1285580 九、發明說明： 【發明所屬之技彳标領域】 發明領域 本發明係有關於一種鎂或鎂合金之殼體，其中，一化 5學轉化膜係於由鎂或鎂合金製得之模製產品表面上簡單地 形成，以改良塗覆物產率，及一種製造此鎂或鎂合金殼體 之方法。 L 前^:冬好;3 相關技藝之描述 10 最近，越來越多機會攜帶行動設備(諸如，筆記型電腦 及個人數位助理(PDA))以供戶外使用。因此，愈來愈需要 使此設備之重量及厚度迷你化及降低，因此，降低佔此設 備整體質量30%之殼體之厚度係需要。但是，於其間設備 厚度被降低之情況’以樹脂殼體係難以維持足夠強度。再 15者，藉由筆記型電腦之微處理器單元(MPU)產生之熱量係 持續增加。AC趨動期間之熱產生量預期係13至16〜，因此， 具高冷卻性能之殼體之發展係急需要。 作為上述問題之解決方式’具低重力及高導熱性之輕 金屬（諸如，A卜鎂、鎂合金等）係變成作為殼體材料之注意 2〇焦點。特別地，鎂或鎂合金係輕的，即，具有A1之約7〇% 重力，且於循環再利用性係優異。作為鎂或鎂合金， Mg、Al-Zn /系統、Mg-Al-Mn 系、統、Mg 或 Mgm統、 稀土元素(RE)系統等已被實際使用。此等材料係藉 由模具鑄造而模製。觸變模製、片材金屬加工處理等，^ 1285580 接叉化學轉化處理，因而獲得之化學轉化產品接受塗覆處 理。模具鑄造係指於加壓下使熔融金屬注射於模具内獲得 模製產品之方法。觸變模製係指使半炼融或炼融之金屬自 約60(TC之擠塑器擠塑於約250t之模具内，藉此獲得模製 5 產品之方法。 化學轉化處理係指於鎭或鎮合金之表面上形成具有财 腐蝕功能之化學轉化塗覆膜之處理。依據此處理，鎂或鎂 合金被浸潰於主要含有六價鉻溶液之鉻酸溶液、不含有六 價鉻之非鉻酸溶液等内，藉此，鉻酸之鉻錯合物鹽之塗覆 10 物膜（一般，xCr03 · yCr2〇3 · 2h2〇、Cr(〇H)2 · Hcr〇4 2出〇 等）於鎖或镁合金之表面上形成。於化學轉化處理後，塗覆 處理被實施。化學轉化處理之方法係由JP11(1999)_131255A 及 JP2000-96255A提出。 使用鎂或鎂合金作為材料製造產品具有下列問題。藉 15由模具鑄造、觸變模製等獲得之模製產品具有毛邊。現今， 毛邊係藉由以壓力機敲打、切割等以手工或機械式地移 除，其等之任一者係笨重操作。亦有一種藉由以空氣噴灑 之顆粒對模製產品進行喷丸處理而移除毛邊之方法。於此 情況，其具有下列問題。鎂、鎂合金之粉塵粒子，或顆粒 2〇可能被產生及分散，造成差的施工性能及粉塵粒子爆炸之 危險性。 再者，實施上述化學轉化處理需進行預處理。一般之 化學轉化處理係如下所述般實施。上述模製產品被脫脂， 然後，以酸清洗。然後，模製產品接受蝕刻，以移除模製 1285580 期間使用之脫模劑。然後，表面調節處理被實施，其間， 板製產品之表面被抛光而獲得光澤整理，如此，鉻酸之絡 錯合物鹽之塗覆物膜可於模製產品之表面上形成。上述處 理係相當於預處理。然後，模製產品被浸潰於上述絡酸^ 5液或非鉻酸溶液以實施化學轉化處理。然後，形成之 產品以水清洗，且於約7(rc乾燥，藉此，使化學轉化塗覆 物膜固化。因此，化學轉化處理之預處理需具有數個處理 方法，諸如，脫脂、清洗、藉由蝕刻之表面調節處理等， 其使操作笨重，使處理裝置複雜化，且增加處理費用。 10 於藉由模具鑄造產生之模製產品，觸變模製等之模製 缺失(諸如’拉曳（draw)、空隙、熱水流曳（fl〇w)等）發生。 於檢查模製缺失(拉曳、空隙、流曳等）期間，模製產品係以 手工方式部份磨光，以使其能輕易見到模製產品，且其後， 實施視覺檢測。此時，磨光係以手工方式實施，使此檢測 15 之實施變笨重，且於磨光期間會產生粉塵粒子。作為調節 表面之方法（諸如，磨光），JP2003-284457A提議濕鼓風處 理。再者，JP2000-263442A提議一種連續實施濕鼓風之方 法，其係作為化學轉化處理之預處理。 上述傳統技術使用濕鼓風作為化學轉化處理之預處 20 理，且此等方法之數目係相似於使用傳統化學處理之處理 數，因此，於費用等之改良效果係小的。再者，有缺失之 模製產品於化學轉化處理前需敷以油灰而校正，此減低產 率且增加費用。 【發明内容】 1285580 發明概要 因此，基於前述，本發明之目的係提供一種麟或鎮合 金之殼體，其間，化學轉化媒係於由鎂或鎮合金製得之模 製產品表面上簡單地形成，以降低藉由敷油灰而校正，塗 5覆物之產率被促進，且費用可被降低，及一種製造錢或鎮 合金殼體之方法。 本發明之錢或鎮合金殼體之特徵在於鎂或鎂合金殼體 之表面係接受使用含化學轉化處理劑及磨料之溶液之濕鼓 風，藉此，化學轉化膜於鎂或鎂合金殼體之表面上形成。 1〇 冑造本發明之鎮或鎂合金殼體之方法之特徵在於鎂或 鎮合金之_面接受使用含化學轉化處理劑及磨料之溶液之 濕鼓風，藉此，由於鼓風而造成之平坦及化學轉化膜係同 時於鎂或鎂合金殼體之表面上形成。 本發明之此等及其它之優點對熟習此項技藝者於參考 15附圖而閱讀及瞭解下列詳細說明時將變明顯。 圖式簡單說明 第1圖係圖示本發明之實施例1之方法流程。 第2圖係圖示比較例1之方法流程。 第3圖係本發明實施例1中之筆記型電腦殼體之表面觀 20察相片。 第4圖係比較例1中之筆記型電腦殼體之表面觀察相 片。 第5A至5C圖係顯示本發明實施例1中之橫切測試結果 之表面觀察相片。 128558〇 面 觀察ιγ至6c圖係顯示比較例l+之橫切測«結果之表 5 10 15 含第7A至7C圖係本發明實施例i藉由鹽喷灑測試咖) 平估耐腐谢4而獲得之表面觀察相片。 第8A至8C圖係比較例！藉由鹽喷灑測試⑻乃評估耐 腐蝕性而獲得之表面觀察相片。 【實施方式】 較佳實施例之說明 風依據本發明，鎮或鎂合金殼體之表面接受使用含有化 學轉化處_及磨料之混合溶液之祕風，而㈣或鎮合 金殼體表面上-起形成化學轉化膜及由於鼓風而造成之不 平坦’此降低藉由敷灰油之校正，藉此，避免產率降低及 費用增加。更特別地，當含有化學轉化處理劑及磨料之混 b溶液藉由濕鼓風注射於鎂或鎂合金殼體之表面上時，此 表面係以磨料刮擦，同時，適當厚且緻密之磷酸鈣_磷酸錳 之錯合物塗覆膜由於鎂及化學轉化處理劑間之反應而產 生。因此，使裸耐腐蝕性、避免生鏽、塗層黏著性及塗層 耐腐蝕性退化之氧化物或氫氧化物膜未於鎂或鎂合金殼體 表面上形成；相反地，磷酸鈣-磷酸錳之錯合物塗覆物膜可 於其間形成，其間，鈣及填有助於促進化學轉化膜之裸耐 腐蝕性，且錳有助於促進塗覆物黏著性。再者，化學轉化 產物表面上之拉曳、空隙、流曳等被去除，使其無需於塗 覆前實施藉由敷灰油之校正，且能降低費用。 本發明之發明人已認真地研究而解決上述問題，且因 20 1285580 而發現’例如’作為以鎮或鎭合金製得之殼體之避免生鑛 及塗覆物處理之預處理，化學轉化處理及濕鼓風係對於鎮 或鎮合金同時實施，藉此，上述問題可被解決。此間，濕 鼓風係指其間液體及磨料被混合且此混合物係於〇1至〇.3 5 MPa範圍之壓力下注射之處理。 較佳係用於本發明之化學轉化處理劑含有鈣離子、錳 離子，及磷酸離子，亦較佳係濕鼓風係使用其間含有氧化 加速劑之水性溶液及磨料(諸如，氧化鋁)被混合之溶液而實 施。於濕鼓風，殼體之表面拋光及化學轉化塗覆係同時實 1〇施。因此，形成之塗覆物膜亦被拋光；但是，充分之塗覆 物膜可藉由滿足上述條件而獲得。 較佳係至少一選自氧化鋁、锆、玻璃及樹脂之顆粒材 料被作為磨料。再者，作為樹脂，蜜胺樹脂、尿素樹脂、 聚酯樹脂、酚樹脂、環氧樹脂、胺基曱酸酯樹脂等可被使 15用。較佳係磨料之平均顆粒直徑係10至300 um之範圍。 作為欲被注射之化學轉化處理劑之鈣離子來源，硝酸 鈣、亞硝酸鈣、硫代硫酸鈣、磷酸四鈣等之一種或至少二 種可被化合。再者，作為錳離子來源，碳酸锰、硝酸錳、 石4酸氫猛、酸式填酸猛、氟硼酸猛等之一種或至少二種可 2〇被化合。再者，作為磷酸離子源，原磷酸、縮合磷酸、亞 石4酉文、次磷酸等之一種或至少二種可被化合。 再者，作為氧化加速劑，氯酸鈉、次氣酸鈉等可被使 用。氧化加速劑可促進化學轉化處理期間之鎂或鎂合金及 上述個別組份離子間之反應性，藉此，具令人滿意 之裸耐 !28558〇 磨蝕性之化學轉化塗覆物膜可更方便地形&。再者，氧化 加速劑之較佳化合量係0.02至2克/公升之範圍，以安定地獲 得具上述性能之化學轉化塗覆物膜。 依據本發明，當化學轉化處理劑及磨料之混合溶液藉 5由濕鼓風注射於鎂或鎂合金之表面上時，表面係以磨料刮 擦，且適當厚且緻密之磷酸鈣-磷酸錳之錯合物塗覆物膜由 於鎂或鎂合金及化學轉化處理劑間之反應而產生。因此， 氧化物或氫氧化物膜未於鎂或鎂合金表面上形成，相反 地，磷酸鈣-磷酸錳之錯合物塗覆物膜可被形成。較佳係藉 10由化學轉化處理形成之複合物塗覆膜之黏著量以Ca重量而 言係5毫克/公尺2至50毫克/公尺2，αΜη重量而言係3毫克/ 公尺至25毫克/公尺2，且以磷重量而言係3〇毫克/公尺2至 100毫克/公尺2。 再者’較佳係化學轉化處理劑之比例係70至90質量 15 %，且磨料之比例係10至30質量％。 化學轉化塗覆物膜係於鎂或鎂合金表面上形成，以含 有上述預定S之鈣、錳，及磷，藉此，具有預定裸耐腐蝕 性、避免生鏽、塗覆物黏著性及塗覆物耐腐蝕性之化學轉 化塗覆物膜可被獲得。特別地，鈣及磷被認為有助於促進 20化學轉化塗覆物膜之裸耐腐蝕性，且錳被認為有助於促進 塗覆物黏著性。 再者，鎂或鎂合金表面以磨料拋光，藉此，鎂或鎂合 金殼體產品表面上之拉曳、空隙、流曳等被去除，且於塗 覆前無需實施敷油灰之校正，藉此，費用可被降低。較佳 !285580 地’由於濕鼓風溶液内所含磨料之拋光功能，鎂或鎂合金 殼1體之表面粗糙度被設定為以10-點平均表面粗糙度而言 為〇·5 um至1〇〇 um之範圍。 於上述處理後，較佳係表面以水清洗，其後乾燥。再 5 者’若於濕鼓風及以水清洗後含有相似於用於濕鼓風之化 學轉化處理劑者之鈣離子、錳離子及磷酸離子及氧化加速 劑之水性溶液被噴淋注射於表面上，塗覆物膜之厚度可被 增加以促進耐腐蝕性。 其後，塗覆處理可被實施。於塗覆處理，可使諸如環 10 氧樹脂之塗覆劑係藉由喷灑塗覆、電沈積等塗敷，且諸如 蜜胺樹脂之塗覆劑被塗敷於其上。另外，各種不同種類之 樹脂之粉末狀塗覆劑亦可藉由靜電式塗覆塗敷。 實施例 其後，本發明將藉由實施例及比較例而更明確地描述。 15 實施例1 作為欲被處理之標的元件，藉由使ASTM AZ91D之鎂 或鎂合金接受觸變模製而製得之筆記型電腦殼體被使用。 觸變模製係以下述般貫施·半炼融或溶融態之鎮或鎮合金 自約60CTC之擠塑器擠塑至約250°C之模具而獲得模製產 2〇 品。第1圖顯示表面處理方法。 作為化學轉化處理劑，含有80質量％之”Grander-Finer MC1000”(Milli〇n化學有限公司製造：15至25質量％之磷 酸、10至15質量％之锰化合物，及10至20質量％之妈化合物） 及20質量％之作為磨料之具40um平均顆粒尺寸之氧化I呂 12 1285580 (MacorundumA#320，Macoho有限公司）之混合物被使用0 濕鼓風係使用Macoho有限公司製造之WFB-2_2C以下列條 件實施：壓縮空氣壓力係0.2 MPa，泵壓力係0.12 MPa，殼 體及噴嘴間之距離係30 mm，且殼體係以40 mm/s向前饋 5 入。殼體以水清洗以便移除化學轉化處理劑及磨料，且進 一步以去離子清洗，其後乾燥。 比較例1 第2圖顯示作為比較例之於蝕刻後實施化學轉化處理 之方法。第2圖中之表面調節1及2代表蝕刻處理。 1〇 作為脫脂劑，”GFMG15SX，，(Million化學有限公司製造) 被使用，且其溫度係保持7〇°C。然後，上述之鎂或鎂合金 殼體被浸潰於脫脂劑内5分鐘以使殼體脫脂，其後以水清 洗。作為餘刻劑，’’Grander-Finer MG104S’，(Million化學有 限公司製造：30至40質量％之磷酸、少於〇·ΐ質量％之表面 15 活性劑，剩餘量之水)被保持於5%之濃度及60°C之溫度。然 後，殼體被浸潰於蝕刻劑内60秒以實施蝕刻作用，其後以 水清洗。其後，接受蝕刻處理之此元件被浸潰於維持於6〇 °C溫度之上述”GFMG15SX，，(Million化學有限公司製造）内7 分鐘，其後以水清洗。作為化學轉化處理劑，”Grander_Finer 20 MC1000”(Million化學有限公司製造：15至25質量％之石粦 酸、10至15質量％之錳化合物、1〇至20質量％之_化合物） 被使用，且保持於35°C。然後，經上述般處理之鎂或鎂合 金殼體被浸潰於化學轉化處理劑内40秒，以水清洗，且進 一步以去離子水清洗，其後乾燥。 13 1285580 實施例1及比較例1被評估外觀。再者，鎂或鎂合金殼 體表面上之元素黏者里係精由勞光X-射線量化而測量。殼 體表面上之五部份被採用，且其變化被檢查。電阻係藉由 Dia儀器有限公司製造之”Loresta MP”(四端子二探針之系 5統)測量。結果係顯示於第1表與第3及4圖。第3圖係顯示比 較例1外觀之相片，且第4圖係顯示實施例1外觀之相片。實 施例1之外觀具有均一表面，而比較例1外觀上觀察到不規 則性。 第1表 實驗編號 外觀 污處 電阻 (Ω 元素黏著量< Ca 實施例1 第3圖 無 0.4 24.4±4 ~592£j^ 比較例1 第4圖 無 0.7 70.4±35 112.6ΪΖΡ ίο 註1:污處係指由於粉末黏著造成之外觀缺失。 再者，環氧型式之二塗覆塗層（於150°C烘烤)被維持於 高溫高濕度環境(60°C，95%RH之相對濕度）内之鎂或鎂合 金殼體上100小時。其後，橫切測試被實施（西洋棋板圖案 被繪於樣品表面上以使表面分割成100部份，且於貼膠帶 15 (tape-up，剝膠帶)後留下之格子數被計算而以下述標準為基 礎測定：當留下之格子數為100時係成功，當留下之格子數 少於100時係失敗。 第5A至5C圖係顯示實施例1之結果之外觀相片，且第 6A至6C圖係顯示實施例1之結果之外觀相片。於第5A-5C至 20 6A-6C圖中，”〇H，，代表”測試前，，，且，，2mm”及”1 mm”個別 代表每一格子之尺寸。 再者，依據JISZ 2371之鹽喷灑測試(SST)被實施8小時 1285580 及24小時，且耐腐蝕性被評估。第7八至7(2圖係顯示實施例 1之結果之外觀相片，且第8人至8(：圖係顯示比較例1之結果 之外觀相片。於第7A-7C圖至第8A-8C圖，，ΌΗ”代表，，測試 前，，，且，，8H”及，，24H”個別代表測試處理時間。 由上述結果破認實相較於比較例1，施例1之殼體具有 均一顏色且係平滑。再者，於實施例i，模製產品表面上之 拉曳、空隙、流曳等被去除。此促進處理後實施之塗覆物 產率，且使其於塗覆前無需施行敷油灰之校正，因此降低 費用。 於實施例1，雖然塗覆物膜之黏著量比比較例，但 與比較例1相比’黏著量係較少改變。其它塗覆物特性(諸 如，電阻、塗覆性質，及耐腐蚀性)於實施及比較例… 展現相似數值。 15 20BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a shell of magnesium or magnesium alloy in which a chemical conversion film is molded from a magnesium or magnesium alloy. The product is simply formed on the surface to improve coating yield, and a method of making the magnesium or magnesium alloy casing. L 前^:冬好;3 Description of Related Techniques 10 Recently, more and more opportunities have been brought to carry mobile devices (such as notebook computers and personal digital assistants (PDAs)) for outdoor use. Therefore, there is an increasing need to miniaturize and reduce the weight and thickness of the device. Therefore, it is necessary to reduce the thickness of the casing which accounts for 30% of the overall mass of the device. However, in the case where the thickness of the apparatus is lowered, it is difficult to maintain sufficient strength in the resin case. In addition, the amount of heat generated by the microprocessor unit (MPU) of the notebook computer continues to increase. The amount of heat generation during AC actuation is expected to be 13 to 16~, and therefore, the development of a housing having high cooling performance is urgently required. As a solution to the above problem, a light metal having a low gravity and a high thermal conductivity (such as A-magnesium, a magnesium alloy, etc.) becomes a focus of attention as a casing material. In particular, the magnesium or magnesium alloy is light, i.e., has a gravity of about 7% by weight of A1, and is excellent in recycling. As the magnesium or magnesium alloy, Mg, Al-Zn/system, Mg-Al-Mn system, Mg or Mgm system, rare earth element (RE) system and the like have been practically used. These materials are molded by die casting. Thixoforming, sheet metal processing, etc., ^ 1285580 is chemically converted, and the chemical conversion product obtained is subjected to coating treatment. Mold casting refers to a method of injecting molten metal into a mold under pressure to obtain a molded product. Thixoforming refers to a method in which a semi-refined or smelted metal is extruded from a mold of about 60 (TC extruder) into a mold of about 250 tons, thereby obtaining a molded product. Chemical conversion treatment refers to 鎭 or A chemical conversion coating film having a corrosive function is formed on the surface of the town alloy. According to the treatment, the magnesium or magnesium alloy is impregnated into a chromic acid solution mainly containing a hexavalent chromium solution, and a non-chromium containing no hexavalent chromium. In an acid solution or the like, a coating film of a chromium complex salt of chromic acid is used (generally, xCr03 · yCr2〇3 · 2h2〇, Cr(〇H)2 · Hcr〇4 2 out, etc.) The surface of the lock or the magnesium alloy is formed. After the chemical conversion treatment, the coating treatment is carried out. The method of the chemical conversion treatment is proposed by JP 11 (1999) _131255 A and JP 2000-96255 A. The product is manufactured using magnesium or a magnesium alloy as a material. Problem: The molded product obtained by die casting, thixotropic molding, etc. has a burr. Nowadays, the burrs are manually or mechanically removed by tapping, cutting, etc. by a press, and the like. Bulk operation. There is also a way to spray by air. A method in which a pellet is subjected to shot peening to remove a burr. In this case, it has the following problems: dust particles of magnesium or magnesium alloy, or particles 2 may be generated and dispersed, resulting in poor workability and dust. The risk of particle explosion is further required. The above chemical conversion treatment requires pretreatment. The general chemical conversion treatment is carried out as follows. The molded product is degreased and then washed with acid. Then, the molded product is accepted. Etching to remove the release agent used during molding 1285580. Then, the surface conditioning treatment is carried out, during which the surface of the plated product is polished to obtain a gloss finish, thus, the coating of the chromic acid complex complex salt The film may be formed on the surface of the molded product. The above treatment is equivalent to pretreatment. Then, the molded product is impregnated into the above-mentioned liquid or non-chromic acid solution to carry out chemical conversion treatment. The product is washed with water and dried at about 7 (rc, whereby the chemical conversion coating film is cured. Therefore, the pretreatment of the chemical conversion treatment requires several treatments. Such as degreasing, cleaning, surface conditioning treatment by etching, etc., which makes the operation cumbersome, complicates the processing apparatus, and increases the processing cost. 10 Molded products produced by die casting, thixotropic molding, etc. Molding is missing (such as 'draw, void, hot water flow (fl〇w), etc.). During the inspection of mold missing (pull, void, flow, etc.), the molded product is manually Partially polished so that it can be easily seen in the molded product, and then visual inspection is performed. At this time, the polishing is performed manually, making the implementation of the test 15 cumbersome and during polishing Dust particles are produced. As a method of adjusting the surface (such as buffing), JP 2003-284457 A proposes a wet blast treatment. Further, JP2000-263442A proposes a method of continuously performing wet blast as a pretreatment for chemical conversion treatment. The above conventional technique uses wet blast as a pre-treatment of chemical conversion treatment, and the number of such methods is similar to the number of treatments using conventional chemical treatment, and therefore, the improvement effect on cost and the like is small. Furthermore, molded products that are missing need to be calibrated with putty prior to chemical conversion treatment, which reduces yield and increases costs. SUMMARY OF THE INVENTION 1285580 SUMMARY OF THE INVENTION Accordingly, based on the foregoing, it is an object of the present invention to provide a shell of a lin or a town alloy in which a chemical conversion medium is simply formed on the surface of a molded product made of magnesium or a town alloy. In order to reduce the correction by putty ash, the yield of the coating 5 is promoted, and the cost can be reduced, and a method of manufacturing a money or a town alloy casing. The money or town alloy casing of the present invention is characterized in that the surface of the magnesium or magnesium alloy casing is subjected to a wet blast using a solution containing a chemical conversion treatment agent and an abrasive, whereby the chemical conversion film is applied to the magnesium or magnesium alloy casing. Formed on the surface. The method for producing a town or a magnesium alloy casing of the present invention is characterized in that the surface of the magnesium or the alloy is subjected to a wet blast using a solution containing a chemical conversion treatment agent and an abrasive, whereby the blast is caused by the blast. The flat and chemical conversion film is formed simultaneously on the surface of the magnesium or magnesium alloy casing. These and other advantages of the present invention will become apparent to those skilled in the <RTIgt; BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart showing the method of the first embodiment of the present invention. Fig. 2 is a flow chart showing the method of Comparative Example 1. Fig. 3 is a view of the surface of the notebook computer case in the first embodiment of the present invention. Fig. 4 is a view of the surface of the notebook computer case in Comparative Example 1. Figs. 5A to 5C are photographs showing the surface observation of the cross-cut test results in Example 1 of the present invention. 128558 〇 观察 ι 至 至 c c c ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι Obtain a surface observation photo. Figures 8A to 8C are comparative examples! The surface observation photograph obtained by evaluating the corrosion resistance by the salt spray test (8). [Embodiment] Description of the Preferred Embodiment According to the present invention, the surface of the town or the magnesium alloy casing is subjected to the use of a secret gas containing a chemical conversion zone and a mixed solution of abrasives, and (4) or the surface of the town alloy casing The formation of a chemical conversion film and unevenness due to blasting is reduced by the ashing oil, thereby avoiding a decrease in yield and an increase in cost. More specifically, when the mixed b solution containing the chemical conversion treatment agent and the abrasive is injected onto the surface of the magnesium or magnesium alloy casing by wet blast, the surface is scraped with an abrasive while being appropriately thick and densely phosphoric acid The calcium-manganese phosphate complex coating film is produced by a reaction between magnesium and a chemical conversion treatment agent. Therefore, an oxide or hydroxide film that degrades the corrosion resistance, corrosion resistance, coating adhesion, and coating corrosion resistance is not formed on the surface of the magnesium or magnesium alloy casing; on the contrary, calcium phosphate-phosphoric acid A manganese complex coating film can be formed therebetween, during which calcium and filling contribute to promoting the bare corrosion resistance of the chemical conversion film, and manganese contributes to the adhesion of the coating. Further, the pulling, voiding, running, and the like on the surface of the chemical conversion product are removed, so that it is not necessary to carry out the correction by the ashing oil before the coating, and the cost can be reduced. The inventors of the present invention have earnestly studied to solve the above problems, and have found, for example, 20 1285580 as a pretreatment for avoiding ore and coating treatment of a shell made of a town or a niobium alloy, chemical conversion treatment The wet blast system is simultaneously applied to the town or the town alloy, whereby the above problems can be solved. Here, the wet blast means that the liquid and the abrasive are mixed and the mixture is injected under the pressure of 〇1 to 5.3 5 MPa. Preferably, the chemical conversion treatment agent used in the present invention contains calcium ions, manganese ions, and phosphate ions, and it is also preferred that the wet blast system is mixed with an aqueous solution containing an oxidation accelerator and an abrasive such as alumina. The solution is carried out. In the case of wet blast, the surface polishing and chemical conversion coating of the shell are simultaneously applied. Therefore, the formed coating film is also polished; however, a sufficient coating film can be obtained by satisfying the above conditions. Preferably, at least one particulate material selected from the group consisting of alumina, zirconium, glass, and resin is used as the abrasive. Further, as the resin, a melamine resin, a urea resin, a polyester resin, a phenol resin, an epoxy resin, an amino phthalate resin or the like can be used. Preferably, the abrasive has an average particle diameter in the range of 10 to 300 um. As a source of calcium ions to be injected into the chemical conversion treatment agent, one or at least two of calcium nitrate, calcium nitrite, calcium thiosulfate, and tetracalcium phosphate may be combined. Further, as a source of manganese ions, one or at least two kinds of manganese carbonate, manganese nitrate, hydrogen tetrahydrogenate, acid acid, and fluoroboric acid may be combined. Further, as the phosphoric acid ion source, one or at least two of orthophosphoric acid, condensed phosphoric acid, sillimanite, and hypophosphorous acid may be combined. Further, as the oxidation accelerator, sodium chlorate, sodium hypocarbonate or the like can be used. The oxidation accelerator can promote the reactivity between the magnesium or magnesium alloy and the above-mentioned individual component ions during the chemical conversion treatment, thereby having a satisfactory bare resistance! 28558 〇 abrasive chemical conversion coating film can be more convenient Terrain & Further, a preferred amount of the oxidizing accelerator is in the range of 0.02 to 2 g/liter to stably obtain a chemical conversion coating film having the above properties. According to the present invention, when the mixed solution of the chemical conversion treating agent and the abrasive is injected onto the surface of the magnesium or magnesium alloy by wet blast, the surface is scraped with an abrasive, and a suitably thick and dense calcium phosphate-manganese phosphate The complex coating film is produced by a reaction between magnesium or a magnesium alloy and a chemical conversion treatment agent. Therefore, an oxide or hydroxide film is not formed on the surface of the magnesium or magnesium alloy, and conversely, a calcium phosphate-manganese phosphate complex coating film can be formed. Preferably, the adhesion of the composite coating film formed by chemical conversion treatment is 5 mg/meter 2 to 50 mg/meter 2 in terms of Ca weight, and 3 mg/meter to α Μη weight. 25 mg / m 2 and 3 mg / m 2 to 100 mg / m 2 in terms of phosphorus weight. Further, the ratio of the preferred chemical conversion treatment agent is 70 to 90% by mass, and the ratio of the abrasive is 10 to 30% by mass. The chemical conversion coating film is formed on the surface of the magnesium or magnesium alloy to contain the above-mentioned predetermined S of calcium, manganese, and phosphorus, thereby having predetermined bare corrosion resistance, avoiding rust, coating adhesion, and coating. A chemical conversion coating film of coating corrosion resistance can be obtained. In particular, calcium and phosphorus are believed to contribute to promoting the bare corrosion resistance of the 20 chemical conversion coating film, and manganese is believed to contribute to the adhesion of the coating. Furthermore, the surface of the magnesium or magnesium alloy is polished by an abrasive, whereby the pulling, voiding, running, etc. on the surface of the magnesium or magnesium alloy casing product are removed, and no correction of the putty is required before coating. The cost can be reduced. Preferably! 285580 Ground' Due to the polishing function of the abrasive contained in the wet blast solution, the surface roughness of the magnesium or magnesium alloy shell 1 is set to 〇·5 um to 1 in terms of 10-point average surface roughness. The range of 〇〇um. After the above treatment, it is preferred that the surface is washed with water and then dried. In addition, if the wet blast and water are washed, an aqueous solution containing calcium ions, manganese ions, phosphate ions and an oxidation accelerator similar to those used for the chemical conversion treatment for wet blast is sprayed onto the surface. Above, the thickness of the coating film can be increased to promote corrosion resistance. Thereafter, a coating process can be carried out. In the coating treatment, a coating agent such as a cyclooxygen resin is applied by spray coating, electrodeposition or the like, and a coating agent such as melamine resin is applied thereto. Further, powder coating agents of various kinds of resins can also be applied by electrostatic coating. EXAMPLES Hereinafter, the present invention will be more specifically described by way of examples and comparative examples. 15 Example 1 As a component to be processed, a notebook computer case which was obtained by subjecting a magnesium or magnesium alloy of ASTM AZ91D to thixotropic molding was used. The thixotropic molding is obtained by extruding a town of a semi-refined or molten state or a town of an alloy from an extruder of about 60 CTC to a mold of about 250 ° C to obtain a molded product. Figure 1 shows the surface treatment method. As a chemical conversion treatment agent, 80% by mass of "Grander-Finer MC1000" (manufactured by Milli〇n Chemical Co., Ltd.: 15 to 25% by mass of phosphoric acid, 10 to 15% by mass of a manganese compound, and 10 to 20% by mass) Mom compound) and 20% by mass of a 40um average particle size of the oxidized Ilu 12 1285580 (Macorundum A #320, Macoho Co., Ltd.) mixture used as a wet blast system using WKB-2_2C manufactured by Macoho Co., Ltd. The column conditions are implemented: the compressed air pressure is 0.2 MPa, the pump pressure is 0.12 MPa, the distance between the casing and the nozzle is 30 mm, and the casing is fed forward at 40 mm/s. The casing is washed with water to remove the chemical conversion treating agent and the abrasive, and further washed by deionization, followed by drying. Comparative Example 1 Fig. 2 shows a method of performing a chemical conversion treatment after etching as a comparative example. The surface adjustments 1 and 2 in Fig. 2 represent an etching process. 1 〇 as a degreasing agent, "GFMG15SX, (manufactured by Million Chemical Co., Ltd.) was used, and its temperature was maintained at 7 ° C. Then, the above magnesium or magnesium alloy case was immersed in the degreaser for 5 minutes. The shell is degreased and then washed with water. As a residual agent, ''Grander-Finer MG104S', (manufactured by Million Chemical Co., Ltd.: 30 to 40% by mass of phosphoric acid, less than 〇·ΐ% by mass of surface 15 active The remaining amount of water was maintained at a concentration of 5% and a temperature of 60 ° C. Then, the casing was immersed in an etchant for 60 seconds to perform etching, followed by washing with water. Thereafter, it was subjected to etching. The treated member was immersed in the above-mentioned "GFMG15SX, (manufactured by Million Chemical Co., Ltd.) maintained at a temperature of 6 ° C for 7 minutes, and then washed with water. As a chemical conversion treatment agent, "Grander_Finer 20 MC1000" (manufactured by Million Chemical Co., Ltd.: 15 to 25% by mass of sulphuric acid, 10 to 15% by mass of a manganese compound, and 1 to 20% by mass of a compound) is used. And kept at 35 ° C. Then, the magnesium or magnesium alloy case treated as described above was immersed in the chemical conversion treatment agent for 40 seconds, washed with water, further washed with deionized water, and then dried. 13 1285580 Example 1 and Comparative Example 1 were evaluated for appearance. Further, the elemental adhesion on the surface of the magnesium or magnesium alloy shell is measured by X-ray quantification of Laoguang. Five parts of the surface of the shell were used and their changes were examined. The resistance was measured by "Loresta MP" manufactured by Dia Instrument Co., Ltd. (four-terminal two-probe system). The results are shown in Tables 1 and 3 and 4. Fig. 3 is a photograph showing the appearance of Comparative Example 1, and Fig. 4 is a photograph showing the appearance of Example 1. The appearance of Example 1 had a uniform surface, while Comparative Example 1 showed irregularity in appearance. Table 1 Experiment No. Appearance Stain Resistance (Ω Element Adhesion) Ca Example 1 Figure 3 No 0.4 24.4 ± 4 ~ 592 £ j^ Comparative Example 1 Figure 4 No 0.7 70.4 ± 35 112.6 ΪΖΡ ίο Note 1: The stain refers to the lack of appearance due to powder adhesion. Furthermore, the epoxy type coating (baked at 150 ° C) is maintained in a high temperature and high humidity environment (60 ° C, 95% RH relative humidity) Inside the magnesium or magnesium alloy casing for 100 hours. Thereafter, the cross-cut test is carried out (the western chessboard pattern is drawn on the surface of the sample to divide the surface into 100 parts, and taped up 15 The number of grids left after stripping the tape is calculated and determined based on the following criteria: when the number of grids left is 100, it is successful, and when the number of grids left is less than 100, it fails. 5A to 5C A photograph showing the appearance of the results of Example 1, and Figures 6A to 6C show the appearance photographs of the results of Example 1. In Figures 5A-5C to 20 6A-6C, "〇H,, stands for" before the test ,,,,,, 2mm" and "1 mm" individually represent the size of each grid. Furthermore, according to the salt spray of JISZ 2371 The test (SST) was carried out for 8 hours 1285580 and 24 hours, and the corrosion resistance was evaluated. The 7th to 7th (2) shows the appearance photograph of the result of Example 1, and the 8th to 8th (: the figure shows The appearance photograph of the result of Comparative Example 1. In Figures 7A-7C to 8A-8C, ΌΗ" represents, before,, and, and, 8H" and, 24H" individually represent the test processing time. The above results were confirmed to be more uniform than that of Comparative Example 1, and the casing of Example 1 was uniform in color and smooth. Further, in Example i, the pulling, the void, the flow, and the like on the surface of the molded product were removed. This promotes the yield of the coating which is carried out after the treatment, and makes it unnecessary to perform the calibration of the putty before coating, thereby reducing the cost. In Example 1, although the adhesion of the coating film is higher than that of the comparative example, it is compared with the comparative example. 1 is less change than the 'adhesive amount. Other coating properties (such as electrical resistance, coating properties, and corrosion resistance) show similar values in the implementation and comparison examples. 15 20
…再者，於實施例i’因為處理數量小，因此塗覆處理 被輕易實施；藉此降低費用。Further, in the embodiment i', since the number of processes is small, the coating process is easily carried out; thereby reducing the cost.
本發明可於未偏離其精神或基本特性下以其它型式 t此中請案中減之實關於所有方㈣、被認為例示 月而非限制。本發明之細係以所㈣請專利範圍表示 之=述描述内容，且申請專利範圍之等化意義及範 有、吏化係欲被包含於内。 式簡單說明】 第1圖係圖示本發明之實施例1之方法流程。 第2圖係圖示比較例1之方法流程。 弟3圖係本發明實施例！中之筆記型電腦殼體之表面 15 1285580 察相片。 第4圖係比較例1中之筆記型電腦殼體之表面觀察相 片。 第5A至5C圖係顯示本發明實施例1中之橫切測試結果 5 之表面觀察相片。 第6 A至6 C圖係顯示比較例1中之橫切測試結果之表面 觀察相片。 第7A至7C圖係本發明實施例1藉由鹽喷灑測試(SST) 評估耐腐蝕性而獲得之表面觀察相片。 10 第8A至8C圖係比較例1藉由鹽喷灑測試(SST)評估耐 腐蝕性而獲得之表面觀察相片。 【主要元件符號說明】 (無）The present invention may be derogated from all other aspects (4) without being deviated from its spirit or basic characteristics, and is considered to be a month and not a limitation. The details of the present invention are expressed in the scope of the patent application, and the meaning of the scope of the patent application and the scope of the patent application are intended to be included. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart showing the method of the first embodiment of the present invention. Fig. 2 is a flow chart showing the method of Comparative Example 1. Brother 3 is an embodiment of the present invention! The surface of the notebook computer case in the middle 15 1285580 Check the photo. Fig. 4 is a view of the surface of the notebook computer case in Comparative Example 1. 5A to 5C are photographs showing the surface observation of the cross-cut test result 5 in the embodiment 1 of the present invention. Figures 6A to 6C show the surface observation photographs of the cross-cut test results in Comparative Example 1. 7A to 7C are photographs of the surface observation obtained by the salt spray test (SST) in the present invention to evaluate corrosion resistance. 10 Figures 8A to 8C are comparative observations of surface observation photographs obtained by evaluating the corrosion resistance by a salt spray test (SST). [Main component symbol description] (none)
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