201024465 六、發明說明： 【發明所屬之技術領域】 本發明是有關於一種金屬基材的表面處理方法，特別 是指一種含鎂基材之表面處理方法。本發明亦有關於藉由 本發明方法所獲得的層疊物，以及該方法所使用之拋光液 與塗裝液。 【先前技術】 ,. 含鎂基材藉由其質輕、比強度（specific strength)高吸 震性強、可隔離電磁波干擾（electromagnetic interference， EMI)等特性，而獲得例如運動器材與3C商品製造商之青睞 ，並成為器材撐架或商品外殼之材質首選。相較於其他的 金屬基材，含鎂基材的活性較高而易腐蝕，因此需要經過 表面處理方法以提升其抗腐蝕性後，才適合作為所欲商 品的一構件，繼而參與商品的組裝。 該表面處理方法通常可分為依序進行之一清潔步驟、 一鈍化步驟，與一有色塗裝步驟。 該清潔步驟是用以先去掉原先附著於該含鎂基材表面 上之氧化物、油脂等非所欲的物質，其通常是視需要地先 將該含錢基材予以鑄型後，再經過驗劑、界面活性劑溶液 、酸劑、水的反覆沖洗或浸泡來清潔該含艤基材。 »亥鈍化步驟則疋藉由—純化液來與經過該清潔步驟後 的含錢基材表面相互接觸，並使該基材表面上之鈍化液乾 燥後形成-鈍化膜，藉以保護經過該清潔步驟而裸露於大 氣中且抗腐钱性極差的該基材，並使其具有一定程度之抗 201024465 腐姓性。 但是，該清潔步驟會使得基材表面喪失原本的金屬光 澤，而，呈現黯淡狀，且該鈍化膜亦多呈透明而不能美化外 觀’因此尚需要一有各塗裝步驟，亦即在該鈍化膜上塗覆 一層有色漆料，如此才能完整地覆蓋該基材的暗沉外觀， 並同時利用所形成出的有色漆料膜之色彩分佈，與漆料的201024465 VI. Description of the Invention: [Technical Field] The present invention relates to a surface treatment method for a metal substrate, and more particularly to a surface treatment method for a magnesium-containing substrate. The present invention also relates to a laminate obtained by the method of the present invention, and a polishing liquid and a coating liquid used in the method. [Prior Art], the magnesium-containing substrate obtains, for example, sports equipment and 3C product manufacturers by its light weight, high specific strength, high shock absorption, and isolation of electromagnetic interference (EMI). It is favored and becomes the material of choice for equipment racks or commodity shells. Compared with other metal substrates, the magnesium-containing substrate has higher activity and is more corrosive. Therefore, it needs to be surface-treated to enhance its corrosion resistance, and then it is suitable as a component of the desired product, and then participates in the assembly of the product. . The surface treatment method can generally be divided into one cleaning step, one passivation step, and a colored coating step. The cleaning step is for removing the undesired substances such as oxides, greases and the like which are originally attached to the surface of the magnesium-containing substrate, and usually, after casting the money-containing substrate, as needed, and then passing through The ruthenium-containing substrate is cleaned by repeated rinsing or soaking of the test agent, surfactant solution, acid agent, or water. The step of passivating is further carried out by contacting the surface of the money-containing substrate after the cleaning step with a purification liquid, and drying the passivation liquid on the surface of the substrate to form a passivation film, thereby protecting the cleaning step. The substrate exposed to the atmosphere and extremely poor in corrosion resistance has a certain degree of resistance to 201024465. However, the cleaning step causes the surface of the substrate to lose its original metallic luster, and is dull, and the passivation film is also transparent and cannot beautify the appearance. Therefore, it is necessary to have a coating step, that is, in the passivation. The film is coated with a colored paint to completely cover the dull appearance of the substrate, and at the same time utilize the color distribution of the formed colored paint film, and the paint
厚實感，來迎合洧費者之視覺偏好，並再加強該基材之抗 腐钱性P 上述表面處理方法的缺點在於操作過程繁複、需耗費❹ 大量的水與有機溶劑，且必須使用有色漆料，來遮蓋經過 該清潔步驟後色澤黯淡的含鎂基材，因而降低了製造商對 於後續之機殼或撐架外觀設計，與商品行銷市場定位規劃 的彈性。此外，該表面處理方法對於該含鎂基材在鑄型時 不慎造成的表面細微凹陷與微小裂縫，亦無彌補之效。 亦有不少的消費者認為外殼具金屬質感與光澤之商品 具有未來感、高級感，與時尚感，而對其情有獨鍾；為使 得一以該含鎂基材而製得的器材撐架或商品外殼符合此等❹ 消費者的需求_ ’常用_.的製備方法是待該含錢基材形成出該. 純化膜後，’再以.電鑛法來使該純化膜上被多層次地錄覆上 .. 他種金屬（例如依序鍍上銅 '鎳、絡等等）而形成的一層疊物-;然而此法因需要消耗大量電能且會引發重金屬污染，特 別是路可能會衍生出具致癌性的Cr6+離子。因此，該習知 方法成本高更不符環保訴求，再者該層疊物中所電鑛上的 金屬並不易分離，因而增加了回收各類金屬的困難度。 201024465 顯見地，本領域需要的是一包含有一含鎂基材層，且 單純地藉由其來散發出金屬光澤的層昼物以利於讓廠商 能更彈性地規劃相關產品之外觀設計並創造龐大的商業利 益；而本領域亦需要一種操作簡便、水與有機溶劑之用量 較少、符合環保訴求、使該含鎂基材能盡量免於被腐蝕， 且更可使該含鎂基材表面呈現金屬光澤的含鎂基材之表面 處理方法。 【發明内容】 因此，本發明之第一目的，即在提供一種可以達成上 述各式目的之含鎂基材表面的處理方法，其包含一拋光步 驟，以及一改質步驟或一塗裝步驟。 該抛光步驟'是將一含鎂基材與由.一固態部分和一液態 部分所構成的抛光液接觸，並拋光該基材，待該拋光液的 固態部分自該基材表面上被移除後，乾燥所留置的液態部 分並使其在該基材表面上形成一披覆膜；其中，該拋光液 之固態部分是包括有多個研磨粒子，該液態部分則包括有 一強鹼、一芳香性化合物、一錯合劑、一磷酸根源，與一 第一溶劑。 該改質步驟與塗裝步驟基本上是擇一地，或該改質步 驟、塗裝步驟依序施行。該改質步驟是將一改質液與形成 在該含鎂基材表面上之披覆膜相接觸後乾燥，藉以使該彼 覆膜被改質而包括有一銜接於該基材表面上之本體區，與 一遠離該基材表面地銜接於該本體區上之改質區；該塗裝 步驟則是將一塗裝液或一漆料來與該彼覆膜接鱗後’使該 201024465 彼覆膜上的塗裝液乾燥而在該坡覆膜上形成出—塗裝膜。 其中，該？冬質液包含有一鈦源、一飢源、一酸根源、一中 和劑，與一第二溶劑，而該塗裝液包含有一塗覆用樹脂， 以及一塗裝添加劑。 上述之本發明方法可視所選擇進行的是改質步驟或塗' 裝步驟，甚至是該等步驟之接績進行，而對應地獲得作為 本發明第二〜四目的之各層疊物。該等層疊物基本上分別 包含有一含鎂基材層以及一形成在該含鎂基材層上之披覆 膜層’或藉該塗裝步驟之選擇性施行，而更包含有一形成❹ 在該披覆膜層上之塗裝膜層’或選擇性地以該改質步驟來 使該彼覆膜層包括有一形成在該含鎂基材層上之本體區， 與一遠離該含鎂基材層地形成在該本體區上的改質區。 本發明之第五、六目的，即分別在於提供一拋光液與 塗裝:液’其等是可被應用.於進行上述本發明第一目的之 方法，而所形成出之披覆膜與塗裝膜亦是呈透明狀，可供 該含鎂基材之金屬光澤穿透。 除了可使所處理的含鎂基材獲得防蝕保護之外，本發〇 明表面處理方法亦具有諸多優勢，例如操作步驟非常簡便 且實施上極具彈性、所需耗水量少而可節約水資源、未使 用録，亦不會產生大量廢水或重金屬污染，且所獲得的層 叠物中之該含鎂基材亦容易被回收，因而極符合環保訴求 ;另一方面，經該拋光步驟後之含鎂基材，除了其上的微 小凹陷及微小裂縫可藉由該拋光液之液態部分而被修飾或 修補以外’所獲得的層疊物之各膜層呈透明且厚度薄，故 201024465 位於最底層之含鎂基材的金屬光澤得以散發出來，而使該 層鲞物具有金屬質感。 另’該塗裝步驟可使用本領域之一般漆料，或選用本 發明塗裝液來進行；而該塗裝液可選擇性地配製為呈水性 或油性者’且視所使用的物料種類，而可形成出耐濕性、 硬度、抗磨性皆佳，且水及髒污皆不易附著於上的塗裝膜 ’故藉由此種特殊塗裝液所形成的塗裝膜之表面除了可長 期維持潔淨以外，亦能對所披覆之該含鎂基材提供更完善 • 的隔離與保護功效。 【實施方式】 基於刖述本發明各目的之基本要件暨所獲功效，於此 將進一步說明其等之實施方式並例示可使用物料或次要操 作條件。 本發明含鎂基材之表面處理方法除了包含有該拋光步 驟，以及基本上於該拋光步驟後所擇一進行的該改質步驟 或塗裝步驟之外，本發明方法亦可為包含有依序施行的該 • 拋光步驟、改質步驟，及塗裝步驟；各步驟之實施程序已 如上所述。而本方法是適用於各式材質之含鎂基材，其中 例如 AZ014D、AM60、AM50、AEx-3、AE44 等本領域常使 用的鎂基材，亦是本案所適用者。 該拋光步驟所使用之本發明拋光液，是由一固態部分 與一液態部分所構成，該固態部分是包括有多個研磨粒子 ，該液態部分則包括有一強鹼、一芳香性化合物、一錯合 劑、一構酸根源，與一第一溶劑。 , 201024465 於本發明拋光液中’相對於其液態部分，該固態部分 可在該雄光液中佔有較大比例’較佳地，該固態部分是佔 拋光液之50 wt%〜99.9 wt%之間；更佳地是佔8〇 〜 98 wt%之間；最佳地是佔90 wt%〜％之間。另，該. 固態部分是可經回收而被重複使用，因此就該拋光液而言 ，具消耗性者僅有其液態部分，且其可僅佔少量而有效節 省了製備商的物料成本，更避免了一般會因使用後廢棄， 所造成的大量廢水。 就該等研磨粒子而言，其材質可擇自於二氧化石夕（Si〇2)參 、三氧化二鋁（Al2〇3)、硬質樹脂【例如環氧樹脂、聚丙烯 酸衍生物樹脂等等】，以及一般常使用之陶瓷材料【例如锆 氧化物、鈦氧化物、鈽氧化物等】；另允許將如以上所述之 不同材質的研磨粒子加以混用。亦建議該等研磨粒子之粒 徑是介於2腿〜15麵之間。 而就該液態部分，建議其強鹼可擇自於氫氧化鉀（k〇h) 、氫氧化鈉（NaOH)、氫氧化鋰（LiOH)、氫氧化鈣【Ca(〇H)2 】、氫氧化鋇【Ba(OH)2】，或此等之一組合；其中較佳的強❾ 鹼是择自於NaQH、KOH，或此等之一組合。另建議在該液 態部分中’該強鹼的含量是佔〇.1 wt%〜5〇 wt%之間較 佳地是佔1 Wt%〜15 wt%之間。 建議該芳香性化合物可使用例如具有芳香性之盼類衍 生物（特別是具芳香性的苯酚類化合物）、具芳香性之雜環衍 生物’或此等之一組合。其中該苯酚類化合物除了具芳香 性之外’其結構亦具有苯環，與銜接於該苯環上，且至少 201024465 一擇自於一OH、一 NH2、一 SH、一 N〇2、_ c〇〇H 等之官 能基；較佳地該笨酚類化合物是擇自於水揚酸、鄰苯二紛 、對苯一紛.、間苯二紛、硝基苯盼、胺基苯盼.、甲基苯酚 、甲基苯二酚，或此等之一組合；更佳地是擇自於水楊酸 、鄰苯二酚、硝基苯胺，或此等之一組合。另建議在該液 態部分中，該.芳香性化合物的含量是佔0丨wt% ~2Q wt% 之間，較佳地是佔0.5 wt%〜5 wt%之間。Thickness, to meet the visual preference of the toll collector, and to strengthen the anti-corrosion property of the substrate. P The above surface treatment method has the disadvantages of complicated operation, large amount of water and organic solvent, and must use colored paint. The material is used to cover the magnesium-containing substrate after the cleaning step, thereby reducing the flexibility of the manufacturer for the subsequent casing or frame design and positioning of the product marketing market. In addition, the surface treatment method does not compensate for the fine dents and minute cracks on the surface of the magnesium-containing substrate which are inadvertently caused by the mold. There are also many consumers who think that the metal texture and luster of the outer casing have a futuristic, high-grade, and fashionable sense, and they have a special liking for it; in order to make the equipment made of the magnesium-containing substrate The shelf or the product casing meets the requirements of the consumer _ 'Commonly used _. The preparation method is to form the money substrate to form the purified film. After the purification film, the electro-mine method is used to make the purified film Hierarchically recording: a metal layer (such as a layer of copper 'nickel, wire, etc.) formed by a stack - however, this method requires a lot of electrical energy and can cause heavy metal pollution, especially the road may It will produce carcinogenic Cr6+ ions. Therefore, the conventional method is costly and inconsistent with environmental protection claims, and the metal in the electric ore in the laminate is not easily separated, thereby increasing the difficulty in recovering various metals. 201024465 Obviously, what is needed in the art is a layer containing a layer of a magnesium-containing substrate and simply emitting a metallic luster by it, so that the manufacturer can more flexibly plan the design of the related product and create a huge Commercial benefits; and there is also a need in the art for an easy operation, less water and organic solvents, environmental compliance, corrosion protection of the magnesium-containing substrate, and rendering of the magnesium-containing substrate surface A surface treatment method for a metallic luster containing magnesium substrate. SUMMARY OF THE INVENTION Accordingly, it is a first object of the present invention to provide a method of treating a surface of a magnesium-containing substrate which achieves the above-described various purposes, comprising a polishing step, and a modifying step or a coating step. The polishing step 'contacts a magnesium-containing substrate with a polishing liquid composed of a solid portion and a liquid portion, and polishes the substrate until the solid portion of the polishing liquid is removed from the surface of the substrate Thereafter, the liquid portion retained is dried and formed on the surface of the substrate to form a coating film; wherein the solid portion of the polishing liquid includes a plurality of abrasive particles, and the liquid portion includes a strong base and a fragrance a compound, a complexing agent, a source of monophosphate, and a first solvent. The upgrading step and the coating step are basically alternatively, or the upgrading step and the coating step are sequentially performed. The modifying step is to dry a modified liquid after contacting the coating film formed on the surface of the magnesium-containing substrate, so that the coating film is modified to include a body attached to the surface of the substrate. And a modified region that is attached to the surface of the substrate away from the surface of the substrate; the coating step is to apply a coating liquid or a paint to the surface of the film to make the 201024465 The coating liquid on the film is dried to form a coating film on the slope film. Among them, what? The winter liquid comprises a titanium source, a source of hunger, an acid source, a neutralizing agent, and a second solvent, and the coating liquid comprises a coating resin and a coating additive. The above-described method of the present invention can be carried out by selectively performing a upgrading step or a coating step, or even performing the steps, and correspondingly obtaining the respective laminates as the second to fourth objects of the present invention. The laminates each comprise a layer comprising a magnesium-containing substrate and a layer of a coating layer formed on the layer of the substrate comprising the magnesium layer, or selectively formed by the coating step, and further comprising a layer formed thereon. Applying a coating layer on the coating layer or selectively modifying the coating layer to include a body region formed on the magnesium-containing substrate layer, and away from the magnesium-containing substrate A modified region is formed layer by layer on the body region. The fifth and sixth objects of the present invention are respectively to provide a polishing liquid and a coating: a liquid which can be applied to the method for carrying out the above first object of the present invention, and the formed coating film and coating The film is also transparent to allow the metallic luster of the magnesium-containing substrate to penetrate. In addition to providing corrosion protection for the treated magnesium-containing substrate, the surface treatment method of the present invention also has many advantages, such as easy operation steps and flexibility in implementation, requiring less water consumption and saving water resources. It is not used, and it does not produce a large amount of waste water or heavy metal pollution, and the magnesium-containing substrate in the obtained laminate is also easily recovered, so that it is highly environmentally friendly; on the other hand, after the polishing step The magnesium substrate, except for the tiny depressions and minute cracks thereon, can be modified or repaired by the liquid portion of the polishing liquid. The layers of the obtained laminate are transparent and thin, so 201024465 is located at the bottom. The metallic luster of the magnesium-containing substrate is emitted, and the layer of the material has a metallic texture. Alternatively, the coating step can be carried out using a general paint in the art, or using the coating liquid of the present invention; and the coating liquid can be selectively formulated to be water-based or oily, depending on the type of material used. The surface of the coating film formed by the special coating liquid can be formed by forming a coating film which is excellent in moisture resistance, hardness and abrasion resistance, and water and dirt are not easily adhered thereto. In addition to maintaining cleanliness for a long time, it can also provide better isolation and protection for the magnesium-containing substrate that is covered. [Embodiment] Based on the description of the essential elements of the various objects of the present invention and the obtained effects, the embodiments thereof will be further described and the usable materials or secondary operating conditions will be exemplified. The surface treatment method of the magnesium-containing substrate of the present invention may include, in addition to the polishing step, and the modification step or the coating step which is basically performed after the polishing step, the method of the present invention may also include The polishing step, the upgrading step, and the painting step are performed in sequence; the implementation procedures of each step are as described above. The method is applicable to magnesium-containing substrates of various materials, and magnesium substrates commonly used in the field, such as AZ014D, AM60, AM50, AEx-3, AE44, etc., are also applicable to the present application. The polishing liquid of the present invention used in the polishing step is composed of a solid portion including a plurality of abrasive particles, and the liquid portion includes a strong base, an aromatic compound, and a wrong portion. A mixture, an acid source, and a first solvent. , 201024465 In the polishing liquid of the present invention, the solid portion may occupy a large proportion in the male liquid relative to the liquid portion thereof. Preferably, the solid portion accounts for 50 wt% to 99.9 wt% of the polishing liquid. More preferably; between 8 〇 and 98 wt%; optimally between 90 wt% and %. In addition, the solid portion can be recycled and reused, so that in the case of the polishing liquid, the consumable has only its liquid portion, and it can only occupy a small amount, thereby effectively saving the material cost of the manufacturer, and A large amount of waste water caused by waste after use is avoided. For the abrasive particles, the material may be selected from the group consisting of cerium oxide (Si〇2), aluminum oxide (Al2〇3), hard resin [such as epoxy resin, polyacrylic acid derivative resin, etc. 】, and commonly used ceramic materials [such as zirconium oxide, titanium oxide, cerium oxide, etc.]; other materials of different materials as described above are allowed to be mixed. It is also suggested that the particle diameter of the abrasive particles is between 2 and 15 faces. For the liquid portion, it is recommended that the strong base be selected from potassium hydroxide (k〇h), sodium hydroxide (NaOH), lithium hydroxide (LiOH), calcium hydroxide [Ca(〇H)2], hydrogen. Cerium oxide [Ba(OH)2], or a combination of these; wherein the preferred strong saponin is selected from NaQH, KOH, or a combination thereof. It is also suggested that the content of the strong base in the liquid portion is preferably between 1 wt% and 5 wt%, and preferably between 1 wt% and 15 wt%. It is recommended that the aromatic compound be used, for example, an aromatic-derived derivative (particularly an aromatic phenolic compound), an aromatic heterocyclic derivative, or a combination thereof. Wherein the phenolic compound has a benzene ring in addition to its aromaticity, and is bonded to the benzene ring, and at least 201024465 is selected from an OH, an NH2, a SH, a N〇2, a _c The functional group of 〇〇H or the like; preferably, the phenolic compound is selected from the group consisting of salicylic acid, phthalic acid, benzophenone, benzophenone, nitrobenzene, and amide. Methyl phenol, methyl benzene phenol, or a combination thereof; more preferably from salicylic acid, catechol, nitroaniline, or a combination thereof. It is further suggested that the content of the aromatic compound in the liquid portion is between 0% by weight and 2% by weight, preferably between 0.5% and 5% by weight.
建議其錯合劑可擇自於草酸、檸檬酸、酒石酸、葡萄 糖酸、馬來酸、苯二曱酸、單乙醇胺、三乙醇胺、乙二胺 、三聚氰胺、乙二胺四乙酸（EDTA)，或其等之—組合；較 佳地是擇自於EDTA、乙二胺、三聚氰胺，或此等之一組合 。另建議在該液態部分中，該錯合劑的含量是佔〇 ^ wt%〜 20 wt%之間，較佳地是佔〇.5 〜5 wt%之間.。. 建議其磷酸根源是擇自於磷酸、磷酸鹽、亞磷酸、亞 磷酸鹽、次磷酸、次磷酸鹽、焦磷酸、焦磷酸鹽、聚磷酸 、聚磷酸鹽、偏磷酸、偏磷酸鹽、單磷酸酯、亞磷酸酯， 或此等之一組合；較佳地是擇自於焦磷酸、磷酸、亞磷酸 ，或此等之一組合。另建議在該液態部分中，該鱗酸根源 的含量是佔0.1 wt%〜20 wt%之間，較佳地是佔〇5糾％〜 5 wt%之間。 除了以上所述之各種必要成分以外，本發明拋光液中 之固態部分可更包括有一可增進研磨效果之研磨促進劑， 其是擇自於氧化鋁粉、氧化锆粉、氧化鈽粉，或此等之— 組合；基本上相較於上述研磨粒子，所選用之該研磨促進 201024465 劑是硬度更高，或粒徑更小奂 & / ^ 你 者，建議該研磨促進劑之粒徑 疋介於0:5 μηι〜500 μηι之門 口 +之間。另建議在該固態部分 研磨促進劑的含量是佔0〇 " 佔on。 伐〜10吟之間，較佳地是 佔0.05 wt%〜1 wt%之間。 ，^本發㈣光射之液態部分則可更包括卜抗刻 八疋擇自於錳酸根源、釩酸根源、錫酸根源，或此等之 一組合；該抗㈣是藉由其相對所含之酸根，而使得形成 在特定含鎂基材上的纽果更㈣異。 Ο 而就該拋光液的pH值，建議是超過10,甚至可超過 14(亦即其中的[〇『]>1 M);較佳地，其PH值是介於10〜 14之間。 上述各步驟的操作溫度基本上並未予限制，於一般室 溫（例如饥〜35。〇環境下即可進行操作；然、在乾燥該拋光 液之液體部分、改質液、漆料，或者是該塗裝液時，操作 者自可視其需求或所欲乾燥的液體成分，來選擇適合的溫 度範圍。 另建議在施行本發明方法時，可於該拋光液與該含鎂❹ 基材揍觸時’對該拋光液施以一 5 Hz〜200 Hz的震動頻率 ’以提升研磨效果，同時促進該拋光液中之液態部分與該 基材表面之間的反應。該拋光液與含鎂基材接觸時，其液 態部分即自然地沾.附於該基材表面上，而在乾燥該液態部 分之前’只要以清水輕微沖洗，即可使該固態部分自該基 材表面上被移除，隨後乾燥該基材表面上之液體部分而獲 得十形成在該基材表面上之彼覆膜，即完成該研磨步驟。 10 201024465 之後，操作者可視需求（例如所使用之含鎂基材.種類)地選擇 進行該改質步驟或塗裝步驟，或依序地進行該改質步驟及 塗裝步驟；其他因素暫不予考量下，若該三步驟皆有實施 ’則所獲得的層整物中之含鎖基材層，其防㈣護自然是 最為嚴密的。 該改質步驟是將一改質液，與經該抛光步驟而形成在 該含鎂基材表面上之彼覆膜相接觸，並使該彼覆膜上之改 質液乾燥，藉以使該披覆膜被改質而包括有一銜接於該基 • 材表面上之本體區，與一遠離該基材表面地銜接於該本體 區上之改質區；而該改質液則包含有一鈦源、一釩源、一 酸根源、一中和劑，與一第二溶劑。 該鈦源是用以提供鈦離子，可擇自於三氣化鈦【Ticid 、四氣化欽【TiCl4】、硫酸氧鈦【Tios〇4】、四乙氧基欽【 Ti(OEt)4】、欽酸四異丙醋【Ti(〇ipr)4】、硫酸欽（m)【 Ti.2(S〇4)_.3】’或此等之一組合。 該釩源則是用以提供釩離子，可擇自於三氣化釩【 ® VCl3】、五氧化二叙【V2〇5】、氣氧化奴(V)【V〇Cl3】、硫酸 氧叙【vos〇4】、偏鈒酸銨【卵々〇3】、，氟氧化釩（v)【 • vof3】，或此等之一組合。 該酸根源較佳地是選用其所提供的酸根之中心原子的 氧化數未達飽和者，而例如可為亞硝酸、亞硝酸鹽、含有 其氧化態未達+6價之硫的硫化物、亞鱗酸、亞磷酸鹽、草 酸、草酸鹽、酒石酸、酒石酸鹽、次磷酸、次磷酸鹽，或 此等之一組合。當該彼覆膜之改質區形成後，其中源自於 11 201024465 該酸根源的.氧化數未達飽和之中心肩.本 屌子’可在其所覆蓋的 含鎂基材之前，先與所接觸到的腐蝕因子（例如水或空氣）作 用’且亦使得該彼覆膜藉由氧的充填而讓其結構更^緻密 ，從而對其所覆蓋之含鎮基材提供更佳的保護，避免該基 材被腐蚀。 土 該中和劑是屬鹼類，而可將該改質液之ρΗ值作一適各 調整，藉此使得該披覆膜以一較適當的速度被⑨質，而^ 得較佳的品質。 該第二溶劑則是用以將該改質液中的物質，例如上述❹ 之鈦源、飢源、"酸根源、中和劑等加以溶解或分散，故就 第二溶劑之種類並無特殊限制；基於成本與配製便利性之 考量’建議該第二溶劑可選用水。 該塗裝步驟可藉由一本發明塗裝液，或是一漆料來進 行；其中該漆料可為例如在習知表面處理方法之有色塗裝 步驟中使用的有色漆料’或者是透明漆料，或者是本發明 塗裝液。 本發明塗裴液對於其所含之塗覆用樹脂的種類，並未❹ 有特殊限制，而可選用水性PU樹脂（例如型號為『wpc35〇 1之水性PU樹脂，由華寶樹脂公司所生產），或是環氧樹. 知（例如型號為『WP829』之環氧樹脂，由華寶樹脂公司所 生產）等市面上常見的塗覆用樹脂商品；該塗覆用樹脂的性 質將相對地使本發明塗裝液呈水性或油性。 該塗裝添加劑是被溶解於該塗覆用樹脂中，且其使用 目的疋在於加強該塗裝膜與彼覆膜之間的密著性，以及該 12 201024465 塗裂膜的表面疏水.性。建議該塗裝添加劑可選用多醇烧類 化合物（例—如聚乙二醇、三曱醇丙蝝’或此等之一組合）、多 醇鱗類化合物（例如乙二醇醚）、多醇烯類化合物（例如聚丙 烯醇）、多醇胺類化合物、多酚類化合物（意指其結構中在苯 環部位上至少銜接有兩_ 0H)、三聚氰胺、異氰胺衍生物， 或此等之一組合。其中，多醇胺類化合物則例如為三乙醇 胺、二乙酵-胺’或此等之一組合；多酚類化合物則例如為 鄰苯二酚、間苯二酚、對苯二酚、1，2,4苯三酚、1，3 5笨三 • 酚，或此等之一組合；異氰胺衍生物在高分子領域中常被 用以作為交聯劑，其為可具有各種取代基之異氰胺化合物 不同之異氰胺衍生物亦可混合使用。較佳地，該塗裝添 加劑是選用三甲醇丙烷、鄰苯二酚、異氰胺衍生物，或此 等之一組合。 若有需要的話，.該I塗裝液可更含有一稀釋劑，以降低 該塗裝液之黏度而更便於使用。該稀釋劑之種類選擇係依 據該塗覆用樹脂的性質而定；當選用水性樹脂時，直接以 ^ 水為稀釋劑即可，然若選用環氧樹脂，則相對地以非質子 型溶劑（特別是酮類溶劑）為該稀釋劑。該稀釋劑是可擇自於 ' 水、酒精、異丙醇、丁醇、丙酮、2-丁酮、甲基異丁酮、乙 酸乙S曰、乙酸丁酯、二丙酮醇，或此等之可互溶的一組合 〇 除此之外，該塗裝液更可包含有例如水玻璃、矽酸膠 、氫氧化鋁等硬度增進劑，用以增加該塗裝膜的硬度，而 該等物料亦可混合使用。 13 201024465 另’本發明塗裝液更可含有一色料；而若本發明塗裝 液是呈水性，則亦可包含一濕潤劑，其功效是在於降低該 塗裝液之内聚力而使其能更均勻地被附著於該披覆膜上， 並增進該塗裝膜與該披覆膜間的固著性。以上所述之稀釋 劑、硬度增進劑、色料、濕潤劑等可選擇性添加的物料，· 亦是可混合使用，且該等物料已在相關領域中廣被使用， 而可為具有此技藝通常知識者能自行拿捏欲採用的物料種 類與用量，故相關細節在此不予贅述。 塗裝添加劑是為使該塗覆用樹脂發揮較佳功效，而與❺ 其摻混並形成本發明塗裝液；實務上亦發現塗裝添加劑甚 至可在極少含量下（例如低於0.1 Wt% )即可發揮效用。於本 發明塗裝液中’該塗裝添加劑亦可佔〇.i wt%〜5 wt%之間 、或進一步地介於0.5 wt%〜2 wt%之間。 建議本發明塗裝液之pH值是介於5〜丨〗之間，以利於 與該披覆膜反應’進而形成出該塗裝膜，俾以對底下的含 鎂基材提供更佳的防蝕保護；較佳地，該塗裝液的pH值是 介於7〜11之間，更佳地，是介於8〜1〇之間。 _ 值得注意的是’一般漆料中的溶劑多屬有機性，其對 操作人員之生理與整體環境有不可忽略的負面影響，然此. 等漆料卻因可借助該有機性溶劑的表面張力，而形成出厚 度均勻之塗裝膜；換言之，以水性溶劑所配製出的塗裝膜 ’要塗佈得均勻並不容易，且所形成出的塗裝膜常有厚度 不均、表面有皺摺等諸多缺點。 然’本發明呈水性之塗裝液（特別是以水性pu樹脂與 14 201024465 水性溶劑來配製者）在該塗裝添加劑之作用下，並不具有上 述缺點’且該塗裝液易藉由該披覆膜表面之微小縫隙而滲 透其中從而使乾燥後所形成的塗裝膜能與該披覆膜間更 為緊密。 , . 該塗裝液與該披覆膜接觸時應是有化學反應產生，使 得該塗裝液經乾燥之後’所形成的塗裝膜表面將具疏水性 ，不易沾附水分與其他髒污，而能更徹底地將會致使該含 鎮基材腐钱的因子加以隔離，因此可對該含錢基材提供更 Φ 完整的保護。 藉由本發明之含鎂基材的表面處理方法，即可使所製 得的層疊物不但能僅單純地藉由其中之含鎂基材層來散發 出金屬光澤，且覆蓋於該基材層上之披覆膜在經過改質步 驟’及/或者於其上形成出__塗裝膜後，亦能對其等底下的 鎂洽金基材提供足夠的防蝕保護【其中性鹽霧測試（neutrai salt spray test，簡稱rNSST」）是可歷時約至少72小時以上 】。 ❹ 綜上所述，本發明含鎂基材的表面處理方法除了操作 上極為簡便’且物料與溶劑之消耗量極少而大幅降低污染 ' 之可能性以外，亦能有效地去除一含鎂基材表面上之油脂 與氧化物等雜質，並修飾該含鎂基材因鑄型而在表面上所 導致的微小凹陷與微小裂縫，更進一步地使所處理之含鎂 基材能散發出金屬光澤。 另’形成於該基材表面上的披覆膜，以及選擇性地再 形成於該披覆膜上之塗裝膜，不但能供其等底卞之該含鎂 15 201024465 基材的金屬光澤透射而出，還能對該基材提供防蝕保護， 使’得本領域長久以來所企求之單純藉該含鎂基材來呈現金 屬質感之層疊物’能夠藉由本發明方法而獲得，且其在長 久儲存下亦能維持其光亮之金屬質感。而以本發明塗裝液 所形成出的塗裝膜亦可具有良好的耐濕性、硬度，與抗磨 性，且其對於水分、濕氣等易致使該含鎂基材腐蝕的因子 有較佳的隔離能力’因此該塗裝膜的表面不但能長期地維 持潔淨，且對該含鎂基材提供了更佳的保護，使其具有更 優異的抗姓性。 因此，本發明方法不但突破了以往含鎂基材表面處理 方法與各式含鎂基材之諸多成效限制，亦使得廠商在商品 外觀設計上將可具有更多彈性，以符合市場上之各式需求 與期待。顯然地，本發明所提出之各項目的，皆為本領域 長期以來的技術瓶頸提供了一良好的解決方策。 惟以上所述者，僅為本發明之較佳實施例而已，當不 能以此限定本發明實施之範圍，即大凡依本發明申請專利 範圍及發明說明内容所作之簡單的等效變化與修飾，皆仍❹ 屬本發明專利涵蓋之範圍内。 【圖式簡單說明】 無 【主要元件符號說明】 無 16It is suggested that the wrong agent can be selected from oxalic acid, citric acid, tartaric acid, gluconic acid, maleic acid, benzoic acid, monoethanolamine, triethanolamine, ethylenediamine, melamine, ethylenediaminetetraacetic acid (EDTA), or Etc.—combination; preferably selected from EDTA, ethylenediamine, melamine, or a combination of these. It is also suggested that in the liquid portion, the content of the complexing agent is between wt% wt% and 20 wt%, preferably between 55 and 5 wt%. It is recommended that the phosphate source be selected from phosphoric acid, phosphate, phosphorous acid, phosphite, hypophosphorous acid, hypophosphite, pyrophosphoric acid, pyrophosphate, polyphosphoric acid, polyphosphate, metaphosphoric acid, metaphosphate, single Phosphate, phosphite, or a combination of these; preferably selected from pyrophosphoric acid, phosphoric acid, phosphorous acid, or a combination thereof. It is further suggested that in the liquid portion, the scalar source content is between 0.1 wt% and 20 wt%, preferably between 5 and 5 wt%. In addition to the various essential components described above, the solid portion of the polishing liquid of the present invention may further comprise a polishing accelerator which enhances the grinding effect, which is selected from alumina powder, zirconia powder, cerium oxide powder, or the like. Etc. - Combination; basically compared to the above abrasive particles, the selected polishing promotion 201024465 agent is higher in hardness, or smaller in particle size amp & / ^, it is recommended that the particle size of the polishing accelerator Between 0:5 μηι~500 μηι door + between. It is also recommended that the content of the grinding accelerator in the solid portion is 0 〇 " Between ~10 伐, preferably between 0.05 wt% and 1 wt%. The liquid portion of the light (4) light shot may further include a source of manganic acid, a source of vanadic acid, a source of stannate, or a combination thereof; the anti-(four) is by its relative Containing acid, so that the fruit formed on a specific magnesium-containing substrate is more (four) different. Ο The pH of the polishing solution is recommended to be more than 10 or even more than 14 (i.e., [〇『]>1 M); preferably, the pH is between 10 and 14. The operating temperature of the above steps is basically not limited, and can be operated at room temperature (for example, hunger ~ 35 〇 environment; however, drying the liquid portion of the polishing liquid, the modifying liquid, the paint, or In the case of the coating liquid, the operator selects a suitable temperature range by visualizing the demand or the liquid component to be dried. It is also recommended that the polishing liquid and the magnesium-containing ruthenium substrate be used in the method of the present invention. At the time of exposure, a vibration frequency of 5 Hz to 200 Hz is applied to the polishing liquid to enhance the grinding effect, and at the same time, promote the reaction between the liquid portion in the polishing liquid and the surface of the substrate. The polishing liquid and the magnesium-containing group When the material is in contact, the liquid portion is naturally adhered to the surface of the substrate, and the solid portion is removed from the surface of the substrate as long as it is slightly rinsed with water before drying the liquid portion. Subsequently, the liquid portion on the surface of the substrate is dried to obtain a film formed on the surface of the substrate, that is, the grinding step is completed. 10 201024465 After that, the operator can visually select (for example, the magnesium-containing substrate used. Selecting the upgrading step or the coating step, or sequentially performing the upgrading step and the coating step; other factors are temporarily not considered, and if the three steps are performed, the obtained layer is obtained. In the middle of the lock-containing substrate layer, the protection against (4) is naturally the most stringent. The modification step is to contact a modified liquid with the other film formed on the surface of the magnesium-containing substrate through the polishing step. And drying the modifying liquid on the film, so that the coating film is modified to include a body region attached to the surface of the substrate, and a body away from the surface of the substrate a modified region on the region; and the modified liquid comprises a titanium source, a vanadium source, an acid source, a neutralizing agent, and a second solvent. The titanium source is used to provide titanium ions, which can be selected from In the three gasification of titanium [Ticid, Siqihuaqin [TiCl4], titanyl sulfate [Tios〇4], tetraethoxy chin [Ti (OEt) 4], tetraisopropyl vinegar [Ti (〇ipr) 4], sulphuric acid (m) [Ti.2 (S〇4) _.3] ' or a combination of these. The vanadium source is used to provide vanadium ions, which can be selected from three Vanadium [VCl3], V2O5 [V2〇5], VO (V) [V〇Cl3], Oxygen Sulfate [vos〇4], Ammonium Bismuthate [Ovum 3], Vanadium oxyfluoride (v) [vof3], or a combination of the above. The acid source is preferably selected from the central atom of the acid radical provided by the acid atom, and may be nitrous acid, for example, a nitrate, a sulfide containing sulphur having an oxidation state of less than +6, a sulphite, a phosphite, an oxalic acid, an oxalate, a tartaric acid, a tartrate, a hypophosphorous acid, a hypophosphite, or a combination thereof When the modified region of the film is formed, the origin of the acid source originated from 11 201024465 is less than the saturated center shoulder. The scorpion 'before the magnesium-containing substrate covered by it Acting with the corrosive factors (such as water or air) that are in contact with it, and also making the structure of the film more dense by oxygen filling, thereby providing better protection to the coated substrate To avoid corrosion of the substrate. The neutralizing agent is an alkali, and the pH value of the modifying liquid can be adjusted appropriately, so that the coating film is made of a quality at a suitable speed, and the quality is better. . The second solvent is used to dissolve or disperse the substance in the reforming liquid, for example, the above-mentioned titanium source, hunger source, "acid source, neutralizing agent, etc., so that there is no second solvent type Special restrictions; based on considerations of cost and ease of formulation, it is recommended that the second solvent be water. The coating step can be carried out by a coating liquid of the invention, or a paint; the paint can be, for example, a colored paint used in a colored coating step of a conventional surface treatment method' or transparent Paint, or the coating liquid of the present invention. The coating liquid of the present invention does not have any particular limitation on the kind of the coating resin contained therein, and an optional water-based PU resin (for example, the water-based PU resin of the model "wpc35〇1, produced by Huabao Resin Co., Ltd." ), or epoxy tree. Know (such as the epoxy resin of the model "WP829", produced by Huabao Resin Co., Ltd.) and other commercially available coating resin products; the properties of the coating resin will be relatively The coating liquid of the present invention is made water- or oily. The coating additive is dissolved in the coating resin, and is used for the purpose of enhancing the adhesion between the coating film and the film, and the surface hydrophobicity of the coating film of the 201024465. It is recommended that the coating additive be selected from a polyalcoholic compound (for example, such as polyethylene glycol, trisylhydrazone or a combination thereof), a polyol scaly compound (such as a glycol ether), and a polyol. An olefinic compound (for example, a polyhydric alcohol), a polyhydric alcohol amine compound, a polyphenolic compound (meaning that at least two OH groups are attached to a benzene ring moiety in its structure), a melamine, an isocyanide derivative, or the like One combination. Wherein, the polyhydric alcohol amine compound is, for example, triethanolamine, diethylamine-amine or a combination thereof; and the polyphenol compound is, for example, catechol, resorcinol, hydroquinone, 1, 2,4 benzenetriol, 1,3 5 stupid phenol, or a combination of these; isocyanide derivatives are often used as cross-linking agents in the polymer field, which may have various substituents. Different isocyanamide derivatives of cyanamide compounds can also be used in combination. Preferably, the coating additive is selected from the group consisting of trimethylolpropane, catechol, isocyanide derivatives, or a combination thereof. If desired, the I coating may further contain a diluent to reduce the viscosity of the coating and to be easier to use. The type of the diluent is determined according to the nature of the coating resin; when the aqueous resin is selected, the water may be directly used as a diluent, and if the epoxy resin is selected, the aprotic solvent is relatively In particular, a ketone solvent) is the diluent. The diluent is selected from the group consisting of 'water, alcohol, isopropanol, butanol, acetone, 2-butanone, methyl isobutyl ketone, ethyl acetonitrile acetate, butyl acetate, diacetone alcohol, or the like. In addition, the coating liquid may further contain a hardness improving agent such as water glass, phthalic acid gel or aluminum hydroxide to increase the hardness of the coating film, and the materials are also Can be mixed. 13 201024465 In addition, the coating liquid of the present invention may further contain a coloring material; and if the coating liquid of the invention is water-based, it may also contain a wetting agent, which is effective in reducing the cohesive force of the coating liquid to make it more capable. It is uniformly attached to the coating film and improves the adhesion between the coating film and the coating film. The above-mentioned diluents, hardness improvers, colorants, humectants, and the like can be selectively added, and can also be used in combination, and these materials have been widely used in related fields, and can be used in this art. Usually, the knowledge person can handle the type and amount of materials to be used, so the relevant details will not be described here. The coating additive is used to make the coating resin perform better, and is blended with cerium to form the coating liquid of the present invention; it has also been found that the coating additive can be even at a very small content (for example, less than 0.1 Wt%). ) can be effective. In the coating liquid of the present invention, the coating additive may also be between wt.i wt% to 5 wt%, or further between 0.5 wt% and 2 wt%. It is suggested that the pH of the coating liquid of the present invention is between 5 and , to facilitate the reaction with the coating film to form the coating film, thereby providing better corrosion protection to the underlying magnesium-containing substrate. Preferably, the pH of the coating liquid is between 7 and 11, more preferably between 8 and 1 Torr. _ It is worth noting that 'the solvents in general paints are mostly organic, which have a negligible negative impact on the operator's physiology and the overall environment. However, the paints can rely on the surface tension of the organic solvent. , a coating film having a uniform thickness is formed; in other words, the coating film prepared by using an aqueous solvent is uniformly coated and is not easy, and the formed coating film often has uneven thickness and wrinkles on the surface. Folding and many other shortcomings. However, the aqueous coating liquid of the present invention (especially prepared by using aqueous pu resin and 14 201024465 aqueous solvent) does not have the above disadvantages under the action of the coating additive, and the coating liquid is easily used by the coating liquid. A small gap in the surface of the coating film penetrates into the film to make the coating film formed after drying more tightly bonded to the coating film. The coating liquid should be chemically reacted when it comes into contact with the coating film, so that after the coating liquid is dried, the surface of the coating film formed will be hydrophobic, and it is not easy to adhere to moisture and other dirt. The factor that causes the ruthenium containing the substrate to be more thoroughly isolated can provide a more complete protection of the toxic substrate. By the surface treatment method of the magnesium-containing substrate of the present invention, the obtained laminate can not only emit metal luster by simply covering the magnesium-containing substrate layer therein, but also cover the substrate layer. The coating film can also provide sufficient corrosion protection to the underlying magnesium alloy substrate after the modification step 'and/or the formation of the __ coating film thereon. [Neutral salt spray test (neutrai salt spray) Test, referred to as rNSST"), can last for at least 72 hours or more. In summary, the surface treatment method of the magnesium-containing substrate of the present invention can effectively remove a magnesium-containing substrate in addition to the extremely simple operation and the possibility of greatly reducing the consumption of materials and solvents. The surface of the grease and oxides and other impurities, and the micro-depression and micro-cracks caused by the mold on the surface of the magnesium-containing substrate, furthermore, the treated magnesium-containing substrate can emit metallic luster. Further, a coating film formed on the surface of the substrate, and a coating film selectively formed on the coating film, can not only provide the metal gloss transmission of the magnesium-containing 15 201024465 substrate In addition, the substrate can be provided with anti-corrosion protection, so that a laminate which has long been desired in the art to exhibit a metallic texture by the magnesium-containing substrate can be obtained by the method of the present invention, and it is long-lasting. It also maintains its shiny metallic texture under storage. The coating film formed by the coating liquid of the present invention can also have good moisture resistance, hardness, and abrasion resistance, and it has a tendency to cause corrosion of the magnesium-containing substrate by moisture, moisture, or the like. Good isolation ability' Therefore, the surface of the coated film not only maintains cleanliness for a long time, but also provides better protection to the magnesium-containing substrate, making it more excellent in resistance to surnames. Therefore, the method of the present invention not only breaks through many limitations of the surface treatment methods of the magnesium-containing substrate and various magnesium-containing substrates, but also enables the manufacturer to have more flexibility in the design of the product to conform to various forms on the market. Needs and expectations. Obviously, all the objects proposed by the present invention provide a good solution to the long-term technical bottleneck in the field. The above is only the preferred embodiment of the present invention, and the scope of the invention is not limited thereto, that is, the simple equivalent changes and modifications made by the scope of the invention and the description of the invention are All are still within the scope of the patent of the present invention. [Simple diagram description] None [Main component symbol description] None 16