200413572 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、實施方式及圖式簡單說明） (一） 發明所屬之技術領域 本發明係關於由表面上具有導電性優異之陽極氧化覆 膜之鎂或鎂合金所製成之製品。又，係關於該等製品之製 造方法。 (二） 先前技術 鎂及鎂合金係因爲在實用金屬中爲最輕因而比強度高 、放熱性亦良好，比較於樹脂之回收性亦優異，近年來， 正廣泛地被使用於電氣機器或汽車零件用途。特別地，適 合被使用作爲小型輕量化之要求性能高、創意性、回收性 之要求亦高之電氣機器之框體。然而，由於鎂及鎂合金容 易被腐蝕，故必須具有耐腐蝕性之表面處理或塗裝。 藉由對於鎂或鎂合金實施陽極氧化處理，可賦予優異 之耐腐蝕性。代表性地一般進行以稱作Dow 1 7法或HAE法 之處理方法之陽極氧化處理，因而可形成實用上具有足夠 之耐腐触性之陽極氧化覆膜。又，於特表平1 1 - 5 0 2 5 6 7號 公報中（W096 / 2859 1 )中，記載浸漬於含有氨與磷酸鹽化 合物之電解液中來陽極氧化處理鎂或鎂合金之方法。 又’亦可藉由形成處理鎂或鎂合金賦予某程度之耐腐 蝕性、可形成具有導電性之覆膜，則記載於下述之公報中 。於特開2000 - 9 6 2 5 5號公報中，記載含有固定量之鉀、錳 及磷、電阻率爲0·1Ω·〇ιώ以下之形成處理覆膜。又，於 200413572 特開2 0 0 0 - 3 2 8 26 1號公報中記載由於以pH1〜5之酸性水溶 液蝕刻鎂合金表面，接觸含有有機磷化合物之P Η 7〜1 4之鹼 性水溶液，接著接觸形成處理液之鎂合金表面處理方法， 記載著得到表面電阻値小之製品之主旨。 於電發顯不器等之各種顯示器或行動電話等之中，因 而可有效率地遮蔽所產生之電磁波而佳。由於鎂及鎂合金 具有良好之導電性，用其之電氣機器之框體可具有良好之 電磁波遮蔽性。又，多數電氣機器、特別是數位電子機器 中，爲了防止錯誤運轉，接地（地線）來除去電磁干擾雖 然重要，此時，如果框體爲鎂或鎂合金，亦可接地於其上 〇 然而，在如前述之鎂及鎂合金上，具有耐腐蝕性之表 面處理或塗裝是必要的。藉由實施用來賦予耐腐蝕性於鎂 或鎂合金之陽極氧化處理，絕緣性氧化覆膜會覆蓋鎂或鎂 合金而失去電磁波遮蔽性，同時亦變成不可能接地。因此 ’採用例如一方面用於接地之部分進行遮蓋後進行陽極氧 化處理’ 一方面全面陽極氧化處理後硏削除去一部份陽極 氧化膜之手法等。然而，該等方法係因操作繁雜而提高生 產成本。 另外，在藉由形成處理所形成之覆膜方面，最近報告 有如例如記載於特開2000 - 96255號公報或特開 2000 -3 2 82 6 1號公報之覆膜具有導電性。然而，比較於藉由通電 於鎂或鎂合金來形成堅固之氧化覆膜之陽極氧化處理，則 單純僅以浸漬於處理液之形成處理所形成之覆膜，其耐腐 一 8 - 200413572 飩性不足。近年來在行動機器之框體等，由於在多樣之環 境下之耐腐蝕性變得必要，該問題特別重要。因此，在以 形成處理形成覆膜之情況下，現狀爲於其上進一步實施多 數層之塗裝來確保任何之耐腐蝕性。然而，在形狀複雜之 電氣機器之框體上實施均勻之塗裝未必容易，由於進行多 次之塗裝步驟則成本上昇大。 另外’藉由現今廣t之進行作爲陽極氧化處理之Dow 17 法，所得之陽極氧化覆膜含有鉻，以HAE法係含有錳。又 ，形成處理而得製品之多數或該覆膜含有重金屬元素。由 於含有該等之重金屬元素，於回收使用時會混入重金屬於 鎂或鎂合金而不佳。特別地，由於鎂及鎂合金之特徵爲較 於塑膠之回收性優異，不能忽視因重複回收次數所累積之 重金屬元素量。又由於處理液含有重金屬元素，從該廢液 處理或週邊環境保護之觀點而不佳。 本發明係用於解決上述課題者，以提供製造由表面上 具有兼備導電性與優異耐腐飩性之陽極氧化覆膜之鎂或鎂 合金所製成之製品爲目的者。又係以提供製造由該等錶或 鎂合金所製成之製品之方法爲目的者。以本發明所得之陽 極氧化覆膜係亦因未含有重金屬元素而可解決上述課題， 從回收性或環境保護之觀點亦爲優異者。又，亦因所使用 之電解液未含有重金屬元素’由於可形成上述陽極氧化覆 膜，同時賦予工廠週邊之環境保護，亦可減輕廢液處理成 本。 (三）發明內容 一 9 一 200413572 發明說明 上述S果題係藉由提供由表面具有於互相距離1 〇 m m之2 個端子間所測定之覆膜表面電阻値爲1 〇 〇 Ω以下之導電性陽 極氧化覆膜之纟美或鎂合金所製成之製品而達成。 以往，陽極氧化處理鎂或鎂合金而得之覆膜係以氧化 物爲主成分之覆膜，其爲絕緣體。與其說因爲是絕緣體， 不如說認爲是不流通腐蝕電流於鎂或鎂合金，可防止本身 之氧化劣化。然而，本發明者等專心一志硏究之結果，發 現同時爲陽極氧化覆膜及具有導電性之覆膜。而且從以往 以來即具有陽極氧化覆膜，亦明白優異之耐腐鈾性能保持 原貌。因此，提供一種由具有優異之耐腐蝕性同時具有良 好導電性之鎂或鎂合金所製成之製品。特別地，可提供電 磁波遮蔽性、接地特性等優異之電氣機器之框體。其中， 前述陽極氧化覆膜之膜厚爲0.01〜l〇//m，因耐腐鈾性與導 電性平衡之觀點而佳。 本發明中，前述陽極氧化覆膜以含有35〜65重量％鎂 元素、25〜45 %氧元素爲佳。由於含有已氧化之鎂爲主成分 ’雖可推測具有鎂或鎂合金表面之陽極氧化覆膜本來應具 有之耐腐蝕性，但未必爲具有該等耐腐蝕性之理由。又， 前述陽極氧化覆膜以含有4〜15重量％磷元素爲佳，亦以含 有5〜20重量％鋁元素爲佳。由於含有適量之鎂、氧以外之 元素’雖可推測不損及耐腐蝕性並具有良好之導電性，但 亦不一定爲具有該等導電性之理由。又，本發明之陽極氧 化覆膜係亦因未含有如習知之陽極氧化覆膜所含有之重金 -1 0 - 200413572 屬元素，而可發揮優異之性能者。 本發明較佳之實例係由以陽極氧化覆膜覆蓋鎂或鎂合 金表面之全部，而且僅於該陽極氧化覆膜表面之一部分施 行樹脂塗裝並露出殘餘部分之陽極氧化覆膜之鎂或鎂合金 所製成之製品。由於在該一部份設置陽極氧化覆膜之露出 部分，確保電磁遮蔽性或接地特性，同時可藉由樹脂塗裝 來提供外觀美麗、耐摩擦性優異之製品。具體來說，於框 體內面未施行樹脂塗裝、於框體外面施行樹脂塗裝之電氣 機器之框體爲特別佳之實例。 ® 又，本發明之目的在於亦藉由提供由以浸漬鎂或鎂合 金於含有0.1〜lmol/L磷酸根、pH爲8〜14之電解液中，陽 極氧化除理該表面爲特徵之前述鎂或鎂合金所製成之製品 之製造方法而達成。其中，前述電解液以含有0.2〜5mol/L 氨或銨離子爲佳。 如前述，以往之陽極氧化處理中，大致上處理液含有 重金屬離子，亦爲含有使廢液處理困難之氟離子之情況。 相對於此，在由本發明之鎂或鎂合金所製成之製品之製造 ® 方法中，未含有該等成分亦可得性能優異之陽極氧化覆膜 。近年來，一方面由於含有重金屬元素廢液之排出規定變 得嚴格，從本發明之製造方法爲環境保護之觀點來看亦爲 重要的。 本發明之製造方法中’由於在陽極氧化處理時預先浸 漬鎂或鎂合金於酸性水溶液中，而以浸漬於電解液來進行 陽極氧化處理爲佳。由於從適切地前處理之後提供於陽極 - 1 1 - 200413572 氧化處理，容易得到達到本發明效果之製品。 又，於本發明之製造方法中，於陽極氧化處理後，以 僅於陽極氧化覆膜表面塗裝一次樹脂塗膜，於4 〇〜丨2 〇之 溫度加熱來乾燥塗膜爲佳。由於可得到耐腐蝕性優異之陽 極氧化覆膜，僅簡單之塗裝即足夠，結果爲可削減製造成 本。 (四）實施方式 以下，詳細地說明本發明。 本發明係由表面具有於互相距離1 〇mm之2個端子間所 測定之覆膜表面電阻値爲1 〇 〇 Q以下之導電性陽極氧化覆膜 之鎂或鎂合金所製成之製品。 作爲原料之鎂或鎂合金係可由鎂作爲主成分，亦可爲 包含鎂單體之金屬，亦可爲合金。通常，以使用用來賦予 成形性、機械強度、延展性等之鎂合金爲佳。鎂合金方面 ’舉出有鎂-鋁系合金、鎂-鋁-鋅系合金、鎂-鋁-錳系合金 、鎂-鋅-鉻系合金、鎂-稀土族元素系合金、鎂-鋅-稀土族 系合金等。於本發明之實例中係使用鎂-鋁-鋅系合金，於 所得之陽極氧化覆膜中係含有鋁元素。因而，原料之鎂合 金方面係上述各種合金中，推測以含有鋁者爲佳。 供予1½極氧化處理之鎂或鎂合金之形態並無特別之限 制。可使用藉由壓鑄法、觸變成型法、壓機成型法、锻造 法等所形成之成形品。於成形時，有於成形品表面附近所 形成之皺折或中空部分之內部中殘留離型劑之情況。於陽 極氧化處理之情況下，比較於形成處理之情況，所殘留之 -12- 200413572 離型劑容易變少。殘留於製品之離型劑係於加熱時揮發， 而於樹脂塗模產生膨脹。其中，成形時所使用之離型劑方 面，係以由有機矽化合物所製成之離型劑爲代表。 由鎂或鎂合金所製成之成形品，係由於在表面具有由 成形時所附著之離型劑等之有機物而來之污染物，而以施 行脫脂處理爲佳。用於脫脂之液體方面，係以使用含有界 面活性劑或螯合劑之水溶液爲佳。 於必要時進行脫脂處理之後，以浸漬於酸性水溶液之 後，浸漬於電解液來進行陽極氧化處理爲佳。藉由浸漬於 酸性水溶液來適度地蝕刻鎂或鎂合金之表面，可除去既已 形成不充分氧化覆膜或所殘存之有機物之污染。雖然酸性 水溶液方面並無特別之限制，但以磷酸水溶液具有適度之 酸性度爲佳。在使用磷酸水溶液之情況下，在與蝕刻之同 時於表面上亦形成磷酸鎂。又，配合界面活性劑或螯合劑 酸性水溶液中，亦可同時進行脫脂處理。 又，在以如此之酸性水溶液處理之後，亦以進一步以 鹼性水溶液洗淨後供於陽極氧化處理爲佳。在酸性水溶液 中由於不溶解之成分（髒污s m u t )附著於鎂或鎂合金之表 面，而可將其除去。鹼性水溶液方面以使用氫氧化鈉水溶 液或氫氧化鉀水溶液爲佳。 於如前述脫之處理、酸性水溶液處理、鹼性水溶液處 理之各處理步驟之後，必要時亦可施行水洗或乾燥。如此 一來，已施行必要時之前處理之鎂或鎂合金浸漬於電解液 中〇 -13- 200413572 本發明之電解液係以含有磷酸根之鹼性水溶液爲佳， 較具體來說係以含有〇 · 1〜1 m〇l / L磷酸根、pH爲8〜14之水 溶液爲佳。由於含有適量之磷酸根，則於陽極氧化膜中含 有適量之磷元素。又，由於成爲鹼性可防止鎂或鎂合金不 必要之溶出。 其中磷酸根係游離之磷酸、磷酸鹽、磷酸氫鹽、磷酸 二氫鹽並包含於電解液中。又，在磷酸縮合而得之多磷酸 或其鹽類之情況下，僅含有將該等加水分解所得之磷酸根 數目之磷酸根。在鹽之情況下，可爲金屬鹽，亦可爲如銨 · 鹽之非金屬鹽。磷酸根之含有量係以0 · 1〜1 mo 1 / L爲佳。以 0.15mol/L以上爲較佳、而以0.2mol/L以上爲更佳。又較 佳爲0.7mol/L以下、以0.5mol/L以下爲更佳。 電解液之pH係以8〜14爲佳。以PH爲9以上爲較佳、 以1 0以上爲更佳。又以pH爲1 3以下爲較佳、以1 2以下 爲更佳。 又’以電解液含有總量爲0.2〜5mol/L之氨或錢離子爲 佳。因而保持電解液之pH爲適當之鹼性。氨或銨離子之含 ® 有量係以0.5 mol/L以上爲較佳、而以lmol/L以上爲更佳 。又以3mol/L以下爲較佳、而以2mol/L以下爲更佳。 本發明之電解液雖然在不妨害本發明效果之範圍內亦 可含有其他成分，但以實質上不含有重金屬元素爲佳。其 中重金屬元素可爲以作爲單體之比重超過4之重金屬元素 ’爲包含於習知之陽極氧化處理中之代表性之電解液者， 舉例有絡、叙等。特別以未含有排出規定嚴格且有害之鉻 -14- 200413572 爲佳。還有，包含於鎂之重金屬、例如鋅微量溶出而包含 於電解液中係通常不是什麼問題。又，亦以本發明之電解 液未含有氟元素爲佳。由於含有氟元素之水溶液多使廢液 處理變得困難。 於前述電解液中，浸漬已進行必要時之前處理之鎂或 鎂合金，以其爲陽極並以通電來進行陽極氧化處理。所使 用之電源並無特別之限制，雖使用直流電源與交流電源均 可，但以使用直流電源爲佳。又，於使用直流電源時，亦 雖使用定電流電源與定電壓電源均可，但以使用定電流電 源爲佳。陰極材料並無特別之限制，可適當地使用例如不 銹鋼材等。陰極表面積係以比較於所進行陽極氧化處理之 鎂或鎂合金之表面積爲大爲佳，以2倍以上爲較佳，通常 爲1 0倍以下。 使用定電流電源作爲電源時之陽極表面之電流密度通 常爲0.1〜ΙΟΑ/dm2。以0.2A/dm2以上爲佳，以0.5A/dm2以 上爲較佳。又，以5A/dm2以下爲佳，以2A/dm2以下爲較佳 。通電時間通常爲10〜1 000秒。以20秒以上爲佳，以50 秒以上爲較佳。又，以5 0 0秒以下爲佳，以2 0 0秒以下爲 較佳。在以定電流電源通電時，通電開始之施加電壓低， 同時隨時間經過提高施加電壓。結束通電時之施加電壓通 常爲5 0〜4 0 0伏特。以1 0 0伏特以上爲佳，以1 5 0伏特以上 爲較佳。又，以3 00伏特以下爲佳，以2 5 0伏特以下爲較 佳。相對於在作爲習知之陽極氧化處理方法之Dow 1 7法或 HAE法中，大多設定施加電壓於未滿100伏特，於本發明 200413572 之陽極氧化處理中，係以設定於較高電壓爲佳。因此，即 使含有有機矽離型劑等不純物之部分進行氧化反應亦變得 容易，容易於鎂或鎂合金表面全體上形成良好之覆膜。又 ’由於隨著氧化反應從鎂或鎂合金表面會劇烈產生氧氣， 容易於陽極氧化處理中除去上述不純物。通電中電解液溫 度通常爲5〜7 0 °C。以1 (TC以上爲佳。又，以5 0 °C以下爲佳 ，以3 (TC以下爲較佳。 通電結束後，藉由洗淨處理，除去附著於陽極氧化覆 膜表面之電解液。於洗淨時，係以不僅用水，並使用酸性 水溶液來洗淨爲佳。由於電解液爲鹼性，藉由以酸性水溶 液洗淨，在進行樹脂塗裝之情況下，可改善塗膜之密著性 。酸性水溶液方面，可使用硝酸水溶液、鹽酸水溶液、硫 酸水溶液等。洗淨後，進行乾燥，得到由表面具有陽極氧 化覆膜之鎂或鎂合金所製成之製品。 本發明之由鎂或鎂合金製成之製品，係表面具有以相 互距離10mm之2個端子間所測定之覆膜表面電阻値爲100 Ω以下之導電性陽極氧化覆膜者。該電阻値即在陽極氧化 覆膜表面之相互距離1 0mm之任意2點上押著端子所測定之 電阻値（Ω )，本發明之製品亦可爲於該表面至少一處具 有上述値以下之電阻値。由於鎂或鎂合金本身電阻値小， 實質上，爲測定相關於存在於測定用之端子與鎂或鎂合金 間之陽極氧化覆膜之厚度方向之電阻値。因而’該電阻値 係從電磁波遮蔽性或接地特性方面對應於對製品所要求之 性能之數値。以1 0 Ω以下爲佳，以1 Ω以下爲較佳’以0 . 5 - 1 6 - 200413572 Ω以下爲最佳。還有，由未進行表面處理之鎂或鎂合金所 製成之成形品表面之電阻値，在AZ91D之情況下，通常爲 0.02〜0.1Ω左右之値。 以本發明所得之陽極氧化覆膜，亦如於第1圖所示， 存在認爲由表面上通電中之電弧而來之多數個孔洞之情況 很多。該方面與形成處理覆膜不同。陽極氧化覆膜之膜厚 係以0.01〜lO/zrn爲佳。以o.l/zm以上爲較佳，以0.5//m 以上爲更佳。又，以5 // m以上爲較佳，以3 // m以上爲更 佳。膜厚過薄則恐怕耐腐蝕性會惡化，在過厚之情況下， 導電率降低，恐怕降低電磁波遮蔽性或接地特性。 以本發明所得之陽極氧化覆膜之化學組成雖無特別之 限制，以含有35〜65重量％鎂元素、25〜45重量％氧元素者 爲佳。即爲陽極氧化鎂或鎂合金結果之生成物，以含有以 已氧化之鎂爲主成分者爲佳。鎂元素含有量係以4〇重量％ 以上爲較佳，以4 5重量％以上爲更佳。又，以6 〇重量〇/〇 以下爲較佳，以5 5重量％以下爲更佳。氧元素含有量係以 3 0重量％以上爲較佳。又，以4 0重量％以下爲較佳。 前述陽極氧化覆膜以含有4〜1 5重量％磷元素爲佳。磷 元素之含有量係以5重量％以上爲較佳，而以6重量％以 上爲更佳。又，以1 2重量％以下爲較佳，而以1〇重量％ 以下爲更佳。又’亦以a有5〜20重量％鋁元素爲佳。銘元 素之含有量係以7重量％以上爲較佳，而以9重量％以上 爲更佳。又，以17重里％以下爲較佳，而以I〗重量％以 下爲更佳。由於含有適量鎂、氧以外之上述元素，可推測 - 1 7- 200413572 爲無損及耐腐蝕性，具有良好之導電性者。本發明之陽極 氧化覆膜在無妨害本發明效果之範圍內包含上述以外之元 素亦無妨。然而，原料之鎂合金以除去原來含有者，實質 上以不含有重金屬、特別是鉻元素爲佳。又，亦以實質上 不含有氟元素爲佳。 由表面上具有陽極氧化覆膜之本發明之鎂或鎂合金所 製成之製品之用途係無特別之限制，可使用於各種電氣機 器或汽車用零件等。於使用時，雖然必要時於陽極氧化覆 膜之表面上亦可實施上塗層之塗裝，但是爲了活用導電性 良好之本發明陽極氧化覆膜之特徵，不能以絕緣膜構成之 塗裝覆蓋製品之全體。 所使用之塗料係無特別之限制，可使用於金屬表面之 塗裝中所使用之各種塗料。可使用溶劑型塗料、水性塗料 、粉體塗料等來形成樹脂塗膜。於塗布後需要高溫燒成之 熱硬化型塗料、僅於較低溫揮發溶劑或水即可之塗料均可 ，以使用操作容易之後者爲佳。又，爲了使外觀美麗係以 使用透明樹脂塗料爲佳，使用適宜著色者亦可。塗裝方法 亦無特別之限制，可採用噴霧塗裝、浸漬塗裝、電鑛塗裝 、粉體塗裝等之公認之方法。在由以具有一部份無塗膜之 部分爲佳之本發明之鎂或鎂合金所製成之製品中，以採用 噴霧塗裝或藉由溶射法之粉體塗裝爲佳。 於陽極氧化處理之後，以僅於陽極氧化覆膜之表面塗 裝一次樹脂塗膜來形成塗膜爲佳。於電氣機器之框體等， 亦大多具有複雜之形狀，形成均質之塗膜係未必容易。雖 - 18- 200413572 然大多以實施多數次塗裝可提昇一段耐腐鈾性，但是塗裝 次數多則成本上升亦變大。該方面，在由耐腐蝕性良好之 本發明z錶或錶合金所製成之製品中’大多爲僅以一.次塗 裝即得十分良好之耐腐蝕性之情況。 在使用溶劑型塗料或水性塗料之情況下，係以於 40〜120°C之溫度加熱來乾燥塗膜爲佳。以50 °C以上、‘10(TC 以下較佳。在由耐腐蝕性良好之本發明之鎂或鎂合金所製 成之製品中，大多僅以較低溫之加熱步驟來乾燥硬化之樹 脂塗裝即足夠，結果可削減製造成本。加熱乾燥方法係無 ® 特別之限制，可使用泛用之烤箱等。 本發明之較佳之實例係由以陽極氧化覆膜覆蓋鎂或鎂 合金表面之全部，而且僅於該陽極陽化覆膜表面之一部分 實施樹脂塗裝而露出殘餘部分之陽極氧化覆膜之鎂或鎂合 金所製成之製品。由於以陽極氧化覆膜覆蓋該等鎂或鎂合 金表面，可確保製品全體之耐腐蝕性。但是，其中所謂之 全部係實質之全部，僅於陽極氧化處理時與電源相通之接 | 點部分等爲未形成陽極氧化覆膜部分亦無妨。又，由於僅 陽極氧化覆膜表面之一部分實施樹脂塗裝而露出殘餘之部 分陽極氧化覆膜，可確保電磁波遮蔽性或接地特性，同時 藉由樹脂塗裝而提供外觀美麗、耐摩擦性優異之製品。 特佳之實例係於框體內面未實施樹脂塗裝，而於框體 外面實施樹脂塗裝之電氣機器之框體。由於在框體外面實 施樹脂塗裝，不僅可使外觀美麗，亦可防止使用時之損傷 。另外，由於在框體內面露出具有導電性之陽極氧化覆膜 -19- 200413572 ，可容易地確保由電氣配線來之接地，可有效地遮蔽 體內部之電子電路來之電磁波。 由如此得到之本發明之鎂或鎂合金所製成之製品 使用於各種用途。可使用於行動電話、個人電腦、攝 、相機、光碟機、顯示器（CRT、電漿、液晶）、投影 之電氣機器之框體，或汽車用零件等。 用於實施發明之最佳實例 以下，雖然利用實例來更詳細地說明本發明，但 明係不受該等限制者。於本實例中之試驗方法係依照 之方法來進行。 (1 )陽極氧化覆膜之膜厚測定 將試驗片切斷成5mmx 10mm之尺寸，包覆於環氧 中之後，硏磨切斷面而得到鏡面。從試樣之截面方向 用曰本電子株式會社製X射線微量分析儀「jXA_89〇〇 攝影電子顯微鏡相片，並測定膜厚。 (2) 陽極氧化覆膜之化學組成物分析 使用日本電子株式會社製X射線微量分析儀「〗X A _ 」’從覆膜表面及截面之2個方向來進行膜組成物之 。在每個方向進行3點測定，由該等平均値求得化學 物。測定係於1 5kV加速電壓、2χ 10·8Α試樣照射電流 件來進行。數據分析係藉由ΖΑΗ補正來進行。 (3) 陽極氧化覆膜表面之電阻値測定 使用三菱化學株式會社低電阻率計「羅累斯特 MCP-T400」，使用二探針式探針rMCP-Tp〇1」來測定 由框 ，可 影機 機等 本發 以下 樹脂 ，使 」來 8900 分析 組成 之條 -AP 。於 200413572 試驗片中央部分貼附測定端子於覆膜表面地測定電阻値（ Ω ) °前述探針係以1 Omm之間隔配置測定端子者，端子係 於鈹合金上電鍍金者，而該前端形.狀係2mm直徑之圓柱狀 ’貼附端子於覆膜表面之荷重爲每1個端子240g。 (4 )溫水浸漬試驗 將試驗片浸漬於保持於70 °C之溫水中24小時。經過24 小時之後，取出試驗片，擦去水分之後，貫穿樹脂塗膜與 陽極氧化覆膜地以約1 mm之間隔添加棋盤網狀之刻痕，遵 照]IS K5400來進行膠帶剝離試驗，以肉眼觀察塗膜之剝 ® 離狀況或有否其他缺陷之產生。 (5 )鹽水噴霧試驗 於試驗片之表面，貫穿樹脂塗膜與陽極氧化覆膜地添 加十字狀之刻痕（交叉刻痕）之後，遵照；i IS Z- 23 7 1來進 行5%鹽水噴霧試驗1 20小時。經過1 20小時之後，取出試 驗片，以肉眼觀察從交叉刻痕部分開始之膨脹產生狀況或 有否其他缺陷之產生。 $ 【實例1】 以90重量％鎂、9重量％鋁及1重量％鋅所製成之ASTM No . AZ9 1D之鎂合金爲原料，使用藉由熱腔法所鑄造之170mm X 5 0 m m X 2 m m之尺寸之合金板作爲試驗片。浸漬上述試驗片 於含有2 . 2重量％之磷酸與微量界面活性劑之酸性水溶液 中之後，以離子交換水洗淨。接著，浸漬於含有1 8重量％ 之氫氧化鈉之鹼性水溶液中之後以離子交換水洗淨，來前 處理試驗片之表面。 -21- 200413572 混合磷酸水溶液與氨水，並調製含有0 . 25m()1/L磷酸 根、含有總量1 . 5m〇1 /L氨或銨離子之電解液，並保持在 2 〇 °C。該電解液之pH爲1丨。浸漬已實施前處理之鎂合金試 驗片於其中作爲陽極，並進行陽極氧化處理。此時陰極方 面係使用具有前述陽極之4倍表面積之S U S 3 1 6 L板。使用 定電流電源而以陽極表面之電流密度爲lA/dm2來通電120 秒。於通電開始時係低的施加電壓，於通電結束時係上升 至約200伏特。通電結束之後，以離子交換水、硝酸水溶 液、離子交換水之順序洗淨後乾燥。 0 以掃描式電子顯微鏡觀察所得之陽極氧化覆膜表面之 相片示於第1圖。於陽極氧化覆膜表面發現認爲由通電中 之電弧而來之多個孔洞之存在。該陽極氧化覆膜之膜厚爲 約1 · 5 // πι。其中所爲之膜厚係在具有由於具有多數個孔洞 導致之局部膜厚不均勻之覆膜上，從厚的部分表面至基材 之鎂合金面之平均距離。所得之陽極氧化覆膜係含有4 8 . 0 重量％鎂元素、33.5重量％氧元素、7.0重量％磷元素及11.2 重量％鋁元素。陽極氧化覆膜表面之電阻値爲0 . 2 5 Ω。 在所得之陽極氧化覆膜之表面上，空氣噴霧塗裝卡修 株式會社製丙烯酸有機矽系塗料「亞斯克特3 Ο (Π」。此時 ，於塗裝時係非底層塗裝，而爲僅塗裝1次該丙烯酸有機 矽系塗料於陽極氧化覆膜之表面。塗布後，以6(TC加熱20 分鐘，揮發除去溶劑並使塗膜硬化。如此一來，於陽極氧 化覆膜之表面形成約20 // m膜厚之塗膜。 將所得之試驗片供予溫水浸漬試驗及鹽水噴霧試驗時 -22- 200413572 ’在任何情況下，於表面未觀察到外觀上之變化。供予溫 水試驗後之試驗片表面、供予硏水噴霧試驗後之試驗片表 面之相片個別示於第2圖、第3圖。 【比較例1】 . 混合磷酸水溶液與氨水，來調製含有0.0 8mol/L磷酸 根、以其總量含有〇 · 8mo 1 / L氨或銨離子之電解液，保持在 2〇°C。該電解液之pH爲1 1。於其中浸漬已實施與實例1相 同之前處理之鎂合金試驗片作爲陽極，來進行陽極氧化處 理。此時之陰極方面，使用與實例1相同者。使用定電流 電源並以陽極表面之電流密度爲lA/dm2來通電120秒。於 通電開始時係低的施加電壓，於通電結束時係上升至約200 伏特。通電結束之後，以離子交換水、硝酸水溶液、離子 交換水之順序洗淨後乾燥。 所得之陽極氧化覆膜之膜厚爲約1 · 5 μ m，含有5 4 . 8重 量％鎂元素、37.7重量％氧元素、3.2重量％磷元素及4.3 重量％鋁元素。陽極氧化覆膜表面之電阻値係超出測定所 使用之電阻率測定器限制之1 Ο7 Ω。 於所得之陽極氧化覆膜之表面，與實例1相同地形成 樹脂塗膜。將所得之試驗片供予溫水浸漬試驗及鹽水噴霧 試驗時，在任何情況下，於表面均無觀察到外觀之_彳七。 【比較例2】 進行稱爲D 〇 w 1 7之公認陽極氧化覆膜形成方法之試驗 範例。調製含有3 0 0 g / L酸性氟化氨、1 0 〇 g / L重鉻酸鈉[及 9 0 g / L磷酸之電解液，保持在7 5 °C。於其中浸漬已實施與 200413572 實例1相同之前處理之鎂合金試驗片作爲陽極，進行陽極 氧化處理。此時之陰極方面係使用與實例1相同者。使用 定電流電源並以陽極表面之電流密度爲4A/dm2來通電300 秒。於通電開始時係低的施加電壓，於通電結束時係上升 至約7 0伏特。通電結束之後，以離子交換水洗淨後乾燥。 所得之陽極氧化覆膜之膜厚爲約1 . 5 // m，含有26 . 0重 量％鎂元素、25.7重量％氧元素、11.2重量％憐元素、1.〇 重量％鋁元素、23.4重量％氟元素、9.2重量％鉻元素及3.6 重量％鈉元素。陽極氧化覆膜表面之電阻値係超出測定所 使用之電阻率測定器限制之1 Ο7 Ω。 【比較例3】 取代陽極氧化處理，使用市售之形成處理液來進行形 成處理之範例。以離子交換水稀釋成爲含有.7 5 g / L比例之 米力翁化學株式會社製形成處理液「MC- 1 000」來調製處理 液，保持於4 0 °C。雖然該形成處理液之化學組成物之詳細 並不淸楚，但推定爲含有磷酸離子、錳（或錳氧化物）離 子及鉀離子之形成處理液。於該處理液中，浸漬已實施與 實例1相同之前處理之鎂合金試驗片3 0秒。浸漬結束後， 以離子交換水洗淨後乾燥。 所得之形成處理覆膜之膜厚爲0 . 1 // m，爲難以定量地 測定之薄的膜厚。該化合覆膜係以單位面積平均含有量爲 含有85mg/m2鉀元素、95 mg/m2錳元素、220 mg/m2磷元素 者。又，該形成處理覆膜表面之電阻値爲0 . 5 Ω。 於所得之化合覆膜之表面上，與實例1同樣地形成樹 - 2 4 - 200413572 脂塗膜。將所得之試驗片供予溫水浸漬試驗後之外觀、供 予鹽水噴霧試驗後之外觀分別示於第4圖、第5圖。在任 何之情況下’添加於覆膜之割痕周圍明顯地發現樹脂塗膜 之剝離。 【比較例4】 取代陽極氧化處理’，使用與比較例3不同之市售形成 處理液來進行形成處理之範例。以離子交換水稀釋成爲含 有7 5 g / L比例之日本帕卡賴進株式會社製形成處理液「MB -Cl 〇M」來調製處理液，保持於5(rc。雖然該形成處理液之 · 化學組成物之詳細並不淸楚，但推定爲含有以1 4重量％無 水鉻酸及0 . 7重量％氫氟酸爲主成分之形成處理液。於該 處理液中，浸漬已實施與實例1相同之前處理之鎂合金試 驗片6 0秒。浸漬結束後，以離子交換水洗淨後乾燥。 所得之形成處理覆膜之膜厚爲0 · 1 // m更以下，爲難以 定量地測定之薄的膜厚。該化合覆膜係以單位面積平均含 有量爲含有190mg/m2鉻元素者。又，該形成處理覆膜表面 之電阻値爲® 於所得之化合覆膜之表面上，與實例1同樣地形成樹 脂塗膜。將所得之試驗片供予溫水浸漬試驗及鹽水噴霧試 驗後，在任何之情況下，均無發現添加於覆膜之割痕周圍 之樹脂塗膜之剝離或膨脹。然而，溫水浸漬試驗之後，觀 察到在接近試驗片邊緣部分，於塗膜上產生多數個成點狀 之膨脹點（水泡狀）。 如以上之說明，以於實例1中陽極氧化處理所得之本 - 25 - 200413572 發明鎂合金所製成之製品係兼具導電性與優異之耐腐蝕性 者。以如示於比較例1或2之習知陽極氧化處理所得之鎂 合將所製成之製品係耐腐蝕性優異，而無發現導電性。另 外’以如示於比較例3之形成處理所得之鎂合金所製成之 製品，係發現導電性，但耐腐蝕性不足。 【產業上之利用可行性】 以本發明之鎂或鎂合金所製成之製品，係於表面上具 有兼具導電性與優異之耐腐蝕性之陽極氧化覆膜者。因而 ’使用作爲以電磁波遮蔽性或接地特性優異之鎂或鎂合金 所製成之製品，作爲電氣機器之框體特別有用。而且，該 製品不含有重金屬，亦適合於回收。再者，由於以未使用 重金屬離子或氟離子之電解液來進行陽極氧化處理，可提 供境保護之觀點亦優異之製造方法。 (五）圖式簡單說明： 第1圖係以掃描式電子顯微鏡觀察於實例1所得之陽 極氧化覆膜表面之相片。第2圖係供予溫水浸漬試驗後之 實例1試驗片表面之相片。第3圖係供予鹽水噴霧試驗後 之實例1試驗片表面之相片。第4圖係供予溫水浸漬試驗 後之比較例3試驗片表面之相片。第5圖係供予鹽水噴霧 試驗後之比較例3試驗片表面之相片。 - 26 -200413572 发明 Description of the invention (The description of the invention should state: the technical field, prior art, content, embodiments and drawings of the invention are briefly explained) (1) The technical field to which the invention belongs The present invention relates to a surface having excellent conductivity Products made of anodized magnesium or magnesium alloy. It also refers to the manufacturing method of these products. (2) Magnesium and magnesium alloys of the prior art are the lightest among practical metals, so they have high specific strength, good heat release, and excellent recyclability compared to resins. In recent years, they are widely used in electrical equipment or automobiles. Parts use. In particular, it is suitable for being used as an enclosure for electrical equipment that requires high performance, creativity, and recyclability. However, since magnesium and magnesium alloys are susceptible to corrosion, they must be surface treated or painted with corrosion resistance. By performing anodizing treatment on magnesium or a magnesium alloy, excellent corrosion resistance can be imparted. Typically, anodization is generally performed by a treatment method called Dow 17 method or HAE method, so that an anodized film having practically sufficient corrosion resistance can be formed. Also, Japanese Patent Publication No. 1 1-5 0 2 5 6 7 (W096 / 2859 1) describes a method of anodizing magnesium or a magnesium alloy by immersion in an electrolytic solution containing ammonia and a phosphate compound. It is also described in the following publication that a certain degree of corrosion resistance can be imparted by forming and treating magnesium or a magnesium alloy, and a film having conductivity can be formed. Japanese Patent Application Laid-Open No. 2000-9 6 2 5 5 describes a formation treatment film containing a fixed amount of potassium, manganese, and phosphorus and having a resistivity of 0.1 Ω · 00 or less. In addition, Japanese Unexamined Patent Publication No. 200413572 2000- 3 2 8 26 1 discloses that the surface of a magnesium alloy is etched with an acidic aqueous solution of pH 1 to 5 and comes into contact with an alkaline aqueous solution of PΗ 7 to 14 containing an organic phosphorus compound. The surface treatment method of the magnesium alloy which is then contacted to form a treatment liquid describes the purpose of obtaining a product with a small surface resistance. It can be used to effectively shield the generated electromagnetic waves in various displays such as electric displays and mobile phones. Because magnesium and magnesium alloys have good electrical conductivity, the frame of electrical equipment used in them can have good electromagnetic wave shielding properties. In addition, in most electrical devices, especially digital electronic devices, it is important to ground (ground) to remove electromagnetic interference in order to prevent erroneous operation. At this time, if the frame is made of magnesium or magnesium alloy, it can be grounded. In the aforementioned magnesium and magnesium alloys, a surface treatment or coating with corrosion resistance is necessary. By performing an anodizing treatment to impart corrosion resistance to magnesium or a magnesium alloy, the insulating oxide film covers the magnesium or magnesium alloy and loses electromagnetic wave shielding properties, and it becomes impossible to ground. Therefore, ‘for example, on the one hand, the anodic oxidation treatment is performed after covering the part for grounding’, on the other hand, the method of cutting and removing part of the anodic oxidation film after the full anodic oxidation treatment. However, these methods increase production costs due to complicated operations. In addition, the coating film formed by the formation process has recently been reported to have conductivity as described in, for example, Japanese Patent Application Laid-Open No. 2000-96255 or Japanese Patent Application Laid-Open No. 2000-3 2 82 6 1. However, compared with the anodizing treatment in which a strong oxide coating is formed by applying electricity to magnesium or a magnesium alloy, the coating film formed by only the formation treatment immersed in a treatment liquid has a corrosion resistance of 8-200413572. insufficient. In recent years, in the case of mobile equipment, etc., this problem is particularly important because corrosion resistance in various environments becomes necessary. Therefore, in the case where the coating film is formed by the formation process, the current situation is to further apply a plurality of layers of coating thereon to ensure any corrosion resistance. However, it is not necessarily easy to apply uniform coating to the frame of an electric device with a complicated shape, and the cost increases because of multiple coating steps. In addition, by the current Dow 17 method, which is an anodizing treatment, the obtained anodized film contains chromium, and the HAE method contains manganese. In addition, most of the products obtained by the forming process or the coating film contain heavy metal elements. Because it contains these heavy metal elements, it is not good to mix heavy metals with magnesium or magnesium alloys during recycling. In particular, since magnesium and magnesium alloys are characterized by excellent recyclability compared to plastics, the amount of heavy metal elements accumulated due to the number of repeated recycling cannot be ignored. In addition, since the treatment liquid contains heavy metal elements, it is not preferable from the viewpoint of disposal of the waste liquid or environmental protection. The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a product made of magnesium or a magnesium alloy having an anodized film having an electric conductivity and excellent corrosion resistance on the surface. It is also aimed at providing a method for manufacturing products made of these watches or magnesium alloys. The anode oxide film system obtained by the present invention can also solve the above-mentioned problems because it does not contain a heavy metal element, and is also excellent in terms of recyclability and environmental protection. In addition, because the electrolyte used does not contain heavy metal elements, the above-mentioned anodizing film can be formed, and at the same time, environmental protection can be provided around the plant, and the waste liquid treatment cost can be reduced. (III) Summary of the Invention 9-200413572 Description of the Invention The above S-question is to provide the conductivity of the surface of the coating measured by the surface having two terminals at a distance of 10 mm from each other. The conductivity is below 100 Ω. Anodized coatings made of Rami or magnesium alloy products. Conventionally, a film obtained by anodizing magnesium or a magnesium alloy is a film mainly composed of an oxide, which is an insulator. Because it is not an insulator, it is better to think that it does not pass corrosion current to magnesium or magnesium alloys, which can prevent its own oxidative degradation. However, as a result of intensive studies, the present inventors have found that they are both an anodized film and a conductive film. Moreover, it has anodized coatings from the past, and it is clear that the excellent corrosion-resistant uranium performance remains the same. Therefore, an article made of magnesium or a magnesium alloy having excellent corrosion resistance and good electrical conductivity is provided. In particular, it is possible to provide a housing for an electric device having excellent electromagnetic shielding properties and grounding characteristics. Wherein, the thickness of the aforementioned anodized film is 0. 01 to 10 // m is preferred from the viewpoint of the balance between the corrosion resistance and the conductivity. In the present invention, the anodized film preferably contains 35 to 65% by weight of a magnesium element and 25 to 45% of an oxygen element. Since it contains oxidized magnesium as the main component ′, although it is presumed that the anodized film having the surface of magnesium or a magnesium alloy should have corrosion resistance originally, it is not necessarily a reason for having such corrosion resistance. The anodized film preferably contains 4 to 15% by weight of the phosphorus element, and also preferably contains 5 to 20% by weight of the aluminum element. Although it is presumed that an appropriate amount of elements other than magnesium and oxygen 'does not impair corrosion resistance and has good conductivity, it is not necessarily a reason for having such conductivity. In addition, the anodic oxidation film of the present invention does not contain heavy metals such as -10 0-200413572 which are contained in the conventional anodic oxidation film, and can exhibit excellent performance. A preferred example of the present invention is a magnesium or magnesium alloy in which an anodized film is used to cover the entire surface of the magnesium or magnesium alloy, and only a part of the surface of the anodized film is subjected to resin coating to expose the remaining portion of the anodized film. Manufactured products. The exposed part of the anodized film is provided on this part to ensure electromagnetic shielding or grounding characteristics. At the same time, it can provide products with beautiful appearance and excellent abrasion resistance by resin coating. Specifically, a case of an electric machine in which resin coating is not applied to the inside of the frame and resin coating is applied to the outside of the frame is a particularly preferable example. ® Furthermore, the object of the present invention is also to provide by impregnating magnesium or magnesium alloys containing 0. In an electrolytic solution of 1 to 1 mol / L phosphate and a pH of 8 to 14, anodic oxidation removes the surface by the method of manufacturing a product made of the aforementioned magnesium or magnesium alloy, which is characterized by the surface. Wherein, the aforementioned electrolyte contains 0. 2 ~ 5mol / L ammonia or ammonium ion is preferred. As mentioned above, in the conventional anodic oxidation treatment, the treatment liquid generally contains heavy metal ions, and it also contains fluorine ions which make the treatment of waste liquid difficult. In contrast, in the method for manufacturing a product made of the magnesium or magnesium alloy of the present invention, an anodized film having excellent properties can be obtained without containing these components. In recent years, on the one hand, since the discharge regulations for waste liquid containing heavy metal elements have become stricter, it is also important from the viewpoint of environmental protection of the manufacturing method of the present invention. In the manufacturing method of the present invention, since the magnesium or magnesium alloy is impregnated in the acidic aqueous solution in advance during the anodizing treatment, it is preferable to perform the anodizing treatment by dipping in the electrolytic solution. Since it is provided to the anode-1 1-200413572 after a suitable pretreatment, the oxidation treatment is easy to obtain a product that achieves the effects of the present invention. Further, in the manufacturing method of the present invention, it is preferable that after the anodizing treatment, the resin coating film is applied only once on the surface of the anodized coating film, and the coating film is dried by heating at a temperature of 40 to 200 °. Since an anodic oxide film having excellent corrosion resistance can be obtained, simple coating is sufficient. As a result, manufacturing costs can be reduced. (4) Embodiments The present invention will be described in detail below. The present invention is a product made of magnesium or a magnesium alloy having a surface resistance of a coating 测定 which is measured between two terminals at a distance of 10 mm from each other and having a conductive anodized coating of 100 Q or less. The magnesium or magnesium alloy as a raw material may be composed of magnesium as a main component, or may be a metal containing a magnesium monomer, or may be an alloy. Usually, it is preferable to use a magnesium alloy for imparting formability, mechanical strength, ductility, and the like. For magnesium alloys, examples include magnesium-aluminum alloys, magnesium-aluminum-zinc alloys, magnesium-aluminum-manganese alloys, magnesium-zinc-chrome alloys, magnesium-rare earth element alloys, and magnesium-zinc-rare earths. Family alloys and so on. In the examples of the present invention, a magnesium-aluminum-zinc-based alloy is used, and the obtained anodized film contains an aluminum element. Therefore, as for the magnesium alloy of the raw materials, among the above-mentioned various alloys, it is presumed that those containing aluminum are preferred. There is no particular limitation on the form of the magnesium or magnesium alloy to be subjected to the 1½ pole oxidation treatment. A molded product formed by a die casting method, a thixoforming method, a press forming method, a forging method, or the like can be used. During molding, a mold release agent may remain in the inside of a wrinkle or a hollow portion formed near the surface of a molded product. In the case of anodic oxidation treatment, compared with the case of formation treatment, the remaining -12-200413572 release agent is easy to be reduced. The release agent remaining in the product is volatilized when heated, and swells in the resin coating mold. Among them, the release agent used in molding is represented by a release agent made of an organic silicon compound. Molded products made of magnesium or magnesium alloys are preferably degreased because they have contaminants on the surface from organic substances such as release agents attached during molding. As the liquid for degreasing, an aqueous solution containing a surfactant or a chelating agent is preferably used. After performing a degreasing treatment as necessary, it is preferable to immerse it in an acidic aqueous solution and then immerse it in an electrolytic solution to perform anodizing treatment. By immersing the surface of magnesium or magnesium alloy by immersing it in an acidic aqueous solution, it is possible to remove the pollution that has formed an insufficient oxide film or the remaining organic matter. Although the acidic aqueous solution is not particularly limited, it is preferable that the phosphoric acid aqueous solution has a moderate acidity. When an aqueous phosphoric acid solution is used, magnesium phosphate is also formed on the surface at the same time as the etching. In addition, a degreasing treatment may be performed simultaneously in the presence of a surfactant or a chelating agent in an acidic aqueous solution. In addition, it is preferable to treat it with such an acidic aqueous solution, and then wash it with an alkaline aqueous solution before supplying it to an anodizing treatment. In the acidic aqueous solution, insoluble components (dirty smut) adhere to the surface of magnesium or a magnesium alloy, so they can be removed. As the alkaline aqueous solution, an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution is preferably used. After the respective treatment steps such as the aforementioned de-treatment, acidic aqueous solution treatment, and alkaline aqueous solution treatment, water washing or drying may be performed if necessary. In this way, the magnesium or magnesium alloy that has been previously treated is immersed in the electrolytic solution when necessary. 13-13 200413572 The electrolytic solution of the present invention is preferably an alkaline aqueous solution containing phosphate, more specifically, containing · An aqueous solution of 1 to 1 ml / L phosphate and a pH of 8 to 14 is preferred. Since it contains an appropriate amount of phosphate, an appropriate amount of phosphorus is contained in the anodized film. In addition, it becomes alkaline to prevent unnecessary elution of magnesium or magnesium alloy. Among them, the phosphate is free phosphoric acid, phosphate, hydrogen phosphate, and dihydrogen phosphate and is contained in the electrolyte. In the case of polyphosphoric acid or a salt thereof obtained by condensing phosphoric acid, only phosphates having the number of phosphates obtained by hydrolyzing these are included. In the case of a salt, it may be a metal salt or a non-metal salt such as an ammonium salt. The content of phosphate is preferably from 0.1 · 1 to 1 mo 1 / L. With 0. 15mol / L or more is preferred, and 0. 2mol / L or more is more preferable. It is more preferably 0. 7mol / L or less, with 0. It is more preferably 5 mol / L or less. The pH of the electrolyte is preferably from 8 to 14. The pH is preferably 9 or more, and more preferably 10 or more. The pH is preferably 13 or less, and more preferably 12 or less. And ‘to the electrolyte contains a total of 0. 2 ~ 5mol / L of ammonia or ions is preferred. Therefore, the pH of the electrolytic solution is kept appropriately alkaline. The ammonia or ammonium ion content is 0. 5 mol / L or more is preferable, and 1 mol / L or more is more preferable. It is more preferably 3 mol / L or less, and more preferably 2 mol / L or less. Although the electrolytic solution of the present invention may contain other components within a range that does not impair the effects of the present invention, it is preferred that it does not substantially contain heavy metal elements. Among them, the heavy metal element may be a heavy metal element having a specific gravity exceeding 4 as a monomer ′ as a representative electrolytic solution included in the conventional anodizing treatment, and examples thereof include Luo, Xi and the like. In particular, it does not contain chrome -14-200413572, which has strict emission regulations and is harmful. It should be noted that the heavy metals contained in magnesium, such as zinc, are usually dissolved in a small amount and contained in the electrolytic solution. It is also preferable that the electrolytic solution of the present invention contains no fluorine element. Since many aqueous solutions containing fluorine element make waste liquid treatment difficult. In the foregoing electrolytic solution, an anodizing treatment is performed by impregnating magnesium or a magnesium alloy that has been previously treated as necessary, and using this as an anode and energizing. There are no special restrictions on the power source used. Although both DC and AC power sources are acceptable, DC power sources are preferred. When a DC power supply is used, a constant current power supply or a constant voltage power supply can be used, but a constant current power supply is preferred. The cathode material is not particularly limited, and for example, a stainless steel material can be suitably used. The surface area of the cathode is preferably larger than that of the magnesium or magnesium alloy subjected to the anodizing treatment, more preferably 2 times or more, and usually 10 times or less. When a constant current power source is used as the power source, the current density on the anode surface is usually 0. 1 ~ IOA / dm2. With 0. Above 2A / dm2 is preferred, with 0. 5A / dm2 or more is preferable. In addition, it is preferably 5 A / dm2 or less, and more preferably 2 A / dm2 or less. The power-on time is usually 10 to 1,000 seconds. It is preferably at least 20 seconds, and more preferably at least 50 seconds. Further, it is preferably 500 seconds or less, and more preferably 200 seconds or less. When the power is supplied by a constant current power supply, the applied voltage at the start of the application is low, and at the same time, the applied voltage is increased with time. The applied voltage at the end of energization is usually 50 ~ 400 volts. It is preferably 100 volts or more, and more preferably 150 volts or more. Further, it is preferably 300 volts or less, and more preferably 250 volts or less. Compared to the Dow 17 method or the HAE method, which is a conventional anodizing treatment method, the applied voltage is mostly set to less than 100 volts. In the anodizing treatment of 200413572 of the present invention, it is better to set at a higher voltage. Therefore, even if a part containing impurities such as an organosilicon release agent undergoes an oxidation reaction, it becomes easy to form a good film on the entire surface of magnesium or a magnesium alloy. Also, since the oxygen is violently generated from the surface of magnesium or a magnesium alloy in accordance with the oxidation reaction, it is easy to remove the impurities in the anodizing treatment. The electrolyte temperature is usually 5 ~ 70 ° C during energization. 1 ° C or higher is preferred. 50 ° C or lower is preferred, and 3 ° C or lower is preferred. After the current is applied, the electrolytic solution attached to the surface of the anodized film is removed by washing treatment. When washing, it is better not only to use water, but to wash with an acidic aqueous solution. Since the electrolyte is alkaline, by washing with an acidic aqueous solution, the resin film can improve the density of the coating. In terms of acidic aqueous solution, nitric acid aqueous solution, hydrochloric acid aqueous solution, sulfuric acid aqueous solution, etc. can be used. After washing, drying is performed to obtain a product made of magnesium or a magnesium alloy having an anodized film on the surface. The magnesium of the present invention is made of magnesium Products made of magnesium or magnesium alloy are those with a conductive anodized film with a surface resistance 値 of 100 Ω or less measured between two terminals at a distance of 10 mm from each other. The resistance 値 is the anodized film The resistance 値 (Ω) measured by the terminals is pressed at any two points on the surface at a distance of 10 mm from each other. The product of the present invention may also have the above-mentioned resistance 至少 at least one place on the surface. The electric resistance 値 is small. In essence, it is used to measure the electric resistance 相关 related to the thickness direction of the anodized film between the terminal for measurement and magnesium or magnesium alloy. Therefore, the electric resistance 对应 corresponds to the electromagnetic wave shielding property or the grounding characteristic The number of properties required for the product. It is preferably below 10 Ω, and preferably below 1 Ω. 5-1 6-200413572 Ω is the best. Also, the resistance 値 of the surface of a molded article made of magnesium or a magnesium alloy without surface treatment is usually 0 in the case of AZ91D. 02 ~ 0. About 1Ω. As shown in FIG. 1, the anodized film obtained by the present invention may be considered to have a large number of holes due to an electric arc on the surface. This aspect is different from the formation of a treatment film. The thickness of the anodized film is 0. 01 ~ lO / zrn is preferred. With o. Above l / zm is better, with 0. 5 // m or more is more preferable. In addition, it is more preferably 5 // m or more, and more preferably 3 // m or more. If the film thickness is too thin, the corrosion resistance may be deteriorated. If the film thickness is too thick, the conductivity may be reduced, and the electromagnetic wave shielding properties or grounding characteristics may be reduced. Although the chemical composition of the anodized film obtained by the present invention is not particularly limited, it is preferably one containing 35 to 65% by weight of a magnesium element and 25 to 45% by weight of an oxygen element. It is the product of the result of anodized magnesium or magnesium alloy, and it is preferred that it contains oxidized magnesium as the main component. The magnesium element content is preferably 40% by weight or more, and more preferably 45% by weight or more. Furthermore, it is preferably 60% by weight or less, and more preferably 55% by weight or less. The oxygen content is preferably 30% by weight or more. The content is preferably 40% by weight or less. The anodized film preferably contains 4 to 15% by weight of a phosphorus element. The content of the phosphorus element is preferably 5% by weight or more, and more preferably 6% by weight or more. The content is preferably 12% by weight or less, and more preferably 10% by weight or less. It is also preferable that a has 5 to 20% by weight of an aluminum element. The content of Mingyuansu is preferably 7% by weight or more, and more preferably 9% by weight or more. The content is preferably 17% by weight or less, and more preferably 1% by weight or less. Because it contains the above elements other than magnesium and oxygen, it can be inferred that-1 7- 200413572 is non-destructive and corrosion-resistant, and has good electrical conductivity. The anodized film of the present invention may include elements other than the above as long as the effect of the present invention is not impaired. However, it is preferable that the magnesium alloy as a raw material is substantially free of heavy metals, especially chromium. It is also preferable that the element does not substantially contain fluorine. The use of the product made of the magnesium or magnesium alloy of the present invention having an anodized coating on the surface is not particularly limited, and it can be used for various electric machines or automobile parts. In use, although an overcoat coating can be applied to the surface of the anodized film when necessary, in order to take advantage of the characteristics of the anodized film of the present invention with good conductivity, it cannot be covered with a coating made of an insulating film. The whole product. The paint used is not particularly limited, and can be used for various paints used in the coating of metal surfaces. Solvent-based coatings, water-based coatings, powder coatings, and the like can be used to form a resin coating film. Heat-curable coatings that require high-temperature firing after coating, and coatings that only volatilize solvents or water at lower temperatures are acceptable. The latter is easier to use. In order to make the appearance beautiful, it is better to use a transparent resin paint, and it is also possible to use a suitable color. There is no particular limitation on the coating method, and spray coating, dip coating, electric ore coating, powder coating, and other recognized methods can be used. In the product made of the magnesium or magnesium alloy of the present invention, which has a part having no coating film, it is preferable to use spray coating or powder coating by a solvent spray method. After the anodizing treatment, it is preferable to form a coating film by coating the resin coating film only once on the surface of the anodizing film. Most of the frames of electrical equipment have complicated shapes, and it is not necessarily easy to form a uniform coating film. Although-18- 200413572 Most of the coatings can be used to improve the corrosion resistance of a section of uranium. However, the higher the number of coatings, the higher the cost. In this aspect, in the products made of the z-table or table alloy of the present invention with good corrosion resistance, most of them are only one. Sub-coating gives very good corrosion resistance. When using solvent-based paint or water-based paint, it is better to dry the coating film by heating at 40 ~ 120 ° C. Above 50 ° C, preferably below 10 ° C. In the products made of the magnesium or magnesium alloy of the present invention with good corrosion resistance, most of them are dry-hardened resin coatings only with a lower temperature heating step. That is enough, as a result, the manufacturing cost can be reduced. The heating and drying method is not particularly limited, and a general-purpose oven can be used. A preferred example of the present invention is to cover the entire surface of magnesium or a magnesium alloy with an anodized film, and A product made of magnesium or magnesium alloy with anodized coating only exposed on a part of the surface of the anodized coating, and the remaining part of the anodized coating is exposed. Since the surface of the magnesium or magnesium alloy is covered with the anodized coating, The corrosion resistance of the entire product can be ensured. However, the so-called all of them are essentially all, and it is not a problem that the anodized film portion is only formed at the point of contact with the power source during the anodizing treatment. Also, since only the anodized film portion is formed. Part of the surface of the anodized film is coated with resin to expose the remaining part of the anodized film, which can ensure electromagnetic wave shielding or grounding characteristics. It provides products with beautiful appearance and excellent abrasion resistance. A particularly good example is the frame of an electrical machine that is not coated with resin on the inside of the frame, and is coated with resin on the outside of the frame. Because the resin is applied on the outside of the frame Painting can not only make the appearance beautiful, but also prevent damage during use. In addition, the conductive anodized film -19-200413572 is exposed on the inside of the frame, which can easily ensure the grounding from the electrical wiring. Effectively shield electromagnetic waves from electronic circuits inside the body. The products made from the magnesium or magnesium alloy of the present invention thus obtained are used for various purposes. They can be used in mobile phones, personal computers, cameras, cameras, optical disc drives, displays (CRT, plasma, liquid crystal), housings of electrical equipment for projection, or automotive parts, etc. Best Examples for Implementing the Invention The following examples will be used to describe the present invention in more detail, but are not subject to this. Those who are restricted. The test method in this example is performed in accordance with the method. (1) Measurement of the film thickness of the anodized film The test piece is cut into 5mm x 10mm Dimensions are coated with epoxy, and then the cut surface is polished to obtain a mirror surface. From the cross-sectional direction of the sample, an X-ray microanalyzer "jXA_89OO" manufactured by Yoshimoto Electronics Co., Ltd. was used to take an electron microscope photograph and measure the film. (2) The chemical composition of the anodized film was analyzed by using an X-ray microanalyzer "〗 XA _" made by Japan Electronics Co., Ltd. from two directions of the film surface and cross section. Three points were measured in each direction, and the chemical was obtained from the average 値. The measurement was performed with an acceleration voltage of 15 kV and a 2 × 10 · 8A sample was irradiated with a current source. The data analysis was performed by ZOA correction. Measurement of the resistance on the surface of the anodized film Using Mitsubishi Chemical Corporation's low-resistivity meter "Roeste MCP-T400", two-probe probe rMCP-Tp〇1 " Wait for the following resins to analyze the composition of the strip-AP. At the center of the 200413572 test piece, the measurement terminal was attached to the surface of the film to measure the resistance 前述 (Ω) ° The probes were arranged at a distance of 10 mm, and the terminals were plated with gold on a beryllium alloy. . The shape of the cylindrical 2 'diameter cylindrical terminal' is that the load on the surface of the film is 240g per terminal. (4) Warm water immersion test The test piece was immersed in warm water maintained at 70 ° C for 24 hours. After 24 hours, remove the test piece, wipe off the moisture, and add checkerboard-like nicks at intervals of approximately 1 mm through the resin coating and the anodized coating. Follow the] IS K5400 for tape peeling test with the naked eye Observe the peeling condition of the coating film or any other defects. (5) Salt spray test on the surface of the test piece. After adding a cross-shaped notch (cross notch) through the resin coating film and the anodized film, follow the instructions; i IS Z-23 1 to spray 5% salt water Test 1 for 20 hours. After 120 hours, the test piece was taken out, and the occurrence of swelling from the cross-notch portion or other defects were observed with the naked eye. [Example 1] ASTM No. made of 90% by weight magnesium, 9% by weight aluminum and 1% by weight zinc. AZ9 1D magnesium alloy is used as a raw material, and an alloy plate with a size of 170 mm X 50 m X 2 mm m casted by the hot cavity method is used as a test piece. Impregnate the above test piece with 2. After 2% by weight of phosphoric acid and a trace amount of a surfactant in an acidic aqueous solution, it was washed with ion exchanged water. Next, the surface of the test piece was pre-treated by being immersed in an alkaline aqueous solution containing 18% by weight of sodium hydroxide and then washed with ion-exchanged water. -21- 200413572 Mix phosphoric acid aqueous solution and ammonia water, and make it contain 0. 25m () 1 / L phosphate, containing a total amount of 1. 5mO1 / L of ammonia or ammonium ion electrolyte, and maintained at 20 ° C. The pH of the electrolyte is 1 丨. A magnesium alloy test piece which had been subjected to a pretreatment was immersed therein as an anode, and anodized. At this time, the cathode side was a S U S 3 16 L plate having 4 times the surface area of the anode. A constant current power supply was used for 120 seconds at a current density of 1A / dm2 on the anode surface. The applied voltage is low at the beginning of the energization and rises to about 200 volts at the end of the energization. After the energization was completed, it was washed in the order of ion-exchanged water, nitric acid solution, and ion-exchanged water, and then dried. 0 A photograph of the surface of the anodized film obtained by observation with a scanning electron microscope is shown in FIG. 1. On the surface of the anodized film, the existence of a plurality of holes believed to be due to an arc during energization was found. The film thickness of the anodized film is about 1 · 5 // πm. The film thickness is the average distance from the thick part of the surface to the magnesium alloy surface of the substrate on a film with local film thickness unevenness due to a large number of holes. The resulting anodized film contains 4 8. 0% by weight magnesium element, 33. 5 wt% oxygen element, 7. 0% by weight phosphorus and 11. 2% by weight aluminum element. The resistance 値 on the surface of the anodized film is 0. 2 5 Ω. On the surface of the obtained anodized film, an air spray coating of acrylic silicone coating "Yaskite 3 0 (Π") manufactured by Kashu Co., Ltd. is used, and at this time, it is a non-primer coating and is Apply the acrylic silicone coating on the surface of the anodized film only once. After coating, heat it at 6 ° C for 20 minutes to evaporate the solvent and harden the coating film. In this way, apply it to the surface of the anodized film A coating film having a film thickness of about 20 // m was formed. When the obtained test piece was subjected to a warm water immersion test and a salt water spray test-22- 200413572 'In any case, no change in appearance was observed on the surface. Supply The photos of the surface of the test piece after the warm water test and the surface of the test piece after the water spray test are shown in Figure 2 and Figure 3. [Comparative Example 1]. Mix a phosphoric acid aqueous solution with ammonia to prepare a solution containing 0. An electrolytic solution containing 0.8 mol / L phosphate and containing 0.8 m 1 / L of ammonia or ammonium ion in its total amount was maintained at 20 ° C. The pH of the electrolyte was 11. A magnesium alloy test piece which had been subjected to the same pretreatment as in Example 1 was immersed therein as an anode to perform anodizing treatment. For the cathode at this time, the same one as in Example 1 was used. A constant current power supply was used and the current density on the anode surface was 1A / dm2 for 120 seconds. The applied voltage is low at the beginning of the energization and rises to approximately 200 volts at the end of the energization. After the energization was completed, it was washed in the order of ion-exchanged water, nitric acid aqueous solution, and ion-exchanged water, and then dried. The thickness of the obtained anodized film was about 1.5 μm and contained 5 4. 8% by weight magnesium, 37. 7% by weight oxygen element, 3. 2% by weight phosphorus and 4. 3% by weight aluminum element. The resistance of the surface of the anodized film is more than 1 0 7 Ω beyond the limit of the resistivity meter used for the measurement. A resin coating film was formed on the surface of the obtained anodized film in the same manner as in Example 1. When the obtained test piece was subjected to a warm water immersion test and a salt water spray test, in any case, no appearance was observed on the surface. [Comparative Example 2] A test example of a well-known method for forming an anodized film called D 0 w 17 was performed. An electrolytic solution containing 300 g / L of acidic ammonia fluoride and 100 g / L of sodium dichromate [and 90 g / L of phosphoric acid was prepared, and kept at 7 5 ° C. A magnesium alloy test piece which had been subjected to the same pretreatment as in 200413572 Example 1 was immersed therein as an anode, and anodized. At this time, the cathode was the same as in Example 1. A constant current power supply was used for a period of 300 seconds with a current density of 4A / dm2 on the anode surface. The applied voltage is low at the beginning of the energization and rises to about 70 volts at the end of the energization. After the energization was completed, it was washed with ion-exchanged water and then dried. The film thickness of the obtained anodized film was about 1. 5 // m, contains 26. 0% by weight magnesium, 25. 7% by weight oxygen element, 11. 2% by weight element, 1. 〇 Aluminum element by weight, 23. 4% by weight fluorine element, 9. 2% by weight of chromium and 3. 6% by weight sodium. The resistance of the surface of the anodized film is more than 1 0 7 Ω beyond the limit of the resistivity meter used for the measurement. [Comparative Example 3] An example in which a commercially available forming treatment liquid was used instead of the anodizing treatment to perform the forming treatment. Dilute with ion-exchanged water to contain. 7 5 g / L ratio of Million Won Chemical Co., Ltd. formed the treatment liquid "MC-1 000" to prepare the treatment liquid and keep it at 40 ° C. Although the details of the chemical composition of the formation treatment liquid are not intricate, it is presumed to be a formation treatment liquid containing phosphate ions, manganese (or manganese oxide) ions, and potassium ions. In this treatment liquid, a magnesium alloy test piece which had been subjected to the same treatment as in Example 1 was immersed for 30 seconds. After the immersion, it was washed with ion-exchanged water and then dried. The film thickness of the resulting formation treatment film was 0. 1 // m, which is a thin film thickness that is difficult to measure quantitatively. The compound coating film has an average content per unit area of 85 mg / m2 potassium, 95 mg / m2 manganese, and 220 mg / m2 phosphorus. In addition, the resistance 値 of the surface of the forming treatment film is 0. 5 Ω. A tree coating film was formed on the surface of the obtained compound coating film in the same manner as in Example 1. The appearance of the obtained test piece after being subjected to the warm water immersion test and the appearance after being subjected to the salt water spray test are shown in Figs. 4 and 5 respectively. In any case, peeling of the resin coating film was noticeably observed around the cut of the coating film. [Comparative Example 4] An example in which a formation treatment was performed using a commercially available formation treatment liquid different from that in Comparative Example 3 instead of the anodizing treatment '. Diluted with ion-exchanged water to form a forming treatment liquid "MB-Cl OM" manufactured by Nippon Pakalaijin Co., Ltd. at a ratio of 75 g / L. The treatment liquid was prepared and maintained at 5 (rc. The chemical composition is not exhaustive, but it is presumed to contain 14% by weight of anhydrous chromic acid and 0. 7% by weight hydrofluoric acid as the main component of the formation treatment liquid. In this treatment liquid, a magnesium alloy test piece having been subjected to the same treatment as in Example 1 was immersed for 60 seconds. After the immersion, it was washed with ion-exchanged water and then dried. The film thickness of the obtained formation treatment film is 0 · 1 // m or less, which is a thin film thickness that is difficult to quantitatively measure. This compound coating is based on an average content per unit area of 190 mg / m2 of chromium. In addition, the resistance 値 of the surface of the forming treatment film was ® on the surface of the obtained compound coating film, and a resin coating film was formed in the same manner as in Example 1. After the obtained test piece was subjected to a warm water immersion test and a saline spray test, in any case, no peeling or swelling of the resin coating film added around the cut of the coating film was found. However, after the warm water immersion test, it was observed that a plurality of dot-like swelling points (bubbles) were generated on the coating film near the edge portion of the test piece. As explained above, the product made by the anodizing process in Example 1-25-200413572 The magnesium alloy product of the invention is one that has both conductivity and excellent corrosion resistance. The magnesium alloy obtained by the conventional anodizing treatment as shown in Comparative Example 1 or 2 was excellent in corrosion resistance, and no electrical conductivity was found. In addition, a product made of the magnesium alloy obtained by the formation treatment as shown in Comparative Example 3 was found to be conductive, but insufficient in corrosion resistance. [Industrial application feasibility] Products made with the magnesium or magnesium alloy of the present invention are those with an anodized coating on the surface that has both electrical conductivity and excellent corrosion resistance. Therefore, it is particularly useful as a housing for an electrical device, as it is a product made of magnesium or a magnesium alloy having excellent electromagnetic wave shielding properties or grounding properties. Moreover, the product does not contain heavy metals and is also suitable for recycling. Furthermore, since the anodizing treatment is performed using an electrolytic solution that does not use heavy metal ions or fluorine ions, it is an excellent manufacturing method from the viewpoint of providing environmental protection. (V) Brief description of the diagram: Fig. 1 is a photograph of the surface of the anodic oxide film obtained in Example 1 using a scanning electron microscope. Figure 2 is a photograph of the surface of the test piece of Example 1 after being subjected to a warm water immersion test. Figure 3 is a photograph of the surface of the test piece of Example 1 after the salt spray test. Fig. 4 is a photograph of the surface of the test piece of Comparative Example 3 after the warm water immersion test was applied. Figure 5 is a photograph of the surface of the test piece of Comparative Example 3 after the salt spray test. -26-