性pu樹脂、水性胺類樹脂等各種水 性泛用樹脂。載體樹脂可以是自乾型的，但最好是熱硬 化型、或UV硬化型的樹脂。如果透明樹脂是使用1；¥硬化 型電著樹脂，載體樹脂也應該搭配uv硬化樹脂。著色完 成之工件，再一次性的熱硬化或11¥光照硬化，得到完全 硬化的透明有色塗膜。 顏料系統比染料系統在配方組成上來得複雜許多， 而且顏料都有遮蓋力，如果在電著槽漆中顏料的色料比 (P/B ratio)太高的話，遮蓋力太好造成完全不透明塗膜的 話，就會失去金屬薄膜的特點。所以在使用此系統時， 色料比變得非常重要。又顏料大多是無機類礦物，所以 耐光方面比有機顏料來得優異許多。此處所使用的顏 料，並無任何限制，例如：碳黑、二氧化鈦、氧化鐵紅、 氧化鐵黃等等各種型態及結構的顏料均可適用。因顏料 無法像染料類是有機溶劑、甚至是水可溶的，所以使用 顏料系統時，在配方中必須有分散樹脂（grinding vehicle)、分散劑及界面活性劑的成份，並藉助各式研磨 1254078 機的分散，才能將顏料導入樹脂之中。開槽建浴時，依 比例將透明樹脂原漆與色料膏混合，並用純水稀釋之， 電著的條件及參數與前所述雷同，唯電著槽必須維持24 小時循環，防止色料的沉降。 在消光的效果方面，除了在底塗與真空電鍍層作變 化外，也可以在表塗上利用添加消光粉、消光膏之類， 有消光效果之添加到表漆之配方中達到表漆消光之效果 或表漆就直接使用有消光效果之電著塗料為之。 本發明所闡明的是電著塗裝與真空電鍍的結合，由 於電著塗裝所強調的就是被塗物必須是電的導體，而在 本發明中，由於工件都是金屬材質，所以底塗利用電著 的技術來進行塗裝是輕而易舉的，之後的真空電鍍與底 漆塗裝方式無關。但因為金屬工件在底漆塗佈上去時， 就成為電的絕緣體，所以表漆是否能進行電著塗裝，完 全仰賴真空電鍍金屬膜的導電效果是否優良來決定，關 鍵在金屬膜厚不可太薄甚至是不連續膜，而影響到導電 性。一般希望金屬薄膜之膜厚在〇·3μ左右，但為了導電性 的考量，本發明希望金屬薄膜之膜厚可達到0·5〜1μ之 間。另外，吊具與工件的接觸點也是要特別注意的地方。 四、實施方式 需注意的是，本發明之電著塗裝上漆方法中，該電著塗 料原漆較佳係至少一選自一由陽離子型電著塗料、陰離 子型電著塗料所組成之群組，其中該陽離子型電著塗料 較佳係為環氧樹脂型電著塗料、壓克力樹脂型電著塗料 15 1254078 或聚胺酯樹脂型電著塗料，而該陰離子型電著塗料較佳 =為陰離子壓克力樹脂電著塗料或陰離子聚胺酯樹脂型 ^者塗料’ ·本發明之電著塗裝上漆方法之表漆上漆步驟 ，该電著漆工作液之操作固成分係佔該電著漆工作液 之重量百分比並無限制，較佳係介於5〜15 %之間，更佳 係’丨於8〜12%之間；該電著塗裝上漆步驟之操作電壓並無 限制，較佳係介於30〜200伏特之間，更佳係介於5〇〜15〇 伏特之間；施加該操作電壓之電著時間並無限制，較佳 係介於10〜60秒之間，更佳係介於2〇〜45秒之間。本發明 之電著塗裝上漆方法之底漆上漆步驟中，該電著漆工作 液之操作固成分係佔該電著漆工作液之重量百分比並無 限制，較佳係介於5〜20 %之間，更佳係介於8〜15%之間； 忒操作電壓並無限制，較佳係介於3〇〜3〇〇伏特之間，更 佳係介於50〜2〇〇伏特之間；該操作電壓之電著時間並無 限制，較佳係介於20〜180秒之間，更佳係介於3〇〜12〇秒 之間；本發明中所使用之顏色組成物並無限制，較佳係 選自廣泛認知的電著塗料用色料系統，諸如碳黑色系、 二氧化鈦色系、或其他無機色系之顏料系統；本發明中 所使用之之烘乾方式並無限制，基本上係搭配所使用之 料而u周正’較佳係為為熱固化型或紫外線硬化型；本 發明中所使用之水性有色電著漆工作液之配製方法較佳 係將至少一染料溶液加入該電著漆工作液中，其中該染 料溶液係將一染料粉末溶於一溶劑中並調整1>11值，或將 染料粉末用溶劑完全溶解成為染料溶液後，再與電著塗 料原漆混合均勻，最後再加純水稀釋為有色電著漆工作 16 1254078 液，或將染料粉末先用少量溶劑濕潤後，加到電著塗料 原漆中混合均勻，最後再加純水稀釋為有色電著漆工作 液^本發明所使用之之染色浸潰工作液，其配製方法較 佳係包括下列二種：用水、油兩用的染料，溶於強親水 性溶劑之中，再用水稀釋成為染色浸潰工作液，並用酸 或胺類來調整工作液之pH值，使之可與電著濕膜相容； 或者先將染料溶於溶劑之中成為染料溶液，再將此染料 /谷液加到水溶性載體樹脂中，並加純水稀釋到可操作之 黏度範圍，成為染色浸潰工作液；本發明所使用之水溶 性載體樹脂並無限制，較佳可為任何形式的水可分散型 樹脂係任一選自一水性醇酸樹脂、水性環氧樹脂、水性 壓克力樹脂、水性PU樹脂、水性胺類樹脂等各種水性泛 用樹脂。 為能讓貴審查委員能更瞭解本發明之技術内容，特 舉七較佳具體實施例說明如下。 實施例一：透明底塗之電著塗裝 151.5g之TE-2215電著塗料原漆，一邊攪拌、一邊緩 缓加入848.5g之純水，得到1000g、固份1〇%的電著漆工 作液，成分如下表1所列。將前處理完畢的工件，浸入工 作液内’與電源供應器的陰極連接，陽極則為不銹鋼板， 一樣浸入工作液中。在工作液維持28°c並有攪拌的情況 下，通50V直流電開始電著，時間3〇秒，之後，取出工件， 17 1254078 水洗乾淨，置入烤箱中烘烤150°C，時間30分鐘，可得到 膜厚ΙΟμηι、光澤佳的透明底塗。 1) 66% 表1 項目 重量（g) 固成份 TE-22lT*1^ 151.5 99.99 純水 848.5 0 總計 旦业-4- 、士 1000 99.99 ΤΕ-2215是尚漆（股）公司生產之陽^子型壓克力電著 塗料，固成份 實施例二：消光黑色底塗之電著塗裝 400g之ΤΕ-6500電著塗料原漆，i〇〇g之E-54iil黑色 消光色料及500g之純水，依序秤重加入1〇〇〇(：(：•之燒杯 中，利用磁攪拌混合均勻，其成分如下表2所列。同樣工 件置於陰極，電著條件為15〇Vx6〇sec，烘烤條件為18〇它 X30分鐘，最後可得到2〇μ左右的消光黑色底塗，光澤約 30〜40(60° ) 〇 表2 項 目 重量（g) 固成份 ΤΕ-6500^^ 400 144 Ε-541ΙΪΓ^ 100 41 純水 500 0 18 !254〇78 總計 l〇〇〇g 185 1) TE-6500是尚志造漆（股）公司生產之陽離子型環氧電著塗料，固成份36 % 2) Ε-541 1L是尚志造漆（股）公司生產之消光黑色電著用色料，固成份41 %、色料比（P/B ratio) : 140 實施例三：透明表漆之電著塗裝 已完成真空電鍍的工件，可再浸入實施例一的工作 液中，施以相同的電著條件、及相同的烘烤條件，得到 透明、光澤佳的表漆。 實施例四：仿金色表漆之電著塗裝 首先，依重量比1 : 10的配比，將黃色染料及橙色染 料溶於乙二醇單丁謎中，溶解成染料溶液，精秤2 0g的橙 色染料液及1.6g的黃色染料液，加到i56.25g之TE-2213 陽離子壓克力電著樹脂中，充分攪拌均勻。最後，緩緩 加入840.15g之純水，得到固成份為1〇%的仿金色電著工 作液，其成分如下表3所列。將已完成真空電鍍的工件浸 入工作液中並與整流器上之陰極接通，使用不銹鋼或石 墨為陽極，通直流電d.c.50v，時間3〇秒，完成後取出水 洗，置入130 C之熱風循環烤箱3〇分鐘，可得與電鍍金類 似的仿金色電著工件。 表3 項目 重量⑻ 固成份 橙色染料液” 2.0 一 19 1254078 黃色染料液U 1.6 — TE-2213 ” 156.25 100 純水 840.15 — 總計 1000 100 1) orange-251(BASF):乙二醇單丁醚（BCS)=1 : 10 所配置成的 2) yellow-15 7(BASF) : BCS= 1 : 10所配製成的染料液 3) TE-2213是尚志造漆（股）公司生產之陽離子型壓克力電著塗料，固成份 64% 染料液 實施例五：仿青銅色染料液之配製 7g的黃色染料粉末（yellow-141，BASF)先溶於21g的 BCS之中’再加入154g的分散樹脂充分混合，之後，緩緩 加入純水，稀釋到500g，此溶液即為浸潰型青銅色染料 液0 實施例六：仿青銅色表漆之製備 先依實施例三之流程，得到濕膜狀態的工件，將此 工件直接浸到實施例五之中，浸潰時間6〇秒，取出後， 水洗乾淨，放入烤箱之*15〇t：x2〇分鐘硬化完成，即可 得到類似青銅電鍍色澤的工件。 實施例七：珍珠白表漆之電著塗裝 乂 l56.25g之TE-2213中加入3g之E_21〇〇白色色料，充 刀此合均勻。然後，緩緩加入84〇75g之純水，得到1〇〇〇 白色的電著漆工作液’其成分如下表4所列。將已 鍍上鏡面銘膜之工件’浸入其中，進行電著，電著條件 20 1254078 可得到有珍珠白致 50Vx30sec，烘烤條， 果的塗裝工件。1254078 发明, description of the invention (the description of the invention should be clarified: the technical field, prior art, content, embodiment and drawing of the invention belong to the technical field of the invention. 5 The present invention relates to an electric painting lacquering Especially for a method combining vacuum plating and waterborne electrocoating. I. The biggest shortcoming of the prior art Immersion plating is the pollution of heavy metals in wastewater, if there is no perfect prevention. Equipment's will cause extremely serious damage to the whole environment and living things, but the investment in prevention and control is not high. If the management is not good, the equipment is also in vain. In the era when the environmental protection concept has become the first priority, the traditional electroplating has been rendered. Secondly, most of the electroplated metal layers are highly active, and the oxidation rate is very fast when exposed to the atmosphere. In order to prevent oxidation and scratching of the electroplated metal layer, a layer is usually sprayed on it. Clear lacquer is used as a protective layer. Unfortunately, this coating process is solvent-based varnish (Solvent-based Lacquer). Mainly, it will cause a large amount of volatile organic matter (V0C) to overflow. Therefore, the products made by the traditional electroplating process cannot effectively suppress the improvement of wastewater, heavy metals and VOC problems generated in the production process. It is bound to be eliminated by the increasingly stringent % protection regulations. On the other hand, the vacuum plating process has almost no problem of waste water and derivatized heavy metal pollution, which is undoubtedly another opening of the electroplating process. The impact of temperature, at this stage can use this process to evaporate the metal type is not as much as the erosion of the electric mine! 254〇78 end, but with the rapid development of technology, this bottleneck is gradually opening. The most common metal vacuum plating process is to first (a) apply a flat, bright primer to the surface of a cleaned workpiece, then (b) perform a vacuum plating of the metal film, and finally (c) Another layer of protective clear varnish is coated on the metal coating. The above process can obtain a product of metallic primary color, but if other color systems are desired, It is necessary to apply the dyeing process. At this time, after the step (b), two ways can be used to achieve the purpose of coloring: ((>1) dyeing on the metal film, and then applying a transparent protective film, or (c-2) Directly coating the metal film with a clear paint. The paint used in the above coating process is still mainly based on the spray coating of solvent-based paint. This work is undoubtedly for the field workers and surrounding The environment is causing serious harm to us. While the law is becoming more and more stringent for the VOC spillover system, the vacuum plating process itself solves the threat of water pollution caused by traditional electroplating, but the solvent-based spray coating operation before and after it Another aspect of the environmental problem is caused. III. SUMMARY OF THE INVENTION The main object of the present invention is to provide an electrocoating and painting method, which can replace the primer in the metal vacuum plating process with any form of aqueous electrocoating. Spray coating. Another object of the present invention is to provide an electrocoating lacquering method whereby a vacuum filming process is used to obtain a metal film on a (丨) surface to replace a conventional immersion plating process which is cumbersome and highly polluting. 1254078, Still another object of the present invention is to provide an electrocoating and painting method, which can be applied to a metal film, and then use any form of aqueous electrocoating, together with a dyeing system, to obtain a similar gold-like and bronze. , the plating effect of red copper, or the coating effect of any solvent-based dip dyeing or spray paint. Another object of the present invention is to provide an electric painting lacquering surface T, which can replace the spraying line with an aqueous electric coating line, thereby achieving a more environmentally friendly and at the same time improving the quality of the coating and the coating film for the workpiece. Protection effect. In order to achieve the above object, the electrocoating lacquering of the present invention comprises: providing a metal workpiece, wherein the workpiece is subjected to at least one process selected from the group consisting of: degreasing, pickling, surface conditioning, and film formation; Painted on the surface of the workpiece; vacuum plating a metal film on the surface of the workpiece; providing an aqueous electrocoat working solution. The electro-painting working liquid is placed in an electro-working tank, wherein the aqueous electro-coating working liquid is obtained by adding an electro-coating paint original paint to pure water; the workpiece is placed in the electro-groove, and the electro-working The coating is painted on the metal film on the surface of the workpiece, and the workpiece is taken out, washed with water, dried, and painted by electric painting. Jane &, the present invention is a revolutionary improvement of the front and rear coating operations of metal vacuum plating, and coating the primer coating in the metal vacuum plating process (a) by electrocoating. The coating of transparent or colored transparent paint in operation and process (c) is a water-based environmentally friendly electro-coating. 1254078 The metal workpiece referred to in the present invention, including the metal to be used, such as iron, aluminum, iron-aluminum stainless steel, copper, aluminum alloy, aluminum alloy, gold alloy, and alloy. The workpiece is firstly removed by Zioketian#, and the muscles are finely greased and degreased. _...Degreasing, cold degreasing, electrolytic degreasing, ultrasonic degreasing, etc.: Afterwards, if necessary, the pickling operation and the surface adjustment work are clean. The surface of the workpiece. In some cases, in order to enhance the durability of the workpiece, it is also possible to carry out a film formation treatment on the surface of the workpiece, which can produce a film of zinc phosphate, iron sulphate, and acid (four)', which is processed in the above steps, and then 2 to 3 times. Pure water washing operation, basically can get a clean workpiece, you can carry out the first primer coating industry. The electrocoating used for the primer can be a cationic electrocoat, such as an epoxy type electrocoat, an acrylic (acrylic) resin type electrocoat or a polyurethane (PU) resin type electrocoat, or It is an anionic electrocoating, such as anionic acrylic resin electrocoating and anionic polyurethane resin electrocoating. These electrocoatings can be directly purchased or synthesized by the market. Commercially available electrocoats have a solids content of more than 25 wt%, or even as high as 60 wt%, so they must be diluted with pure water before use. The plug coating of the electric paint is about 5 to 20 wt%, and the optimum range is between 8 and 15 wt%. The operating voltage can be from 30 to 300V, and the optimum range is between 50 and 200V. The electric time is between 20 and 180 seconds, and the best time is between 30 and 120 seconds. Other control parameters vary by brand and species. The wet film that has been completed by electricity is washed with 2 to 3 channels of pure water and then enters the oven for cross-linking hardening. Baking temperature and time are different depending on the electro-coating used. Generally, the baking temperature is between 90 and 220 °C, and the most 1254078 is between 130 and 180C. The baking time is between 1 and 5 minutes. The best range is between 20 and 35 minutes. In addition to the above use of only transparent electrocoating, it is also possible to use an electroless coating which has been added as an undercoating paint, and the added coloring material can be a coloring material for electrocoating which is widely recognized on the market, such as A carbon black, titanium dioxide, or other inorganic color pigment system. It is also possible to use a colorant system using other additives, and to use a matte type electric paint such as matting powder, matting or matting resin. When the matting system is used as a primer, a matte vacuum metal film can be obtained. The flattened primer has been completed, and under the absolute cleanliness, enter the real work dad to carry out the metal film steaming. In the present invention, the vacuum plating process is not limited to any one of the metals and alloys which can be vacuum-plated as long as the vacuum equipment can reach it. The biggest advantages of vacuum electric ore are: (1) The working environment is clean and safe, and there is no traditional immersion electroplating of highly toxic electric mineral liquid (2) Water saving (7) No heavy metal pollution (4) Saving man-hours, can be in 1〇~4 The evaporation of the entire metal film is completed in minutes. Metal shovel film will have different effect and different color of metal ore film, such as mirror surface film, matte film, titanium film, tin film, etc., depending on the performance of the primer and the type of metal being distilled. - After the completion of the vacuum plating operation, the electric paint application operation of the paint immediately follows. The most important purpose of this work is the change in protection. As the electrocoat resin for the surface coating, since the gloss, weather resistance, hardness, and the like are considered, the resin to be used is often limited. Although the oxy-resin type electrocoat has excellent resistance to (four) force, but the weather resistance is not good, and 254〇78 has yellowing (yellowing) and insufficient transparency, it is not suitable for electrocoating of paint. Therefore, the electroless paint applied to the paint is mainly a commercially available cationic acrylic resin and polyurethane resin, or an anionic acrylic resin. The coating composition of the surface painter's paint is maintained at 5 to 15 wt%, and the optimum range is 8 to 12 wt%. The operating voltage is between 3 〇 and 200 volts, and the optimum condition is between 50 and 150 volts. The electric time is between 10 and 60 seconds, and the optimum time is between 2 and 45 seconds. The hardening temperature of the coating film can be between 9 〇 and 17 〇, but the yellowing of the coating film (yeU〇wing) is prevented to prevent 咼/hardening, and the hardening temperature is preferably below 150 ° C, and i 〇 〇~13 (rc is the best. The baking time should not be too long, preferably within 40 minutes, preferably in 2〇~3〇 minutes. In addition to the above thermosetting electropaint, UV curing ( UV-curable electrocoating can also be used in the primer and topcoating operations of the present invention. As for the change in color of the coating film, the present invention utilizes two approaches to achieve this purpose. Dye or pigment is added to the electro-coating lacquer. When electro-working, the dye or pigment is electrodeposited onto the metal film to form the desired color. For the dye system, the present invention The dye system used in the present invention may be an oily dye, a water-oil dye, or an aqueous dye. The type of the dye may be a metal compound, an organic dye or an inorganic dye. The dye is added to the electrocoat. Three kinds: () direct use of water soluble The dye solution is added to the electro-coating paint. When using this method, the compatibility of the dye solution with the aqueous electro-coating must be considered. Since the solid content of the trough paint is about ι〇% left 11 1254078 right 'table It does not contain more than 85% water. Therefore, it is best to use a water-based dye type. The solvent used to dissolve the dye powder is also specially selected. ' Suitable solvents include water and alcohols; for example, ethanol, isopropanol 'Alcohol ethers such as butanol and isobutanol, such as ethylene glycol monoethyl ether and 2 glycol monobutyl ether. Different dyes are completely dissolved in the solvent to prepare a dye solution according to the solubility of different solvents. Add the groove two system to adjust the positive value of the dye solution'. For example, the cationic electro-coating lacquer, the p^H value is mostly acidic. At this time, if the dye solution to be added is for the test, it is better to adjust the dye with an organic acid. The solution is acidic, and the organic acid used may be: acetic acid, glacial acetic acid or lactic acid, etc. Conversely, if it is an anionic electrocoating, it is an experimental one, and the dye solution can be adjusted with an amine or ammonia water. Amine, triethanolamine, etc. (2) The dye powder is completely dissolved in a suitable solvent, and then thoroughly mixed with a high portion of the electro resin, and then diluted with pure water to become an electric channel paint. The dye using this method is It is an oily dye, so it cannot be directly added to the electrocoat of the aqueous phase. The procedure used is to completely dissolve the dye powder in an oily solvent such as toluene, xylene, = isobutyl ketone, or hydrophilic. Solvent, for example: [alcohol, isopropanol, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, and then this dye solution and high solid resin original paint (water content is preferably less than 1 (%)) After thorough mixing, dilute to the electric channel paint. (2) In the method of item (2) above, the dye powder requires a high proportion of solvent to obtain a stable dye solution, and (4) excess solvent also enters the electricity. Among the groove paints, it will cause the appearance of the film, water marks, and defects. In order to change the σ, the method of the second item is to wet the dye powder 12 1254078 with a solvent, and the ratio of the dye to the solvent is between 1: 1 and i: 5, preferably at 1. 1 to 1: The type of solvent used between 3 may be the type of solvent mentioned in item (2), but with alcohol ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl j, ethylene glycol monohexyl ether, Or PPH (propylene glycol single bond) is preferred. When the dye is completely wet, add a high-solid epoxy resin base paint to make it completely uniform, and add pure water to dilute it into an electric channel paint. In order to make the dye and the resin sufficiently mixed and dissolved uniformly, the solid component of the high-solid epoxy resin original paint to be added should be 40% or more, preferably maintained at 55% or more, and the dye can be preferably dissolved. The operating conditions of the colored electro-coating lacquer are substantially the same as those of the transparent electro-coating lacquer, and basically operate in accordance with the mode of operation and management of the transparent electric lacquer. The only thing worth noting is that the thickness of the film will directly affect the color depth change, so it must be more precise in the control of the film thickness. Another way to color the film is to use Dipping. The method comprises the steps of: firstly forming a transparent resin coating film on the surface of the metal film by means of electric drawing, and after the water-washing and drying, the transparent coating film is directly immersed in the dye tank for coloring operation. After immersing for a certain period of time, the workpiece is taken out, washed with water, and bake hardened at one time to obtain a coating film of the desired color. In this method of operation, the transparent electrocoat can be coated with an electrocoating resin of any of the above-mentioned forms. As for the dye system used in the dipping dye tank, it will change depending on the charging system of the electro resin used in the front. The easiest way is to use water and oil dyes in a strong hydrophilic solvent, such as ethylene glycol monoethyl sulphate, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, etc., 13 1254078 Dilute to an aqueous dye solution and adjust the pH of the solution with an acid or an amine to make it compatible with the wet film. In another method, the dye is first dissolved in a solvent, and the solvent used may be an aromatic, an ester, a ketone, an alcohol or an alcohol ether, but it is preferred to use a hydrophilic solvent such as an alcohol or an alcohol ether. good. Thereafter, the dye solution is added to the water-soluble carrier resin and diluted with purified water to an operable viscosity range. The water-soluble carrier resin mentioned herein may be any form of water-dispersible resin, such as water-based alkyd resin, water-based epoxy resin, water-based acrylic resin, water-based pu resin, water-based amine resin, and the like. General purpose resin. The carrier resin may be a self-drying type, but is preferably a heat-hardening type or a UV-curing type resin. If the transparent resin is a 1; ¥ hardened type of resin, the carrier resin should also be combined with a uv hardening resin. The finished workpiece is colored and then cured by one-time heat hardening or 11 ¥ light to obtain a completely hardened transparent colored film. The pigment system is much more complicated in formulation than the dye system, and the pigment has opacity. If the pigment ratio (P/B ratio) is too high in the electro-coating paint, the hiding power is too good to cause complete opacity coating. If the film is used, it will lose the characteristics of the metal film. So when using this system, the pigment ratio becomes very important. In addition, most of the pigments are inorganic minerals, so the light resistance is much better than organic pigments. There are no restrictions on the pigments used herein, for example, carbon black, titanium dioxide, iron oxide red, iron oxide yellow, and the like, and various types and structures of pigments can be applied. Since pigments cannot be organic solvents or even water-soluble like dyes, when using pigment systems, there must be components of grinding vehicles, dispersants and surfactants in the formulation, and with various types of grinding 1254078 The dispersion of the machine can introduce the pigment into the resin. When the bath is opened, the transparent resin original paint and the color paste are mixed according to the ratio, and diluted with pure water. The conditions and parameters of the electric drawing are the same as those described above, but the electric tank must be maintained for 24 hours to prevent the color material. Settlement. In terms of the effect of matting, in addition to the changes in the primer coating and the vacuum plating layer, it is also possible to use a matting powder, a matting paste or the like on the surface coating, and a matting effect is added to the formulation of the paint to achieve the matting finish. The effect or paint is directly applied to the electric paint with matting effect. The invention clarifies the combination of electro-coating and vacuum plating. Since electro-coating emphasizes that the object to be coated must be an electrical conductor, in the present invention, since the workpiece is made of metal, the primer is applied. It is a breeze to use electro-technical techniques for painting, and the subsequent vacuum plating has nothing to do with the way the primer is applied. However, since the metal workpiece becomes an electrical insulator when the primer is applied, whether the paint can be electropainted or not depends entirely on whether the conductive effect of the vacuum-plated metal film is excellent, and the key is not to be too thick. Thin or even discontinuous film affects conductivity. It is generally desired that the film thickness of the metal thin film is about 〇3μ, but in order to consider the conductivity, the present invention desirably has a film thickness of between 0.5 and 1 μ. In addition, the point of contact between the spreader and the workpiece is also a special place to pay attention. 4. Embodiments It should be noted that in the electrocoating and painting method of the present invention, the electrocoat primer is preferably at least one selected from the group consisting of a cationic electrocoat and an anionic electrocoat. a group, wherein the cationic electrocoating material is preferably an epoxy resin type electrocoating, an acrylic resin type electrocoating material 15 1254078 or a polyurethane resin type electrocoating, and the anionic electrocoating is preferably = The invention relates to an anionic acrylic resin electrocoating or an anionic polyurethane resin type coating. The coating lacquering step of the electrocoating lacquering method of the invention, the operating solid component of the electrocoating working fluid occupies the electricity The weight percentage of the paint working liquid is not limited, and is preferably between 5 and 15%, more preferably between 8 and 12%; the operating voltage of the electrocoating painting step is not limited. Preferably, the system is between 30 and 200 volts, more preferably between 5 and 15 volts; the duration of the application of the operating voltage is not limited, preferably between 10 and 60 seconds. The better system is between 2〇~45 seconds. In the primer painting step of the electrocoating lacquering method of the present invention, the operating solid component of the electrocoating working fluid is not limited by the weight percentage of the electrocoating working fluid, and preferably is 5~ Between 20%, better between 8 and 15%; 忒 operating voltage is not limited, preferably between 3〇~3〇〇V, better than 50~2〇〇V The duration of the operation voltage is not limited, and is preferably between 20 and 180 seconds, more preferably between 3 and 12 seconds; the color composition used in the present invention is Without limitation, it is preferably selected from a widely recognized pigment system for electrocoating, such as a carbon black system, a titanium dioxide color system, or other inorganic color pigment systems; the drying method used in the present invention is not limited. Basically, it is preferably used as a thermosetting type or an ultraviolet curing type; and the method of preparing the aqueous colored electrocoating working liquid used in the present invention is preferably at least one dye solution. Adding to the electrocoat working solution, wherein the dye solution dissolves a dye powder Adjusting the value of 1>11 in a solvent, or completely dissolving the dye powder into a dye solution with a solvent, and then uniformly mixing it with the original paint of the electro-coating paint, and finally diluting it with a pure water to a colored electro-painting work 16 1254078 liquid, Or the dye powder is first wetted with a small amount of solvent, then added to the original paint of the electro-coating paint to be evenly mixed, and finally diluted with pure water to be colored into the working liquid of the colored paint. The dyeing and dipping working liquid used in the invention is prepared. Preferably, the method comprises the following two methods: a dye for water and oil, dissolved in a strong hydrophilic solvent, diluted with water to form a dyeing and immersing working solution, and adjusted with an acid or an amine to adjust the pH of the working fluid. It can be compatible with the electro-wet film; or the dye is dissolved in the solvent to form a dye solution, and the dye/gluten solution is added to the water-soluble carrier resin, and diluted with pure water to an operable viscosity range. It is a dye-impregnated working solution; the water-soluble carrier resin used in the present invention is not limited, and preferably any form of water-dispersible resin is selected from a water-based alkyd resin, water-based epoxy resin, water. A variety of aqueous acrylic resin, aqueous PU resin, an amine resin, the aqueous resin pan. In order to enable the reviewing committee to better understand the technical contents of the present invention, the seventh preferred embodiment will be described below. Example 1: Electroless coating of 151.5 g of TE-2215 electrocoat original paint, while slowly stirring, 848.5 g of pure water was added to obtain 1000 g of solid paint work of 1% by weight. The liquids are as listed in Table 1 below. The pre-processed workpiece is immersed in the working fluid to be connected to the cathode of the power supply, and the anode is a stainless steel plate, which is immersed in the working fluid. When the working fluid is maintained at 28 ° C and stirred, the electricity is started by 50 V DC for 3 sec. After that, the workpiece is taken out, washed at 17 1254078, and placed in an oven for baking at 150 ° C for 30 minutes. A transparent undercoat having a film thickness of ημηι and good gloss can be obtained. 1) 66% Table 1 Item Weight (g) Solid Content TE-22lT*1^ 151.5 99.99 Pure Water 848.5 0 Total Danye -4-, Shi 1000 99.99 ΤΕ-2215 is the yang of the lacquer company Acrylic electro-coating, solid component example 2: matte black primer coating 400g of ΤΕ-6500 electric paint original paint, i〇〇g E-54iil black matting color and 500g of pure water In the order of 1: (: (: • beaker), use magnetic stirring to mix evenly, the composition is listed in Table 2. The same workpiece is placed on the cathode, the electrical condition is 15〇Vx6〇sec, bake The baking condition is 18 〇 it is X30 minutes, and finally a matte black primer of about 2 〇μ is obtained, and the gloss is about 30~40 (60°). Table 2 Item Weight (g) Solid Content ΤΕ-6500^^ 400 144 Ε- 541ΙΪΓ^ 100 41 Pure water 500 0 18 !254〇78 Total l〇〇〇g 185 1) TE-6500 is a cationic epoxy electrocoat produced by Shangzhi Lacquer Co., Ltd., solid content 36% 2) Ε -541 1L is a matte black electric coloring material produced by Shangzhi Lacquer Co., Ltd., solid content 41%, color ratio (P/B ratio): 140 Example : The transparent paint is applied to the workpiece which has been vacuum-plated, and can be immersed in the working fluid of the first embodiment, and subjected to the same electrical conditions and the same baking conditions to obtain a transparent and glossy paint. . Example 4: Electro-coating of imitation gold paint First, according to the ratio of weight ratio of 1:10, the yellow dye and the orange dye are dissolved in the ethylene glycol single-dragon puzzle, dissolved into a dye solution, and the fine scale is 20 g. The orange dye solution and 1.6 g of the yellow dye solution were added to i56.25 g of TE-2213 cationic acrylic resin and stirred well. Finally, 840.15 g of pure water was slowly added to obtain a gold-like working liquid having a solid content of 1%, and the composition thereof is shown in Table 3 below. The vacuum-plated workpiece is immersed in the working fluid and connected to the cathode on the rectifier. The stainless steel or graphite is used as the anode. The DC dc50v is applied for 3 seconds. After completion, the water is taken out and placed in a hot air circulating oven of 130 C. In 3 minutes, you can get a gold-like electric workpiece similar to electroplated gold. Table 3 Item Weight (8) Solid Orange Dye Solution 2.0 19 1954078 Yellow Dye Liquid U 1.6 — TE-2213 ” 156.25 100 Pure Water 840.15 — Total 1000 100 1) orange-251 (BASF): Ethylene Glycol Monobutyl Ether ( BCS)=1 : 10 2) yellow-15 7 (BASF): BCS= 1 : 10 formulated dye liquid 3) TE-2213 is a cationic pressure produced by Shangzhi Lacquer Co., Ltd. Cree electro-coating, solid content 64% dye solution Example 5: Preparation of imitation bronze dye solution 7g yellow dye powder (yellow-141, BASF) is first dissolved in 21g of BCS' plus 154g of dispersion resin After thorough mixing, slowly add pure water and dilute to 500g. This solution is the impregnated bronze dye solution. Example 6: Preparation of imitation bronze paint First, the wet film state is obtained according to the procedure of the third embodiment. The workpiece is directly immersed in the fifth embodiment, the immersion time is 6 sec., after taking out, the water is washed clean, and it is hardened by *15 〇t: x2 〇 minutes in the oven to obtain a similar bronze plating color. The artifact. Example 7: Electro-coating of pearl white paint 乂 Add 3g of E_21 〇〇 white coloring material to TE5613 of l56.25g, and fill it evenly. Then, 84 〇 75 g of pure water was slowly added to obtain 1 〇〇〇 white electrocoat working solution. The composition thereof is as listed in Table 4 below. The workpiece which has been plated with the mirror film is immersed in it, and the electric workpiece is obtained under the condition of 20 1254078. The coated workpiece with pearl white 50Vx30sec, baking strip and fruit can be obtained.
0 志造漆 色色耳 從以上實施财可知，本發明所提供之方法 101.4 、仃’摒除了傳統浸潰電鍍的繁㈣ 代之以環保的真空金屬電鍍，另 〜 荽泠壯t ,、 乃卜也以％保的水性電 者主波取代溶劑型的喷塗作辈 問題。 貝言作業’改善了 VOC的溢散污染 上述實施例僅係為了方便說明而舉例而已，本發明 所主張之權利範圍自應以申喑專 僅限於上述實施例。“專利-圍所述為準，而非 210 造漆色色耳 As can be seen from the above implementation, the method provided by the present invention 101.4, 仃 '摒 in addition to the traditional immersion plating (4) replaced by environmentally friendly vacuum metal plating, another ~ 荽泠 t t,, 卜The solvent-based spray is also replaced by the water-based main wave of %. The present invention has been exemplified for the convenience of the description, and the scope of the claims claimed herein is exclusively limited to the above embodiments. "Patent - as described above, not 21