200938663 九、發明說明 【發明所屬之技術領域】 本發明係關於一種鋁材料的保護膜之製造方法，特別 係關於鋁的陽極氧化薄膜上形成緻密層（保護膜）之方法。 【先前技術】 ' 鋁、鋁合金，與不銹鋼等比較時，除較輕、熱傳導性 0 佳外，因無鉻等重金屬污染的影響，廣泛地被使用作爲真 空處理裝置的真空槽之內壁構件。 傳統上，鋁、鋁合金的耐腐蝕處理，係廣泛地使用稱 爲氧皮鋁（alumite )處理之陽極氧化處理。 但是，即使是真空處理裝置，特別是使用反應性氣體 或其電漿、自由基之裝置（CVD裝置、蝕刻裝置等）， 被要求高耐腐蝕性，傳統的陽極氧化處理並不足夠。 陽極氧化處理係以硫酸、草酸等水溶液作爲電解液， φ 處理對象物作爲陽極，浸漬於電解液中。浸漬於相同的電 解液之陰極，在與上述陽極之間引起電解，於處理對象物 的表面，使鋁的氧化物或氫氧化物所成的陽極氧化薄膜成 長。 如此所形成的陽極氧化薄膜，其厚度爲數μιη至數十 μιη，一般係於薄膜中由從表面往深度方向形成數ι〇ηιη的 無數的孔之多孔性構造所成。孔底（孔的底壁）之氧化薄 膜的厚度爲數ΙΟηιη’該薄的氧化薄膜決定陽極氧化薄膜 整體的耐腐蝕性。 -5- 200938663 爲了提高陽極氧化薄膜的耐腐蝕性，必須進行埋孔的 封孔處理。作爲封孔處理，已知將形成有陽極氧化薄膜之 處理對象物浸漬於沸騰的水之方法、在蒸氣釜中暴露於 100 °c以上的高溫蒸氣之方法。 根據該方法，已知於陽極氧化薄膜的多孔性構造上形 成緻密層。一般該層被稱爲水鋁土（ boehmite )層，緻密 的水鋁土層被認爲可提高耐腐触性。但是，即使以該方法 進行封孔處理，不會再現性良好地形成顯示高耐腐蝕性之 水鋁土層，耐腐蝕性不足。 [專利文獻1]日本專利第3 803 3 5 3號公報 【發明內容】 [發明所欲解決之課題] 本發明人等得知使陽極氧化薄膜接觸1 〇〇°c以上的沸 騰水進行封孔處理時，即使全部在相同的條件下進行陽極 氧化處理與封孔處理，無法完全形成緻密層，可成爲1 μιη 以上的厚膜，緻密層的膜厚產生不均勻。 即使以1 〇〇°C以上的水蒸氣取代沸騰水，進行封孔處 理，仍發生相同的不均勻。 爲了提高封孔性，將封孔時間從一般約3 0分鐘，延 長爲2小時，無法消除緻密層的膜厚不均勻的問題。再 者，考慮封孔處理前污染的影響時’即使封孔處理前充分 地洗淨處理對象物後進行封孔處理’也無法改善緻密層的 膜厚之不均勻。 -6 - 200938663 而且，考慮陽極氧化薄膜的膜構造之影響時’於陽極 氧化薄膜成膜中使外加電壓改變，改變薄膜構造，進行封 孔處理，仍無法改善緻密層的膜厚之不均勻。 [解決課題之手段] 爲了解決上述課題，本發明係鋁的陽極氧化薄膜形成 於表面之處理對象物之使前述陽極氧化薄膜緻密化而製造 保護膜的保護膜之製造方法，前述陽極氧化薄膜之緻密化 係使7〇°C以上90°C以下之第一溫度的溫水接觸前述陽極 氧化薄膜後’使比前述第一溫度高之第二溫度之熱水或前 述第二溫度之水蒸氣接觸前述陽極氧化薄膜的保護膜之製 造方法。 本發明係保護膜之製造方法，前述第二溫度爲l〇(rc 以上的保護膜之製造方法。 本發明係保護膜之製造方法，前述溫水爲純水的保護 膜之製造方法。 本發明係保護膜之製造方法，前述溫水爲鹼性的保護 膜之製造方法。 [發明的效果] 陽極氧化薄膜的緻密層（保護膜）爲厚膜，且由於其 膜厚變均勻，耐腐蝕性提高。 【實施方式】 200938663 圖1的符號2表示陽極氧化裝置。爲了形成薄膜，於 陽極氧化裝置2的電解槽21的內部，放入電解液26。 於連接電源25的正端子之安裝器具23，使處理對象 物11密合而安裝。該處理對象物n在安裝於安裝器具 23的狀態下浸漬於電解液26，同時連接電源25的負端子 之陰極板22浸漬於電解液26。 一邊使電解液26維持既定的氧化溫度，一邊使電源 25動作’於處理對象物1 1與陰極板22之間，外加既定 的氧化電壓’使既定的電流密度之直流電壓以既定的氧化 時間流過處理對象物1 1。 於處理對象物1 1的至少表面部份露出鋁材料，鋁材 料係由例如鋁與鋁合金的任一者或兩者所成。電流密度係 流過處理對象物11之電流除以處理對象物11的鋁材料露 出部份之面積的値。 電流流過處理對象物11時，從表面部份鋁變成離子 溶出。該鋁離子與因水的電解產生的氧、氫氧基結合，於 處理對象物1 1的表面，生成氧化鋁（Al2〇3 )與氫氧化鋁 (aih3o3 )的任一者或兩者，而形成鋁的陽極氧化薄膜。 電解液26含有草酸、硫酸等酸，於如此的電解液26 中，陽極氧化薄膜變成多孔性構造。 形成有陽極氧化薄膜1 2之處理對象物1 1，從電解液 26中撈起，從安裝器具23卸下，以純水洗淨。 圖2的符號4表示第一封孔處理裝置。於第一封孔處 理裝置4的第一加熱處理槽41，配置第一溫度（70°C以上 -8 - 200938663 90C以下）的溫水46。一邊維持溫水46的溫度爲第一溫 度，一邊使形成有陽極氧化薄膜12之處理對象物H以既 定的第一處理時間（5分鐘以上60分鐘以下）浸漬於該 溫水4 6。 陽極氧化薄膜12與第一溫度的溫水46接觸時，表面 形成不連續的面，陽極氧化薄膜12內的空隙變成露出的 狀態（第一熱處理步驟）。 第一熱處理步驟後’使陽極氧化薄膜12以既定的第 一處理時間（5分鐘以上60分鐘以下）接觸比第一溫度 高的第二溫度之熱水或第二溫度之水蒸氣。 如上述，藉由第一熱處理步驟，陽極氧化薄膜12內 的空隙露出後，熱水或水蒸氣不僅接觸陽極氧化薄膜12 的表面，亦進入空隙。 陽極氧化薄膜12的構成材料（氧化鋁、氫氧化鋁） 與熱水或水蒸氣接觸時，吸收水，變成水鋁土 (Α12〇3·Η2〇 )、三經銘石（bayerite ) ( Α12〇3·3Η2〇 )等 水合物’體積膨脹’使陽極氧化薄膜12的空隙封孔，於 陽極氧化薄膜12的表面部份，形成緻密的保護膜（第二 熱處理步驟）。 而且，於第二熱處理步驟使用熱水的情況，例如處理 對象物11繼續浸漬於與第一熱處理步驟同槽之溫水46, 使該溫水46升溫，溫水46變成第二溫度的熱水後，處理 對象物11在浸漬於該熱水的狀態下，維持第二處理時 間。 -9- 200938663 或者，將處理對象物11從溫水46撈出，浸漬於與第 一熱處理步驟不同槽之第二溫度的熱水，熱水繼續維持第 二溫度’處理對象物1 1浸漬於該熱水的狀態下，維持第 二處理時間。 於第二熱處理步驟使用水蒸氣的情況，將處理對象物 1 1從溫水46撈出後，於圖3所示的蒸氣封孔裝置（第二 封孔處理裝置5)的釜（處理槽51)內，配置處理對象物 1 1 〇 藉由水蒸氣產生裝置55，使第二溫度的水蒸氣充滿 該處理槽51內，繼續維持該水蒸氣的溫度爲第二溫度， 處理對象物Η在暴露於該水蒸氣的狀態下，維持第二處 理時間。在第二熱處理步驟使用水蒸氣的情況，處理槽 51的內部壓力可爲常壓（1大氣壓），也可超過常壓。 [實施例] 以寬度30mm、長度 45mm、厚度 2mm的銘合金板 (A5052P、參照JIS H4000 )作爲基板，作爲形成陽極氧 化薄膜之前處理，係將該基板浸漬於4(TC的10 %氫氧化 鈉水溶液1分鐘，脫脂後，進行水洗，於室溫下浸漬於 3 5 %硫酸水溶液，進行污斑（黑色附著物）的除去。 以前處理後的基板作爲處理對象物，使用對純水1公 升溶解30g的草酸之電解液，氧化溫度爲15°C以上25°c 以下，氧化電壓爲6 0 V以上1 0 0 V以下，電流密度、氧化 時間及陽極氧化薄膜1 2的膜厚係在下述表1所示的條件 -10- 200938663 下，形成陽極氧化薄膜12。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a protective film of an aluminum material, and more particularly to a method for forming a dense layer (protective film) on an anodized film of aluminum. [Prior Art] 'Aluminum, aluminum alloy, compared with stainless steel, etc., except for lighter weight and better thermal conductivity, it is widely used as a vacuum chamber inner wall member due to the influence of heavy metal contamination such as chromium. . Conventionally, the corrosion-resistant treatment of aluminum and aluminum alloys has been extensively used for anodizing treatment called alumite treatment. However, even in a vacuum processing apparatus, particularly a device using a reactive gas or a plasma or a radical thereof (CVD device, etching device, etc.), high corrosion resistance is required, and conventional anodizing treatment is not sufficient. In the anodizing treatment, an aqueous solution such as sulfuric acid or oxalic acid is used as an electrolytic solution, and an object to be treated as an anode is immersed in an electrolytic solution. The cathode is immersed in the same electrolytic solution to cause electrolysis between the anode and the anode, and an anodized film made of an oxide or hydroxide of aluminum is grown on the surface of the object to be treated. The anodized film thus formed has a thickness of several μm to several tens of μm, and is generally formed by a porous structure in which a plurality of pores are formed from the surface to the depth direction by a number of pores. The thickness of the oxidized film at the bottom of the hole (the bottom wall of the hole) is several ΙΟηηη', and the thin oxide film determines the overall corrosion resistance of the anodized film. -5- 200938663 In order to improve the corrosion resistance of the anodized film, it is necessary to perform the plugging treatment of the buried via. As a method of sealing the pores, a method of immersing an object to be treated having an anodized film in boiling water and a method of exposing it to a high-temperature vapor of 100 ° C or more in a vapor chamber is known. According to this method, it is known to form a dense layer on the porous structure of the anodized film. Generally, this layer is called a boehmite layer, and a dense bauxite layer is considered to improve the corrosion resistance. However, even if the sealing treatment is carried out by this method, a bauxite layer exhibiting high corrosion resistance is not formed with good reproducibility, and corrosion resistance is insufficient. [Patent Document 1] Japanese Patent No. 3 803 3 5 3 [Explanation] The present inventors have found that the anodized film is sealed with boiling water of 1 〇〇 ° or more. At the time of the treatment, even if the anodizing treatment and the sealing treatment are all performed under the same conditions, the dense layer cannot be completely formed, and the thick film of 1 μm or more can be formed, and the film thickness of the dense layer is uneven. Even if the boiling water is replaced by steam of 1 〇〇 ° C or more and the sealing treatment is performed, the same unevenness occurs. In order to improve the sealing property, the sealing time is generally from about 30 minutes to 2 hours, and the problem of uneven film thickness of the dense layer cannot be eliminated. In addition, when the influence of the contamination before the sealing treatment is considered, "the sealing treatment is performed after sufficiently cleaning the object to be processed before the sealing treatment", the unevenness of the film thickness of the dense layer cannot be improved. -6 - 200938663 Further, when the influence of the film structure of the anodized film is considered, the applied voltage is changed in the film formation of the anodic oxide film, the film structure is changed, and the sealing treatment is performed, and the film thickness unevenness of the dense layer cannot be improved. [Means for Solving the Problems] The present invention provides a method for producing a protective film in which an anodized film of aluminum is formed on a surface of an object to be treated, and the anodized film is densified to produce a protective film, and the anodized film is used. The densification system contacts the hot water of the first temperature of 7 ° C or more and 90 ° C or less to contact the anodized film, and then contacts the hot water of the second temperature higher than the first temperature or the water vapor of the second temperature. A method of producing a protective film of the foregoing anodized film. The present invention relates to a method for producing a protective film, wherein the second temperature is a method for producing a protective film of rc or more. The present invention relates to a method for producing a protective film, and a method for producing a protective film of warm water which is pure water. A method for producing a protective film, wherein the warm water is an alkaline protective film. [Effect of the Invention] The dense layer (protective film) of the anodized film is a thick film, and the film thickness becomes uniform and corrosion resistance [Embodiment] 200938663 An anodizing device is denoted by reference numeral 2 in Fig. 1. In order to form a thin film, an electrolytic solution 26 is placed inside the electrolytic cell 21 of the anodizing device 2. The mounting device 23 for connecting the positive terminal of the power source 25 is provided. The object to be processed 11 is attached to the electrolyte solution 26 while being attached to the mounting tool 23, and the cathode plate 22 connected to the negative terminal of the power source 25 is immersed in the electrolytic solution 26. The electrolyte solution 26 maintains a predetermined oxidation temperature, and operates the power source 25 between the object to be processed 1 1 and the cathode plate 22, and applies a predetermined oxidation voltage to make the current density constant. The flow voltage flows through the object 1 to be treated for a predetermined oxidation time. At least a surface portion of the object 1 1 is exposed to an aluminum material, and the aluminum material is made of, for example, either or both of aluminum and aluminum alloy. The density is the enthalpy of the current flowing through the object to be processed 11 divided by the area of the exposed portion of the aluminum material of the object to be processed 11. When the current flows through the object to be processed 11, the aluminum is ion-dissolved from the surface portion. The oxygen and the hydroxyl group generated by the electrolysis of water are combined to form the surface of the object 1 1 to form either or both of alumina (Al 2 〇 3 ) and aluminum hydroxide (aih 3 o 3 ) to form anodization of aluminum. The electrolyte solution 26 contains an acid such as oxalic acid or sulfuric acid, and the anodized film has a porous structure in the electrolytic solution 26. The object to be treated 1 1 in which the anodized film 12 is formed is picked up from the electrolytic solution 26, It is detached from the attachment tool 23 and washed with pure water. The first sealing treatment device is denoted by reference numeral 4 in Fig. 2. The first temperature (70 ° C) is disposed in the first heat treatment tank 41 of the first plugging device 4 Above -8 - 200938663 90C below) Water 46. While maintaining the temperature of the warm water 46 at the first temperature, the object to be treated H on which the anodized film 12 is formed is immersed in the warm water for a predetermined first treatment time (5 minutes or more and 60 minutes or less). When the anodized film 12 is in contact with the warm water 46 at the first temperature, the surface forms a discontinuous surface, and the voids in the anodized film 12 become exposed (first heat treatment step). After the first heat treatment step, the anode is oxidized. The film 12 contacts the hot water of the second temperature higher than the first temperature or the water vapor of the second temperature for a predetermined first treatment time (5 minutes or more and 60 minutes or less). As described above, the first heat treatment step is anodized. After the voids in the film 12 are exposed, hot water or water vapor not only contacts the surface of the anodized film 12 but also enters the gap. When the anodic oxide film 12 is made of aluminum hydroxide or aluminum hydroxide, it absorbs water and turns into aluminous earth (Α12〇3·Η2〇) and bayerite (bay12〇). 3·3Η2〇) The hydrate 'volume expansion' causes the void of the anodized film 12 to be sealed, and a dense protective film is formed on the surface portion of the anodized film 12 (second heat treatment step). Further, in the case where the hot water is used in the second heat treatment step, for example, the object 11 to be processed is continuously immersed in the warm water 46 in the same tank as the first heat treatment step, the warm water 46 is heated, and the warm water 46 becomes the second temperature hot water. Thereafter, the object to be processed 11 is maintained in the second processing time while being immersed in the hot water. -9- 200938663 Alternatively, the object to be treated 11 is taken out from the warm water 46, immersed in hot water at a second temperature different from the first heat treatment step, and the hot water continues to maintain the second temperature. In the state of the hot water, the second processing time is maintained. In the case where steam is used in the second heat treatment step, the object to be treated 1 1 is taken out from the warm water 46, and then in the vessel of the vapor sealing device (second plugging device 5) shown in FIG. 3 (processing tank 51) In the inside, the object to be processed 1 1 is filled with water vapor of the second temperature in the treatment tank 51 by the steam generating device 55, and the temperature of the water vapor is maintained at the second temperature, and the object to be treated is exposed. The second treatment time is maintained in the state of the water vapor. In the case where water vapor is used in the second heat treatment step, the internal pressure of the treatment tank 51 may be normal pressure (1 atm) or may exceed normal pressure. [Examples] A metal alloy plate (A5052P, JIS H4000) having a width of 30 mm, a length of 45 mm, and a thickness of 2 mm was used as a substrate, and before the anodized film was formed, the substrate was immersed in 4 (TC of 10% sodium hydroxide). The aqueous solution was degreased for 1 minute, and then washed with water, and immersed in a 35% sulfuric acid aqueous solution at room temperature to remove stains (black deposits). The substrate after the previous treatment was used as a treatment object, and dissolved in 1 liter of pure water. 30 g of oxalic acid electrolyte, the oxidation temperature is 15 ° C or more and 25 ° C or less, the oxidation voltage is 60 V or more and 100 V or less, and the current density, the oxidation time, and the film thickness of the anodized film 12 are as follows. An anodized film 12 is formed under the condition of -10 to 200938663 shown in FIG.
表1 :第一熱處理條件 陽 匯氧化薄膜 第—熟J 電流密度 氧化時間 膜厚 溫水 第一溫度 參考例1 5A/dm2 30分 28μπι 純水 60°C 參考例2 5A/dm2 30分 28μιη 純水 70°C 參考例3 5A/dm2 30分 28μιη 純水 80°C 參考例4 5A/dm2 30分 28μιη 純水 90°C ^處理時間 一30分 一30分 一30分 3〇分 ❹ 使用形成有陽極氧化薄膜12之處理對象物n，以上 述表1所示的條件’進行第一熱處理步驟，製作各5個參 考例1〜4的樣品。 各樣品的斷面以掃描型電子顯微鏡（SEM )觀察時， 第一溫度爲60 °C時，陽極氧化薄膜12 (空隙層）上沒有 形成任何東西，進行第一熱處理前及後，表面狀態沒有改 ❹ 變。 相對地，於第一溫度爲70 °C、80 °C、90 °C時，從陽極 氧化薄膜12表面至Ιμιη深度之間，顯示不連續的面，露 出陽極氧化薄膜12中的空隙。第一溫度爲60t、80 °C、 90°C時的SEM相片分別記載於圖4〜6。 然後，使用上述前處理後的基板，以下述表2所示的 條件形成陽極氧化薄膜1 2後，浸漬於純水洗淨後’以下 述表2所示的條件，進行第一、第二熱處理’製作各複數 片之實施例1〜5、比較例1〜3的樣品。 -11 - 200938663 [表2] 表2 :封孔處理條件 場極氣化 Δ I 一熱處 理 第二熱處理 一 電流 密度 氧化 時間 膜厚 溫水 第一 誠 第一處 理時間 熱水 第二 溫度 第二處 理時間 mmm 1 5Α/άχη^ 30分 28μ ra 純水 80°C 15分 沸騰水 (不同槽） 100°c 30分 實施例 2 SAJdm1 30分 28μηι 純水 80°C 15分 加壓蒸氣 130。。 30分 實施例 3 5Α/άπί^ 30分 28μπι 純水 80°C 15分 沸騰水 (同槽） loot 30分 實施例 4 5Α/άπ^ 30分 28μ m 0.3% 氨水 80°C 15分 沸騰水 (不同槽） loot： 15分 實施例 5 δΑ/dm1 10 A/dm2 15分 15分 35μιη 純水 15分 沸騰水 (不同槽） loot 30分 比較例 1 5A/(W 30分 28μιη 無 沸騰水 loot： 30分 比較例 2 5A/dm2 30分 28μπι 蒸氣 80°C 30分 加壓蒸氣 130°C 30分 比較例 3 5A/dm2 10A/dm2 15分 35μηι 無 沸騰水 100°c h〇分 *上述表中「無」係表示不進行第一熱處理的情況。 而且，第二熱處理步驟的熱水（包含沸騰水、蒸氣） 全部使用純水。於實施例1〜4、比較例I、2，陽極氧化 薄膜12的成膜條件與上述參考例1〜4相同。於實施例5 及比較例3，雖使用與參考例1〜4相同的電解液’在最 初的1 5分鐘，電流密度爲5A/dm2 ’氧化電壓爲60V以上 70V以下，氧化溫度爲15°C以上17°C以下，於其後的15 分鐘，電流密度爲1 〇A/dm2，氧化電壓爲70V以上1 30V 以下，氧化溫度爲1 7 t以上3 0 °C以下’進行總共3 0分鐘 的陽極氧化薄膜12之成膜。 〈SEM (掃瞄式電子顯微鏡）相片〉 對上述實施例1的樣品1 〇片、比較例1的樣品6 -12- 200938663 片、比較例2的樣品6片，進行斷面的SEm相 照。實施例1的SEM相片表示於圖7，比較例1 相片表示於圖8，比較例2的SEM相片表示於圖9 由圖7可見，實施例1之10片樣品，全部確 1 μιη程度的緻密層。相對地，由圖8、9可見，依 異，有形成有緻密層者，如比較例1的樣品1、2 例2的樣品1、2、6係不確定是否形成有緻密層者 由於以上之情事，得知陽極氧化薄膜12暴露 或水蒸氣前，使其接觸溫水46而非水蒸氣，可確 成緻密層。 對實施例1、比較例1的各樣品，再進行下述 測試。 〈耐腐蝕測試〉 將各樣品於室溫下浸漬於3 5 %鹽酸水溶液後 直到從樣品目視可確認的程度之大量氣泡開始產 間。該測定結果，與從SΕΜ相片測定的緻密層之 起記載於下述表3。 片之拍 的SEM 〇 認膜厚 樣品而 及比較 0 於熱水 實地形 耐腐蝕 ，測定 生的時 厚度一 -13- 200938663 [表3] 表3 :緻濟層的厚度、耐腐蝕測試(實施例1、比較例1) 緻密層的厚度 (μιη) 直至大量產生氣泡的時間 (分） 實施例1 樣品1 1.3 350 樣品2 1.3 370 樣品3 1.2 320 樣品4 1.3 400 樣品5 1.4 350 樣品6 1.3 370 樣品7 1.0 350 樣品8 1.0 450 樣品9 1.0 330 樣品10 1.0 380 比較例1 樣品1 0.1 240 樣品2 0.1 200 樣品3 0.9 350 樣品4 0.7 310 樣品5 0.2 200 樣品6 0.3 270 由上述表3得知，緻密層的膜厚增加，直到開始產生 氣泡的時間有變長的傾向。 只要緻密層的膜厚爲Ιμηι程度，直到大量產生氣泡 的時間爲350分鐘至400分鐘，相對地沒有形成緻密層之 樣品爲2 0 0分鐘左右。得知若形成緻密層，耐腐蝕性高。 比較實施例1與比較例1時，實施例1的各樣品與比 較例1比較，緻密層較厚，且各樣品的厚度不均勻亦小。 14 - 200938663 由於以上之情事，得知由本發明所形成的 層）厚，且膜厚的不均勻少。 而且，對於實施例3 ’與實施例！同樣 的膜厚時，膜厚及其不均勻度係與實施例1 於以上之情事，確認即使將第一熱處理時的 樣加熱而進行第二熱處理，與在不同槽進行 相同。 對於實施例2、4、5、比較例3的樣品 同樣地測定保護膜的膜厚。其測定結果記載 7 ° [表4] ❹ 表4 :緻密層的厚度（實施例2) 緻密層的厚度 (μιη) 樣品1 1.4 樣品2 1.6 樣品3 1.0 樣品4 1.8 樣品5 1.4 樣品6 1.6 樣品7 1.5 護膜（緻密 測定保護膜 同程度。由 水4 6依原 情況下效果 與實施例1 下述表 4〜 -15- 200938663 [表5] 表5 :緻密層的厚度（實施例4) 緻密層的厚度 (μπι) 樣品1 1.8 樣品2 2.0 樣品3 1.7 樣品4 1.7 樣品5 1.9 [表6] [表7] 表6:緻密層的厚度（實施例5) 緻密層的厚度 (μπι) 樣品1 1.2 樣品2 1.5 樣品3 1.5 樣品4 1.6 樣品5 1.7 表7 :緻密層的厚度（比較例3) 緻密層的厚度 (μτη) 樣品1 0.9 樣品2 0.1 樣品3 0.2 樣品4 0.8 樣品5 0.1 200938663 表4與上述表2的結果沒有大差異，得知在第二熱處 理，接觸陽極氧化薄膜12者’與熱水、水蒸氣無關’只 要是第二溫度，緻密層厚，其膜厚的不均勻亦小。 在實施例4所使用的弱鹼性水溶液（氨水），係一般 習知爲了促進封孔處理者。由表5可見，實施例4使用純 水（中性），與其他實施例比較，緻密層較厚，得知於本 發明，溫水46爲鹼性之情事，與其說對緻密層的形成無 不良影響，不如說是促進緻密層的形成。 實施例5、比較例3係如上述表2之記載，形成陽極 氧化薄膜1 2時，前半段爲低電流密度，後半段爲高電流 密度，在形成陽極氧化薄膜1 2的後半段，陽極氧化包覆 膜的空隙（孔）的尺寸變大，在非空隙之壁的部份之膜厚 亦變厚，使陽極氧化包覆膜的構造在膜厚方向上改變。 但是，比較表6、7與上述表2時，即使改變陽極氧 化包覆膜的構造，第一、第二熱處理後緻密層的膜厚沒有 大差異。所以，得知本發明係與陽極氧化包覆膜形成時的 條件、陽極氧化包覆膜的構造無關，可形成緻密層。 而且’電解液由草酸水溶液變成硫酸水溶液，形成陽 極氧化薄膜1 2時，與使用草酸水溶液的情況相同地得到 多孔性陽極氧化薄膜12。使用該陽極氧化薄膜12，與上 述實施例1〜5相同的條件下進行第一、第二熱處理步驟 時’與使用草酸水溶液的情況相同地得到緻密的保護膜。 由以上之情事’得知本案的發明，即使改變電解液，可形 成緻密的保護膜。 -17- 200938663 以上，說明在第一熱處理步驟，處理對象物u德、 授潰 於溫水46的情況，但本發明不限於該情況，只要是處理 對象物1 1與溫水46接觸，可使溫水46流過處理對象物 11的表面’也可將溫水46噴霧於處理對象物u $ W表 面。 再者’於第二熱處理步驟，只要熱水接觸處理對象物 11，可使熱水流過處理對象物11的表面，也可將熱水噴 霧於處理對象物11的表面。 只要第二溫度爲第一溫度以上即可，爲了使氧化銘與 〇 氫氧化鋁充分水合，期望爲1 oot以上。 電解液只要是可形成多孔性陽極氧化薄膜12者，無 特別限制。作爲形成多孔性陽極氧化薄膜1 2之電解液， 係將選自草酸、硫酸、蘋果酸、丙二酸所成群的至少1種 以上的酸溶解於水之水溶液。 用於第一熱處理之溫水46不限於純水、氨水。例如 可使用純水中添加選自氨、三乙醇胺、聯胺（hydrazine ) _ 所成群之任一種鹼之鹼性水溶液。 而且’用於第二熱處理之熱水與水蒸氣亦不限於純 水。例如可使用純水中添加選自氨、三乙醇胺、聯胺所成 群之任一種鹼之驗性水溶液。 而且，添加於上述溫水46、熱水、水蒸氣之鹼無特 別限制，爲了使第一、第二熱處理步驟後的洗淨步驟簡 潔，期望揮發性者。 本發明之封孔處理所形成的緻密層之厚度爲0.5 μηι以 -18- 200938663 上2 μ m以下。 處理對象物只要是表面形成有陽極氧化包覆膜者，無 特別限制。例如可使用全部以鋁材料構成者，也可使用鋁 材料以外的材料所構成的芯材之表面形成有鋁材料的薄膜 者。 ' 而且’鋁材料只要是以鋁爲主成份者，無特別限制。 ' 於該情況，所謂主成份係指含有50原子％以上的鋁者， 鋁的形態可爲鋁單體，亦可爲合金。 ❹ [產業上的利用可能性] 使用於提高鋁材料所構成的構件之耐腐蝕性用的表面 處理。特別適合構成CVD裝置、蝕刻裝置等的真空槽內 壁之內壁構件、天線構件等、露出真空槽內部、有與反應 氣體、反應氣體的電漿、自由基接觸之虞的構件。 ^ 【圖式簡單說明】 ❹ 圖1係說明形成陽極氧化薄膜的步驟之剖面圖。 圖2係說明第一熱處理步驟用之剖面圖。 ‘圖3係說明第二熱處理步驟用之剖面圖。 圖4係參考例1 ( 60°C )之斷面的SEM相片。 圖5係參考例3 (80 °C)之斷面的SEM相片。 圖6係參考例4 ( 9〇°C )之斷面的SEM相片。 圖7係實施例1之斷面的SEM相片。 圖8係比較例1之斷面的SEM相片。 -19- 200938663 圖9係比較例2之斷面的SEM相片。 【主要元件符號說明】 2 :陽極氧化裝置 1 1 :處理對象物 21 :電解槽 22 :陰極板 23 :安裝器具 2 5 :電源 2 6 :電解液 4:第一封孔處理裝置 1 2 :陽極氧化薄膜 41 :第一加熱處理槽 46 :溫水 5:第二封孔處理裝置 5 1 :處理槽 5 5 :水蒸氣產生裝置 -20-Table 1: First heat treatment conditions Yanghui oxide film first-cooked J current density oxidation time film thickness warm water first temperature reference example 1 5A/dm2 30 minutes 28μπι pure water 60°C Reference example 2 5A/dm2 30 minutes 28μιη pure Water 70 °C Reference Example 3 5A/dm2 30 minutes 28μιη Pure water 80°C Reference Example 4 5A/dm2 30 minutes 28μιη Pure water 90°C ^Processing time 30 minutes 30 minutes 30 minutes 3 minutes Distribution using The object to be treated n having the anodized film 12 was subjected to the first heat treatment step under the condition 'described in Table 1 above, and samples of each of the five reference examples 1 to 4 were prepared. When the cross section of each sample was observed by a scanning electron microscope (SEM), when the first temperature was 60 ° C, nothing was formed on the anodized film 12 (void layer), and the surface state was not obtained before and after the first heat treatment. Change it. In contrast, at the first temperature of 70 ° C, 80 ° C, and 90 ° C, a discontinuous surface is shown from the surface of the anodized film 12 to a depth of Ιμη, and voids in the anodized film 12 are exposed. The SEM photographs at the first temperatures of 60t, 80 °C, and 90 °C are shown in Figures 4-6, respectively. Then, using the pretreated substrate, the anodized film 1 2 was formed under the conditions shown in Table 2 below, and after immersing in pure water, the first and second heat treatments were performed under the conditions shown in Table 2 below. 'Examples 1 to 5 and Comparative Examples 1 to 3 of each of the plurality of sheets were produced. -11 - 200938663 [Table 2] Table 2: Sealing treatment conditions Field gasification Δ I A heat treatment Second heat treatment One current density Oxidation time Film thickness Warm water First honest First treatment time Hot water Second temperature Second treatment Time mm1 1 5Α/άχη^ 30 minutes 28μ ra Pure water 80°C 15 minutes boiling water (different tank) 100°c 30 minutes Example 2 SAJdm1 30 minutes 28μηι Pure water 80°C 15 minutes Pressurized vapor 130. . 30 points Example 3 5Α/άπί^ 30 minutes 28μπι Pure water 80°C 15 minutes boiling water (same tank) loot 30 points Example 4 5Α/άπ^ 30 minutes 28μm 0.3% ammonia water 80°C 15 minutes boiling water ( Different tanks) loot: 15 points Example 5 δΑ/dm1 10 A/dm2 15 minutes 15 minutes 35μιη Pure water 15 points boiling water (different tanks) loot 30 points Comparative example 1 5A/(W 30 points 28μιη No boiling water loot: 30 points Comparative Example 2 5A/dm2 30 minutes 28μπι Vapor 80°C 30 minutes Pressurized vapor 130°C 30 minutes Comparative Example 3 5A/dm2 10A/dm2 15 minutes 35μηι No boiling water 100°ch〇 points* In the above table The absence of the first heat treatment is shown. The hot water (including boiling water and steam) in the second heat treatment step is all pure water. In Examples 1 to 4, Comparative Examples I and 2, the anodized film 12 is used. The film formation conditions were the same as in the above Reference Examples 1 to 4. In Example 5 and Comparative Example 3, the same electrolytic solution as in Reference Examples 1 to 4 was used, and the current density was 5 A/dm 2 'oxidation in the first 15 minutes. The voltage is 60V or more and 70V or less, and the oxidation temperature is 15°C or more and 17°C or less, and 15 minutes thereafter. The current density is 1 〇A/dm2, the oxidation voltage is 70 V or more and 1 30 V or less, and the oxidation temperature is 1 7 t or more and 30 ° C or less. The film formation of the anodized film 12 is performed for a total of 30 minutes. Sight Electron Microscope) Photograph> The sample 1 〇 of the above Example 1, the sample of the sample of Comparative Example 1 of 6-12-200938663, and the sample of the sample of Comparative Example 2 were subjected to SEm of the cross section. The SEM photograph is shown in Fig. 7, the photograph of Comparative Example 1 is shown in Fig. 8, and the SEM photograph of Comparative Example 2 is shown in Fig. 9. It can be seen from Fig. 7 that the 10 samples of Example 1 are all dense layers of about 1 μm. As can be seen from Figures 8 and 9, depending on the above, the sample 1, 2, and 6 of the sample 1 and 2 of the sample 1 of Comparative Example 1 are not determined whether or not the dense layer is formed. It is known that the anodized film 12 is exposed to warm water 46 instead of water vapor before exposure to water vapor, and a dense layer can be obtained. For each of the samples of Example 1 and Comparative Example 1, the following test was carried out. Test > Each sample was immersed in a 35% hydrochloric acid aqueous solution at room temperature until it was sampled A large number of bubbles can be confirmed at the beginning of production. The results of this measurement are shown in Table 3 below from the dense layer measured from the SΕΜ photo. The SEM of the film is taken to identify the film thickness and the comparison is 0 in hot water. The terrain is corrosion-resistant and the thickness is measured. 1--13- 200938663 [Table 3] Table 3: Thickness and corrosion resistance test of the meso layer (Example 1, Comparative Example 1) Thickness of the dense layer (μιη) until a large amount of bubbles are generated Time (minutes) Example 1 Sample 1 1.3 350 Sample 2 1.3 370 Sample 3 1.2 320 Sample 4 1.3 400 Sample 5 1.4 350 Sample 6 1.3 370 Sample 7 1.0 350 Sample 8 1.0 450 Sample 9 1.0 330 Sample 10 1.0 380 Comparative Example 1 Sample 1 0.1 240 Sample 2 0.1 200 Sample 3 0.9 350 Sample 4 0.7 310 Sample 5 0.2 200 Sample 6 0.3 270 It is known from Table 3 above that the film thickness of the dense layer increases until the time at which bubble generation starts is lengthened. . As long as the film thickness of the dense layer is about Ιμηι, the time until a large amount of bubbles are generated is from 350 minutes to 400 minutes, and the sample in which the dense layer is not formed relatively is about 200 minutes. It is known that if a dense layer is formed, corrosion resistance is high. When Comparative Example 1 and Comparative Example 1 were compared, each of the samples of Example 1 was thicker than Comparative Example 1, and the thickness of each sample was not uniform. 14 - 200938663 It is known from the above that the layer formed by the present invention is thick and the unevenness of the film thickness is small. Moreover, for Example 3' and the embodiment! In the case of the same film thickness, the film thickness and the unevenness thereof were the same as those in Example 1, and it was confirmed that the second heat treatment was performed even when the sample at the time of the first heat treatment was heated, and the same was carried out in the different grooves. The film thicknesses of the protective films were measured in the same manner as in the samples of Examples 2, 4, and 5 and Comparative Example 3. The measurement results are described as 7 ° [Table 4] ❹ Table 4: Thickness of dense layer (Example 2) Thickness of dense layer (μιη) Sample 1 1.4 Sample 2 1.6 Sample 3 1.0 Sample 4 1.8 Sample 5 1.4 Sample 6 1.6 Sample 7 1.5 Protective film (dense measurement of protective film to the same extent. Effect by water 4 6 and Example 1 Table 4 to -15- 200938663 [Table 5] Table 5: Thickness of dense layer (Example 4) Densification Thickness of layer (μπι) Sample 1 1.8 Sample 2 2.0 Sample 3 1.7 Sample 4 1.7 Sample 5 1.9 [Table 6] [Table 7] Table 6: Thickness of dense layer (Example 5) Thickness of dense layer (μπι) Sample 1 1.2 Sample 2 1.5 Sample 3 1.5 Sample 4 1.6 Sample 5 1.7 Table 7: Thickness of dense layer (Comparative Example 3) Thickness of dense layer (μτη) Sample 1 0.9 Sample 2 0.1 Sample 3 0.2 Sample 4 0.8 Sample 5 0.1 200938663 Table 4 There is no significant difference from the results of Table 2 above. It is known that in the second heat treatment, the contact with the anodized film 12 is 'independent of hot water and water vapor'. As long as it is the second temperature, the dense layer is thick and the film thickness is not uniform. The weak alkaline water solution used in Example 4 Liquid (ammonia water) is generally known to promote sealing treatment. It can be seen from Table 5 that Example 4 uses pure water (neutral), and the dense layer is thicker than other examples, and it is known that the present invention is warm. The water 46 is alkaline, and it does not adversely affect the formation of the dense layer, but rather promotes the formation of the dense layer. Example 5 and Comparative Example 3 are as described in Table 2 above, when the anodized film 1 2 is formed. The first half is a low current density, and the second half is a high current density. In the second half of the formation of the anodized film 12, the size of the void (hole) of the anodized film becomes large, and the portion of the wall of the non-void is The film thickness also became thick, and the structure of the anodized film was changed in the film thickness direction. However, when Tables 6 and 7 and Table 2 above were compared, the first and second heat treatments were changed even if the structure of the anodized film was changed. The film thickness of the rear dense layer is not greatly different. Therefore, it is understood that the present invention can form a dense layer regardless of the conditions at the time of formation of the anodized film and the structure of the anodized film. Sulfuric acid water When the anodic oxide film 12 was formed, the porous anodized film 12 was obtained in the same manner as in the case of using an aqueous oxalic acid solution. The anodized film 12 was used to carry out the first and second conditions under the same conditions as in the above Examples 1 to 5. In the heat treatment step, a dense protective film was obtained in the same manner as in the case of using an aqueous oxalic acid solution. From the above, the invention of the present invention was found to form a dense protective film even if the electrolytic solution was changed. -17- 200938663 In the first heat treatment step, the object to be processed and the cold water 46 are treated, but the present invention is not limited to this case, and the object to be treated 1 1 may be in contact with the warm water 46. The warm water 46 may be sprayed on the surface of the object to be treated 11 or the warm water 46 may be sprayed on the surface of the object to be treated. Further, in the second heat treatment step, hot water may flow on the surface of the object to be treated 11, as long as the hot water contacts the object to be processed 11, and hot water may be sprayed on the surface of the object 11 to be processed. As long as the second temperature is equal to or higher than the first temperature, it is desirable to be 1 ot or more in order to sufficiently hydrate the oxidized aluminum hydroxide with hydrazine. The electrolytic solution is not particularly limited as long as it can form the porous anodized film 12. The electrolyte solution for forming the porous anodized film 12 is obtained by dissolving at least one acid selected from the group consisting of oxalic acid, sulfuric acid, malic acid, and malonic acid in an aqueous solution of water. The warm water 46 used for the first heat treatment is not limited to pure water or ammonia water. For example, an alkaline aqueous solution of any one selected from the group consisting of ammonia, triethanolamine, and hydrazine can be added to pure water. Further, the hot water and water vapor used for the second heat treatment are not limited to pure water. For example, an aqueous test solution of any one selected from the group consisting of ammonia, triethanolamine, and hydrazine may be added to pure water. Further, the base added to the warm water 46, hot water or steam is not particularly limited, and in order to make the washing step after the first and second heat treatment steps simple, it is desirable to be volatile. The thickness of the dense layer formed by the plugging treatment of the present invention is 0.5 μm to 2 μm or less on -18-200938663. The object to be treated is not particularly limited as long as it is formed with an anodized film on its surface. For example, a film made of an aluminum material or a film made of a material other than an aluminum material may be used. 'And' aluminum materials are not particularly limited as long as they are mainly composed of aluminum. In this case, the main component means aluminum containing 50 atom% or more, and the form of aluminum may be an aluminum monomer or an alloy. ❹ [Industrial Applicability] Surface treatment for improving the corrosion resistance of members made of aluminum materials. It is particularly suitable for an inner wall member, an antenna member, or the like which constitutes an inner wall of a vacuum chamber such as a CVD apparatus or an etching apparatus, and a member which is exposed inside the vacuum chamber and which is in contact with a plasma of a reaction gas or a reaction gas or a radical. ^ [Simple description of the drawings] Fig. 1 is a cross-sectional view showing the steps of forming an anodized film. Figure 2 is a cross-sectional view showing the first heat treatment step. Figure 3 is a cross-sectional view showing the second heat treatment step. Figure 4 is a SEM photograph of a section of Reference Example 1 (60 ° C). Figure 5 is a SEM photograph of a section of Reference Example 3 (80 °C). Figure 6 is a SEM photograph of a section of Reference Example 4 (9 ° C). Figure 7 is a SEM photograph of the cross section of Example 1. Figure 8 is a SEM photograph of a section of Comparative Example 1. -19- 200938663 Fig. 9 is a SEM photograph of a section of Comparative Example 2. [Description of main component symbols] 2 : Anodizing device 1 1 : Processing target 21 : Electrolytic cell 22 : Cathode plate 23 : Mounting device 2 5 : Power supply 2 6 : Electrolyte 4 : First sealing treatment device 1 2 : Anode Oxidized film 41: first heat treatment tank 46: warm water 5: second plugging treatment device 5 1 : treatment tank 5 5 : water vapor generating device -20-