201030189 六、發明說明： 【發明所屬之技術領域】 本發明涉及一種製造以鋁合金或純鋁作爲基材的半導 體液晶製造裝置用表面處理構件的方法，所述半導體液晶 製造裝置作爲表面處理構件適用作在乾式蝕刻裝置、CVD 裝置、離子注入裝置、濺射裝置等半導體或液晶的製造設 備等的真空腔，或該真空腔的內部中設置的構件的材料。 【先前技術】 過去廣泛採用的是在將鋁合金或純銘作爲基材的構件 的表面上形成陽極氧化覆膜，在該基材賦予耐電漿性或耐 氣體腐蝕性等的陽極氧化處理。 例如，通常使用鋁合金形成在半導體製造設備的電漿 處理裝置中使用的真空腔以及在該真空腔的內部設置的電 極等各種構件。但是，如果在無垢的狀態下使用該鋁合金 # ，則不能維持耐電漿性或耐氣體腐蝕性等，所以通過在利 用鋁合金形成的構件的表面實施陽極氧化處理從而形成陽 極氧化覆膜，從而賦予耐電漿性或耐氣體腐蝕性等來對應 〇 在半導體製造設備的電漿處理裝置中使用的真空腔以 及在該真空腔的內部設置的電極等各種構件在電漿的物理 能量的作用下，陽極氧化覆膜的磨損劇烈，陽極氧化覆膜 必需爲高硬度，另外，如果在陽極氧化覆膜中存在裂縫， 則會通過裂縫侵入氣體從而腐蝕作爲基材的鋁合金，所以 -5- 201030189 陽極氧化覆膜最好盡可能地不存在裂縫。 過去，作爲使陽極氧化覆膜成爲高硬度化的方法，採 用將形成陽極氧化覆膜時的電解液控制成低溫的方法或利 用高電流密度進行電解的方法，但如果利用這些方法使陽 極氧化覆膜高硬度化，則存在使陽極氧化覆膜的裂縫的發 生增加的趨勢，另外，這些方法還存在必需高的能量的問 題。因此，對應各種構件的使用環境或要求價格來調整陽 極氧化覆膜的硬度與裂縫的平衡，但目前不能充分地對應 高硬度與低裂縫、還有對低價格的要求。 另外，作爲使陽極氧化覆膜成爲高硬度化的方法，作 爲專利文獻1，提出了使用添加有醇的硫酸系電解液來形 成高硬質的陽極氧化覆膜的方法。但是，該方法具有利用 陽極氧化處理的電解液中的醇的濃度變化的管理變得繁雜 的問題點。 另外，作爲專利文獻2，記載了在對鋁合金實施陽極 氧化加工的表面處理構件的表面，進一步形成氧化物噴鍍 覆膜的方法，得到的覆膜爲高硬度。但是，該方法存在的 課題在於，用於形成氧化物噴鍍覆膜的處理非常複雜，而 且必需高價的設備，另外，不能適用於複雜形狀部位。 專利文獻1 :特開2006-3 3608 1號公報 專利文獻2:特開2004-332081號公報 專利文獻3 :特開平7-2 1 6588號公報 【發明內容】 -6 - 201030189 _ 本發明正是爲了解決上述以往的問題而提出的，其課 題在於提供一種能夠利用簡便的方法形成硬度高於利用以 往方法形成的陽極氧化覆膜而且沒有發生裂縫的方面的問 題、高硬度且低裂縫的平衡出色的陽極氧化覆膜的半導體 液晶製造裝置用表面處理構件的製造方法。 本發明之一是一種半導體液晶製造裝置用表面處理構 件的製造方法，其是在將鋁合金或純鋁作爲基材的構件的 φ 表面形成陽極氧化覆膜，然後在純水中浸漬來水合處理所 述陽極氧化覆膜的半導體液晶製造裝置用表面處理構件的 製造方法，其特徵在於， 在滿足處理溫度：80°C〜100°C、處理時間（分鐘） hi.5x處理溫度) +2 70的條件下實施所述水合處理。 本發明之二是根據本發明之一所述的半導體液晶製造 裝置用表面處理構件的製造方法，其特徵在於， 在所述水合處理之後，在滿足處理溫度：120°C~450 • °C、處理時間（分鐘）2-O.lx處理溫度（t ) +71的條件 下實施熱處理。 如果利用本發明之一所述的半導體液晶製造裝置用表 面處理構件的製造方法，則可以利用規定了水合處理的處 理時間及處理溫度的極爲簡便的方法，形成硬度高於利用 以往方法形成的陽極氧化覆膜而且沒有發生裂縫的方面的 問題、高硬度且低裂縫的平衡出色的陽極氧化覆膜。 另外’本發明的半導體液晶製造裝置用表面處理構件 的製造方法中的水合處理是使用處理溫度爲8(rc〜10(rc 201030189 的熱水的處理，也不像使用加壓蒸氣的水合處理那樣必需 特別的設備。 如果利用本發明之二所述的半導體液晶製造裝置用表 面處理構件的製造方法，則由於在水合處理之後進一步實 施熱處理，所以可以在也沒有裂縫發生的方面的問題的範 圍內，進一步使陽極氧化覆膜成爲高硬度。 【實施方式】 @ 以下基於實施方式更詳細地說明本發明。 陽極氧化覆膜是通過將鋁合金等基材浸漬於電解液中 成爲陽極，通電流，來氧化陽極側的鋁合金等基材的表面 從而形成的，根據電解液的組成、電解溫度、電流密度（ 每單位面積的電流値）不同而形成的陽極氧化覆膜的性狀 即陽極氧化覆膜的硬度或發生的裂縫密度等不同。 陽極氧化覆膜目前主要使用硫酸電解液，通過在低溫 且高電流密度下電解來形成，如果利用該方法形成陽極氧 0 化覆膜，則存在如下矛盾，即：儘管能夠得到高硬度的陽 極氧化覆膜，但另一方面，在陽極氧化覆膜上發生的裂縫 的密度（例如每單位表面積的裂縫長度）.變大。 另外，在半導體液晶製造裝置用表面處理構件中，從 氣體與陽極氧化覆膜的化學反應抑制的觀點出發，有時對 陽極氧化覆膜實施水合處理（通稱：封孔處理），但如果 實施水合處理，則例如像在專利文獻3中所記載“利用封 孔處理形成的封孔層4具有結晶化的趨勢，會成爲覆膜強 -8- 201030189 . 度降低的原因”，通常已知陽極氧化覆膜的硬度降低，設 定了在允許的硬度降低的範圍內的水合處理時間。 本發明人等著眼於該水合處理，進行潛心硏究、探究 。結果發現，通過充分地加長水合處理時間，相反，陽極 氧化覆膜高硬度化，發生的裂縫的密度也沒有變得很高， 以至完成本發明。 具體而言，通過使對陽極氧化覆膜進行水合處理時的 〇 處理溫度成爲80°c ~100°c，而且使實施水合處理時的處 理時間滿足“處理時間（分鐘）1 · 5 X處理溫度（°c ) + 270”的條件，從而實施水合處理，陽極氧化覆膜高硬度 化，發生的裂縫的密度也沒有變得很高。 另外，還發現，在水合處理之後，通過實施熱處理， 陽極氧化覆膜進一步高硬度化，發生的裂縫的密度也沒有 高到成爲問題的程度。 使具體的熱處理的條件滿足處理溫度成爲120 °C〜4 50 Φ °C、實施熱處理時的處理時間成爲“處理時間（分鐘） 之-0.1 X處理溫度（°C ) +71”的條件，從而對陽極氧化覆 膜實施熱處理，通過在這樣的條件下對陽極氧化覆膜實施 熱處理，可以高硬度化，以至使維氏硬度高於實施熱處理 之前的已高硬度化的陽極氧化覆膜Hv. 25以上，另外，發 生的裂縫的密度也沒有高到成爲問題的程度。 (水合處理的處理溫度） 水合處理的溫度處於80 °C〜100 °C的範圍。在水合處 201030189 理的溫度不到8 0 °C的情況下’即使利用滿足“處理時間 (分鐘）2-1.5X處理溫度（°C ) +270”的條件的處理時間 來實施水合處理，陽極氧化覆膜也不會高硬度化。對其原 因尙不明確，但認爲這是因爲’與利用水合反應形成的陽 極氧化覆膜的氧化物狀態爲80°C以上的情況不同。另一 方面，爲了使水合處理的溫度超過1〇〇 °C，必需使水成爲 水蒸氣等特別的設備。 水合處理的溫度在爲l〇〇°C以下的盡可能高的溫度時 _ ，處理時間變短，從生產的觀點來看是較佳的，但相反， 越是高溫，則水的蒸發量越大，從而變得必需補充水，處 理變得繁雜。另外，由於可以挪用在工廠內其他設備中使 用的80°C以上的水，所以考慮到這些觀點，水合處理的 溫度只要在80°C〜l〇〇°C的範圍內適當地設定即可。 (水合處理的處理時間） 即使將水合處理的處理溫度規定在80°C 〜100°C的範 © 圍內，如果其處理時間短，則陽極氧化覆膜的硬度反而降 低，所以必需規定對應處理溫度的最低處理時間。具體而 言，通過使其滿足“處理時間（分鐘）2-1.5 X處理溫度（ °C ) +270”的條件，只要實施水合處理即可。對於由於水 合處理時間不同而陽極氧化覆膜的硬度改變的原因，尙不 能充分地解釋，但可以認爲水合反應引起的陽極氧化覆膜 的氧化物的狀態變化與氧化物的體積膨脹的平衡並不是起 因。 -10- 201030189 另外，在使水合處理的處理時間滿足“處理時間（分 鐘）2-1·5χ處理溫度（°C ) +270”的條件的範圍內，如果 盡可能地延長，則陽極氧化覆膜的硬度變高，但另一方面 ，還存在裂縫密度也略微上升的趨勢，所以只要對應要求 性能適當地設定處理時間即可。不過，由於如果處理時間 過長，則生產率差，所以水合處理的處理時間較佳者爲 480分鐘以下，更佳者爲3 00分鐘以下。 ❹ (熱處理的處理溫度） 熱處理的溫度處於120°C〜450t的範圍。在熱處理的 溫度不到12(TC的情況下，即使以滿足“處理時間（分鐘 )2-0. lx處理溫度（°C ) +71”的條件的處理時間實施熱 處理，陽極氧化覆膜也不會高硬度化。對其理由尙不能充 分地解釋，但認爲這是因爲，伴隨水合反應後的脫水反應 的陽極氧化覆膜的結構變化不充分。另一方面，如果使熱 φ 處理的溫度超過450 t，則變得容易發生作爲基材的鋁合 金等的變形，製品的尺寸公差有可能會偏離。因而，熱處 理的溫度處於120°C〜450°C的範圍。 (熱處理的處理時間） 即使將熱處理的處理溫度規定成120°C〜45 0°C的範圍 ，如果其處理時間短，則陽極氧化覆膜的硬度以維氏硬度 計算，只上升Hv.20左右或其以下，幾乎沒有實施熱處理 的工業上的意義，所以規定對應處理溫度的最低處理時間 -11 - 201030189 。具體而言，只要使其滿足“處理時間（分鐘）2·〇·1Χ處 理溫度（°C ) +71”的條件，來實施熱處理即可。對於根 據熱處理時間不同而陽極氧化覆膜的硬度變化的原因，尙 不能充分地解釋，但可以認爲伴隨水合反應後的脫水反應 的陽極氧化覆膜的結構變化並不是起因。 另外，在使熱處理的處理時間滿足“處理時間（分鐘 )2-0. lx處理溫度（°C ) +71”的條件的範圍內，如果盡 可能地延長，則陽極氧化覆膜的硬度變高，但另一方面， 還存在裂縫密度也略微上升的趨勢，所以只要對應要求性 能適當地設定處理時間即可。不過，由於如果處理時間過 長，則生產率差，所以熱處理的處理時間較佳者爲120分 鐘以下，更佳者爲90分鐘以下。 [實施例] 以下舉出實施例，更具體地說明本發明，但本發明根 本不受下述實施例限制，也可以在能夠適合本發明的主旨 的範圍內適當地變更進而實施，這些變更均被包括在本發 明的技術範圍內。 首先，熔煉JIS規定的606 1鋁合金，成爲鋁合金鑄 鏡（尺寸：220mmWx250mmLxtl00mm，冷谷卩速度：15~10 °C )，切斷該鑄錠，進行端面切削（尺寸·· 220mmWx 1 50mmLxt60mm )，然後實施均熱處理（540°Cx4h)。在 均熱處理後，利用熱軋，將60mm厚的坯料壓延成 6mm 厚的板材，切斷（尺寸：220mmWx400mmLxt6mm )之後 -12- 201030189 . ，實施固溶處理（510〜520 tx30min)。在固溶處 ’實施水淬，實施時效處理（160〜18〇t：x8h)，得 合金板。 從該供試合金板，切下25mmx35mm (壓延j t3mm的試片，對其表面進行端面切削加工。接著 °C -1 〇%NaOΗ水溶液中浸漬2分鐘，然後水洗，進 3 0°C -2 0%ΗΝ〇3水溶液中浸漬2分鐘，然後水洗， Φ 表面’然後在表1〜4所示的各條件下實施陽極氧化 在試片的表面形成陽極氧化覆膜。陽極氧化覆膜的 部爲5 0 μ m。 另外，水合處理是在純水中浸漬各試片，在表 示的各水合處理溫度及各水合處理時間下實施的。 進而，對一部分的試片實施了熱處理。熱處理 氣熱處理爐中加入各試片，在表1~4所示的各熱處 及各熱處理時間下實施。 ® 利用光學顯微鏡，在400倍的倍率下觀察利用 法製作的各試片的表面，求出裂縫密度。觀察例的 照片如圖3所示。該裂縫密度是通過測定在各試片 0.235x0.1 80mm的範圍內發生的裂縫的長度的總^ )’以mm/mm2的單位換算該長度總和從而求得的 接著’將各試片埋入樹脂中，使陽極氧化覆膜 露出’然後利用維氏硬度計（Akashi，MVK-G2) 極氧化覆膜的截面的中央部的硬度。 對水合處理後的各試片，在各試片的測定中得 理之後 到供試 J向）X ，在60 而，在 洗滌化 覆膜， 膜厚全 1~4所 是在大 理溫度 以上方 顯微鏡 的表面 Ϊ] ( mm 〇 的截面 測定陽 到的維 -13- 201030189 氏硬度爲沒有實施水合處理的No.l的維氏硬度以上時， 結果爲陽極氧化覆膜爲高硬度，爲合格。另外，對熱處理 後的各試片’在各試片的測定中得到的維氏硬度比熱處理 前的維氏硬度上升Η v.25以上時，結果爲陽極氧化覆膜爲 高硬度，爲合格。 在表1〜4中示出其試驗結果，分別，將No.l〜No.29 的水合處理時間及水合處理溫度與維氏硬度的關係以及 No.32〜No.43的水合處理時間及水合處理溫度與維氏硬度 的關係示於圖1 ’將No.l〜No.29的水合處理時間及水合 處理溫度與裂縫密度的關係以及No·32〜N〇·43的水合處理 時間及水合處理溫度與裂縫密度的關係示於圖2。 201030189 【1® 試驗結果 裂縫密度 (mm/mm2) 〇〇 ON Ο CN 卜 CN (N 1〇 維氏硬度 ! (Hv.) 452 434 m 432 00 Os s m 574 in 00 ί—Η … 522 熱處理 熱處理 時間 (分鐘） 1 1 1 1 1 I 1 幽 1 § (Ν Ο 熱處理 溫度 (°C) 1 1 1 1 1 I 1 1 1 300 400 Ο m 400 水合處理 水合處理 時間 (分鐘） 沒有水合處理 〇 Ο § I 240 240 240 240 240 240 240 -1.5x處理 溫度+270 (分鐘） 水合處理 溫度 (°C) 〇 r-H 覆膜形成 電解電 流密度 (A/dm2) 〇 CN 處理液 溫度 CO 〇 陽極氧化 處理液 硫酸 150g/L 備註 比較例 比較例 比較例 比較例 比較例 比較例 實施例 實施例 實施例 實施例 實施例 實施例 比較例 比較例 比較例 No. <N 寸 VO 卜 〇〇 ON CM m m m 'Ο Ρ； -15- 201030189[Technical Field] The present invention relates to a method of manufacturing a surface treatment member for a semiconductor liquid crystal manufacturing apparatus using aluminum alloy or pure aluminum as a substrate, and the semiconductor liquid crystal manufacturing apparatus is applied as a surface treatment member The vacuum chamber of a semiconductor or liquid crystal manufacturing apparatus such as a dry etching apparatus, a CVD apparatus, an ion implantation apparatus, or a sputtering apparatus, or a material of a member provided in the inside of the vacuum chamber. [Prior Art] In the past, an anodized film was formed on the surface of a member made of an aluminum alloy or a pure substrate, and an anodizing treatment such as plasma resistance or gas corrosion resistance was applied to the substrate. For example, various members such as a vacuum chamber used in a plasma processing apparatus of a semiconductor manufacturing apparatus and an electrode provided inside the vacuum chamber are usually formed using an aluminum alloy. However, if the aluminum alloy # is used in a non-scale state, the plasma resistance, the gas corrosion resistance, and the like cannot be maintained. Therefore, the surface of the member formed of the aluminum alloy is anodized to form an anodized film, thereby forming an anodized film. Providing plasma resistance, gas corrosion resistance, etc., corresponding to various components such as a vacuum chamber used in a plasma processing apparatus of a semiconductor manufacturing apparatus and an electrode provided inside the vacuum chamber, under the action of physical energy of the plasma, The anodic oxide film is severely worn, and the anodic oxide film must have high hardness. In addition, if there is a crack in the anodic oxide film, the gas is intruded through the crack to corrode the aluminum alloy as the substrate, so -5 - 201030189 anode Preferably, the oxide film is free of cracks as much as possible. In the past, as a method of increasing the hardness of the anodic oxide film, a method of controlling the electrolyte solution when the anodic oxide film is formed to a low temperature or a method of performing electrolysis using a high current density is employed. When the film is increased in hardness, the occurrence of cracks in the anodic oxide film tends to increase, and these methods also have a problem that high energy is required. Therefore, the balance between the hardness and the crack of the anodic oxide film is adjusted in accordance with the use environment or the required price of various members, but at present, the requirements for high hardness and low crack, and low price are not sufficiently satisfied. In addition, as a method of increasing the hardness of the anodic oxide film, Patent Document 1 proposes a method of forming a highly hard anodized film using a sulfuric acid-based electrolyte solution to which an alcohol is added. However, this method has a problem that the management of the change in the concentration of the alcohol in the electrolytic solution treated by the anodizing becomes complicated. Further, Patent Document 2 describes a method of forming an oxide sprayed film on the surface of a surface-treated member which is subjected to anodizing treatment on an aluminum alloy, and the obtained film has high hardness. However, this method has a problem in that the process for forming an oxide sprayed film is very complicated, and expensive equipment is required, and it is not suitable for a complicated shape portion. Patent Document 1: Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2004-332081. In order to solve the above-mentioned conventional problems, an object of the present invention is to provide a problem that a hardness can be formed higher than that of an anodic oxide film formed by a conventional method and cracks are not formed by a simple method, and a high hardness and a low crack balance are excellent. A method for producing a surface treatment member for a semiconductor liquid crystal device for anodized film. One of the methods for producing a surface treatment member for a semiconductor liquid crystal manufacturing apparatus is an anodic oxide film formed on a surface of φ of a member made of an aluminum alloy or pure aluminum as a substrate, and then immersed in pure water to be hydrated. The method for producing a surface treatment member for a semiconductor liquid crystal manufacturing apparatus of the anodized film, characterized in that the processing temperature is satisfied: 80 ° C to 100 ° C, processing time (minutes) hi. 5 x processing temperature) + 2 70 The hydration treatment is carried out under the conditions. According to a second aspect of the present invention, in a method of manufacturing a surface treatment member for a semiconductor liquid crystal manufacturing apparatus according to the present invention, after the hydration treatment, a processing temperature of 120 ° C to 450 • ° C is satisfied. Treatment time (minutes) 2-O.lx treatment temperature (t) +71 was carried out under heat treatment. According to the method for producing a surface treatment member for a semiconductor liquid crystal manufacturing apparatus according to the present invention, it is possible to form an anode having a hardness higher than that of the conventional method by an extremely simple method in which the treatment time and the treatment temperature of the hydration treatment are specified. The oxide film is not problematic in that cracks occur, and an anodized film having excellent hardness and low crack balance is excellent. In the hydration treatment in the method for producing a surface treatment member for a semiconductor liquid crystal manufacturing apparatus of the present invention, the treatment temperature is 8 (rc 〜 10 (the heat treatment of rc 201030189, and the hydration treatment using pressurized steam is not used). In the method of manufacturing a surface treatment member for a semiconductor liquid crystal manufacturing apparatus according to the second aspect of the present invention, since the heat treatment is further performed after the hydration treatment, it is possible to have a problem in which no crack occurs. Further, the anodic oxide film is made to have a high hardness. [Embodiment] The present invention will be described in more detail below based on an embodiment. The anodic oxide film is formed by immersing a substrate such as an aluminum alloy in an electrolytic solution to form an anode, and a current is supplied thereto. An anodic oxide film which is formed by oxidizing the surface of a base material such as an aluminum alloy on the anode side, and having an anodic oxide film formed according to the composition of the electrolytic solution, the electrolysis temperature, and the current density (current 每 per unit area) The hardness or crack density that occurs is different. The anodized film is currently mainly used. The sulfuric acid electrolyte is formed by electrolysis at a low temperature and a high current density. If the anode oxide film is formed by this method, there is a contradiction in that although an anodic oxide film having a high hardness can be obtained, on the other hand, The density of the crack (for example, the crack length per unit surface area) which occurs on the anodized film is increased. Further, in the surface treatment member for a semiconductor liquid crystal manufacturing apparatus, the chemical reaction between the gas and the anodized film is suppressed. In view of the above, the anodic oxide film may be subjected to a hydration treatment (commonly referred to as a plugging treatment). However, when the hydration treatment is performed, for example, as described in Patent Document 3, the plugging layer 4 formed by the plugging treatment has crystals. The tendency of the film formation is a decrease in the hardness of the film -8 - 201030189. It is generally known that the hardness of the anodic oxide film is lowered, and the hydration treatment time within the range of the allowable hardness reduction is set. Focusing on the hydration treatment, it is painstakingly studied and explored. It is found that by sufficiently lengthening the hydration treatment time, on the contrary, The polar oxide film is made to have a high hardness, and the density of cracks that have occurred is not so high, so that the present invention is completed. Specifically, the enthalpy treatment temperature at the time of hydrating the anodic oxide film is 80° C to 100. °c, and the treatment time when the hydration treatment is carried out satisfies the condition of "treatment time (minutes) 1 · 5 X treatment temperature (°c) + 270", thereby performing hydration treatment, and the anodic oxide film is increased in hardness, which occurs. The density of the cracks did not become too high. Further, it was found that after the hydration treatment, the anodic oxide film was further increased in hardness by performing the heat treatment, and the density of the cracks generated was not so high as to cause a problem. The heat treatment conditions satisfy the treatment temperature of 120 ° C to 4 50 Φ ° C, and the treatment time when the heat treatment is performed becomes "treatment time (minutes - -0.1 X treatment temperature (°C) +71"), thereby anodizing The coating is subjected to heat treatment, and by subjecting the anodic oxide film to heat treatment under such conditions, the hardness can be increased, so that the Vickers hardness is higher than the heat treatment. The previous anodized film Hv. 25 or higher having a high hardness has not been so high that the density of cracks generated is too high. (Processing temperature of hydration treatment) The temperature of the hydration treatment is in the range of 80 ° C to 100 ° C. In the case where the temperature at the hydration point 201030189 is less than 80 °C, 'the hydration treatment is performed even with the treatment time satisfying the condition of "treatment time (minutes) 2-1.5X treatment temperature (°C) + 270", anode The oxide film also does not have a high hardness. The reason for this is not clear, but this is considered to be because the case where the oxide state of the anodic oxide film formed by the hydration reaction is 80 ° C or more is different. On the other hand, in order to make the temperature of the hydration treatment exceed 1 〇〇 ° C, it is necessary to make water a special device such as water vapor. When the temperature of the hydration treatment is as high as possible below 10 ° C, the treatment time becomes shorter, which is preferable from the viewpoint of production, but conversely, the higher the temperature, the more the evaporation amount of water It is so large that it becomes necessary to replenish water and the handling becomes complicated. Further, since it is possible to divert water of 80 ° C or higher which is used in other equipment in the factory, the temperature of the hydration treatment may be appropriately set within the range of 80 ° C to 10 ° C in consideration of these points. (Processing time of hydration treatment) Even if the treatment temperature of the hydration treatment is set within the range of 80 ° C to 100 ° C, if the treatment time is short, the hardness of the anodic oxide film is rather lowered, so it is necessary to specify the corresponding treatment. The minimum processing time of the temperature. Specifically, the hydration treatment can be carried out by satisfying the conditions of "treatment time (minutes) 2-1.5 X treatment temperature (°C) + 270"). The reason why the hardness of the anodized film changes due to the difference in the hydration treatment time is not fully explained, but the balance of the state change of the oxide of the anodized film caused by the hydration reaction and the volume expansion of the oxide may be considered. Not the cause. -10- 201030189 In addition, in the range where the treatment time of the hydration treatment satisfies the condition of "treatment time (minutes) 2-1·5 χ treatment temperature (°C) + 270", if it is extended as much as possible, the anodic oxidation coating Although the hardness of the film is high, on the other hand, there is a tendency that the crack density also slightly increases. Therefore, the treatment time may be appropriately set in accordance with the required performance. However, if the processing time is too long, the productivity is poor. Therefore, the treatment time of the hydration treatment is preferably 480 minutes or less, and more preferably 300 minutes or less. ❹ (treatment temperature of heat treatment) The temperature of the heat treatment is in the range of 120 ° C to 450 t. When the heat treatment temperature is less than 12 (TC), even if the heat treatment is performed to satisfy the treatment time of the "treatment time (minutes) 2-0. lx treatment temperature (°C) +71", the anodized film is not The reason for the increase in hardness is not fully explained, but it is considered that this is because the structural change of the anodized film accompanying the dehydration reaction after the hydration reaction is insufficient. On the other hand, if the temperature of the heat φ treatment is made When it exceeds 450 t, deformation of an aluminum alloy or the like as a substrate tends to occur, and dimensional tolerances of the product may deviate. Therefore, the temperature of the heat treatment is in the range of 120 ° C to 450 ° C. (Processing time of heat treatment) Even if the treatment temperature of the heat treatment is set to a range of 120 ° C to 45 ° ° C, if the treatment time is short, the hardness of the anodized film is calculated by Vickers hardness, and only increases by about Hv. 20 or less, and there is almost no The industrial significance of the heat treatment is implemented, so the minimum processing time corresponding to the processing temperature is specified -11 - 201030189. Specifically, as long as it satisfies the "processing time (minutes) 2 · 〇 · 1 Χ treatment The heat treatment may be carried out under the conditions of temperature (°C) +71". The reason for the change in the hardness of the anodized film depending on the heat treatment time may not be fully explained, but the dehydration reaction accompanying the hydration reaction may be considered. The structural change of the anodized film is not the cause. In addition, in the range where the processing time of the heat treatment satisfies the condition of "processing time (minutes) 2-0. lx processing temperature (°C) +71", if possible When the ground length is increased, the hardness of the anodized film is increased. On the other hand, the crack density tends to increase slightly. Therefore, it is only necessary to appropriately set the processing time in accordance with the required performance. However, if the processing time is too long, Since the productivity is inferior, the treatment time of the heat treatment is preferably 120 minutes or less, and more preferably 90 minutes or less. [Examples] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not at all described below. The embodiment is not limited, and may be appropriately modified and implemented within the scope of the gist of the present invention, and these modifications are all included in the present invention. First, the 606 1 aluminum alloy specified by JIS is melted to form an aluminum alloy cast mirror (size: 220mmWx250mmLxtl00mm, cold valley speed: 15~10 °C), and the ingot is cut to perform end face cutting (size·· 220mmWx 1 50mmLxt60mm), and then subjected to soaking treatment (540°C×4h). After the soaking treatment, the 60mm thick billet is rolled into a 6mm thick sheet by hot rolling, and cut (size: 220mmWx400mmLxt6mm) after -12-201030189. The solution treatment was carried out (510 to 520 tx30 min). Water quenching was carried out in the solid solution, and aging treatment (160 to 18 〇t: x8 h) was carried out to obtain an alloy plate. From the test alloy plate, 25 mm x 35 mm (rolling j t3 mm test piece was cut, and the surface was subjected to end face cutting. Then, it was immersed in a °C -1 〇% NaO Η aqueous solution for 2 minutes, then washed with water to enter 30 ° C -2 The mixture was immersed in a 0% ΗΝ〇3 aqueous solution for 2 minutes, then washed with water, and the surface of Φ was subjected to anodization under the conditions shown in Tables 1 to 4 to form an anodic oxide film on the surface of the test piece. The portion of the anodic oxide film was Further, the hydration treatment is carried out by immersing each test piece in pure water, and performing each hydration treatment temperature and each hydration treatment time shown in the hydration treatment. Further, heat treatment is performed on a part of the test piece. Each test piece was added, and it was carried out at each heat point shown in Tables 1 to 4 and each heat treatment time. ® The surface of each test piece produced by the method was observed by an optical microscope at a magnification of 400 times to determine the crack density. The photograph of the observation example is shown in Fig. 3. The crack density is obtained by measuring the total length of the cracks occurring in the range of 0.235 x 0.1 80 mm of each test piece, and converting the length sum in units of mm/mm 2 The next step ' Each test piece was buried in a resin, the anodic oxidation coating film is exposed 'and using Vickers hardness tester (Akashi, MVK-G2) the hardness of the central portion of the cross section of the electrode oxide film. For each test piece after the hydration treatment, after the measurement of each test piece, the test J direction) X is obtained, and at 60, the film thickness is 1 to 4, and the film thickness is above the Dali temperature. The surface of the microscope Ϊ] (When the thickness of the cross section of the mm 〇 was measured, the Vickers hardness was equal to or higher than the Vickers hardness of No. 1 which was not subjected to the hydration treatment. As a result, the anodic oxide film was high in hardness and was acceptable. In addition, when the Vickers hardness obtained by the measurement of each test piece after the heat treatment was higher than the Vickers hardness before the heat treatment Η v. 25 or more, the anodic oxide film was high hardness and was qualified. The test results are shown in Tables 1 to 4, and the relationship between the hydration treatment time and the hydration treatment temperature of No. 1 to No. 29 and the Vickers hardness, and the hydration treatment time and hydration of No. 32 to No. 43, respectively. The relationship between the treatment temperature and the Vickers hardness is shown in Fig. 1 'The relationship between the hydration treatment time and the hydration treatment temperature of No. 1 to No. 29 and the crack density, and the hydration treatment time and hydration treatment of No 32 to N 〇 43 The relationship between temperature and crack density is shown in Figure 2. 20103018 9 [1® Test results Crack density (mm/mm2) 〇〇ON Ο CN 卜CN (N 1〇Vickers hardness! (Hv.) 452 434 m 432 00 Os sm 574 in 00 ί—Η ... 522 Heat treatment heat treatment time (minutes) 1 1 1 1 1 I 1 sec 1 § (Ν Ο Heat treatment temperature (°C) 1 1 1 1 1 I 1 1 1 300 400 Ο m 400 Hydration treatment hydration treatment time (minutes) No hydration treatment 〇Ο § I 240 240 240 240 240 240 240 -1.5x treatment temperature +270 (minutes) hydration treatment temperature (°C) 〇rH film formation electrolytic current density (A/dm2) 〇CN treatment liquid temperature CO 〇 anodizing treatment liquid sulphuric acid 150g/L Remarks Comparative Example Comparative Example Comparative Example Comparative Example Comparative Example Embodiment Example Embodiment Example Example Comparative Example Comparative Example No. <N inch VO 〇〇 〇〇 ON CM mmm 'Ο Ρ ; -15- 201030189
CTS 試驗結果 [ 裂縫密度 (mm/mm2) 〇〇 Os 〇 〇 〇 f-H <N m \〇 〇〇 Γ 維氏硬度 (Hv.) 〇 (N t·^ 寸 寸 艺 ΓΟ Ό … in cn 熱處理 讓1| 1 1 1 1 1 1 1 1 ο \〇 s 熱處理 溫度 CC) 1 1 1 1 1 1 1 1 宕 〇 ΓΟ o 寸 水合處理 水合處理 時間 (分鐘） 沒有水合處理 S 〇 V% g y—^ Ο Ο 〇 CN o (N -1·5χ處理 溫度+270 (分鐘） 水合處理 溫度 ΓΟ 覆膜形成 _他$ $ Hi M J 〇 r4 處理液 溫度 (°C) 〇 陽極氧化 處理液 硫酸 150g/L 備註 比較例 比較例 比較例 比較例 比較例 實施例 實施例 實施例 實施例 實施例 實施例 1 〇 (N 2 00 CO 〇\ m o -16- 201030189 【ε·】 試驗結果 裂縫密度 (mm/mm2) 00 〇〇 ON On On 〇 〇 1—Η 2 ! 維氏硬度 (Hv.) 寸 <Ν 00 m 5 OO <Ν ν〇 寸 00 00 Os 寸 CO m OO ON m 熱處理 in 1 1 1 1 ( 1 I ( § 熱處理 溫度 CC) 1 1 1 1 1 1 1 1 ο m 〇 寸 水合處理 水合處理 時間 (分鐘） Ο g 〇 〇 ο o (N -1.5x處理 溫度+270 (分鐘） 沒有水合處理 水合處理 溫度 CC) § 覆膜形成 電解電 流密度 (A/dm2) 〇 處理液 溫度 (0〇 〇 陽極氧化 處理液 硫酸 150g/L 備註 比較例 比較例 比較例 比較例 比較例 實施例 實施例 實施例 實施例 實施例 1實施例 6 卜 00 Os 1—1 -17- 201030189CTS test results [fracture density (mm/mm2) 〇〇Os 〇〇〇fH <N m \〇〇〇Γ Vickers hardness (Hv.) 〇(N t·^ inch inch geisha Ό ... in cn heat treatment let 1 | 1 1 1 1 1 1 1 1 ο \〇s Heat treatment temperature CC) 1 1 1 1 1 1 1 1 宕〇ΓΟ o Inch hydration treatment hydration treatment time (minutes) No hydration treatment S 〇V% gy—^ Ο Ο 〇CN o (N -1·5χ treatment temperature +270 (minutes) hydration treatment temperature 覆 film formation _ he $ $ Hi MJ 〇r4 treatment liquid temperature (°C) 〇 anodizing treatment liquid sulfuric acid 150g / L Remarks Comparative Example Comparative Example Comparative Example Comparative Example Comparative Example Embodiment Example Example Example Example 1 N(N 2 00 CO 〇\ mo -16- 201030189 [ε·] Test result Crack density (mm/mm2) 00 〇〇 ON On On 〇〇1—Η 2 ! Vickers hardness (Hv.) inch <Ν 00 m 5 OO <Ν ν〇 inch 00 00 Os inch CO m OO ON m Heat treatment in 1 1 1 1 ( 1 I ( § Heat treatment temperature CC) 1 1 1 1 1 1 1 1 ο m Hydration treatment hydration treatment time (minutes) Ο g 〇〇ο o (N -1.5x treatment temperature +270 (minutes) without hydration treatment hydration treatment temperature CC) § Film formation electrolytic current density (A/dm2) 〇 treatment liquid temperature (0 〇〇 anodizing treatment liquid sulphuric acid 150g/L Remarks Comparative Example Comparative Example Comparative Example Comparative Example Comparative Example Embodiment Example Example 1 Example 6 Bu 00 Os 1-1 -17- 201030189
【寸®[inch®
試驗結果 裂縫密度 •J (mm/mm ) 00 00 00 00 OS Ο (N m m 維氏硬度 (Hv.) yn 00 m 〇 rj 〇 (N 寸 〇 m Os 熱處理 U ^ s 震您φ 1 1 1 1 1 1 1 1 1 熱處理 溫度 (°C) 1 1 1 1 1 1 1 1 1 水合處理 水合處理 時間 (分鐘） s § 1-H 〇 (N _1·5χ處理 溫度+270 (分鐘） 沒有水合處理 VO 沒有水合處理 1 rml 脚 8 Μ <n il e Ο 〇 覆膜形成 電解電 流密度 (A/dm2) 〇 CS 〇 — 處理液 溫度 rc) 〇 〇 1 陽極氧化 處理液 硫酸 150g/L 備註 比較例 比較例 比較例 比較例 比較例 比較例 比較例 比較例 比較例 (N -18- 201030189 . 根據表1~4’在使水合處理的處理溫度成爲80°C、90 °C、l〇〇°C時，作爲滿足“處理時間（分鐘）2_ΐ·5χ處理 溫度（°C ) +2 7 0 ”的條件的處理時間的滿足本發明的水合 處理的要件的發明例的 No.7〜No.9、No.14~No.16、 Νο·21〜Νο·23在試驗中得到的裂縫密度變高，維氏硬度滿 足合格評定標準。 另一方面，在使水合處理的處理溫度成爲 80 °C、90 φ °C、1〇〇 °C時，不滿足“處理時間（分鐘）之-1.5 X處理溫 度（°C ) +270 ” 的條件的 Ν〇.2~Ν〇·6、Ν〇·10~Ν〇·13、 No.17~Νο.20與作爲沒有實施水合處理的比較例的No.1 的維氏硬度相比，硬度變小。 另外，無論水合處理的處理溫度爲 70 °C的 Ν〇·24〜Νο·29是否滿足“處理時間（分鐘）2-1·5χ處理溫 度（t ) +2 70”的條件，與作爲沒有實施水合處理的比較 例的No. 1的維氏硬度相比，硬度變小。 Φ No. 30或No.31是利用過去的高硬度化方法（低溫、 高電流密度處理）形成陽極氧化覆膜的事例。維氏硬度與 No.7、8、15、16爲相同程度，但裂縫密度遠遠比其高， 極差。另一方面，No·2、3、10、11、17、18相當於重現 過去的裂縫密度的陽極氧化覆膜，如上所述，維氏硬度小 。就是說，通過使其滿足“處理時間（分鐘）2-1.5 X處理 溫度（°C ) +2 70”之類的水合處理的條件’可以形成硬度 高於利用以往方法形成的陽極氧化覆膜而且裂縫發生的方 面也沒有問題的陽極氧化覆膜。 -19- 201030189 另外，No. 3 2〜4 3是在水合處理之後實施熱處理的試 片。根據表1〜4,使熱處理的處理溫度成爲120 °C、3 00 °C 、40 0 °C，作爲滿足“處理時間（分鐘）2-0. lx處理溫度 (°C ) +7 1 ”的條件的處理時間的滿足本發明的熱處理的 要件的發明例的 Νο.32~Νο.34、Νο·38〜No.43在試驗中得 到的裂縫密度遠遠低於利用過去的高硬度化方法形成陽極· 氧化覆膜的No.30或No.31，不是成爲問題的發生密度， 另外，維氏硬度也滿足合格評定標準。 _ 另一方面，熱處理的處理溫度爲120°C、3 00°C、400 °C，但不滿足“處理時間（分鐘）2-0. lx處理溫度（t ) + 71”的條件的No.35~N〇.37與熱處理前相比，維氏硬度 沒有上升Hv.25以上。 如果歸納以上試驗結果，則可以確認通過以滿足本發 明的要件的條件製造半導體液晶製造裝置用表面處理構件 ，能夠利用簡便的方法形成硬度高於用以往方法形成的陽 極氧化覆膜而且在裂縫發生的方面也沒有問題的高硬度且 ❹ 低裂縫的平衡出色的陽極氧化覆膜。 【圖式簡單說明】 圖1是對實施例的試驗結果進行歸納的圖，是表示水 合處理時間及水合處理溫度與維氏（Vickers )硬度的關 係的曲線圖。 圖2是對實施例的試驗結果進行歸納的圖，是表示水 合處理的處理時間及處理溫度與裂縫密度的關係的曲線圖 -20- 201030189 圖3是表示在實施例中用光學顯微鏡以400倍的倍率 觀察試片的表面的觀察例的裂縫的發生狀況的顯微鏡照片Test results Crack density • J (mm/mm) 00 00 00 00 OS Ο (N mm Vickers hardness (Hv.) yn 00 m 〇rj 〇 (N inch 〇m Os heat treatment U ^ s shock you φ 1 1 1 1 1 1 1 1 1 Heat treatment temperature (°C) 1 1 1 1 1 1 1 1 1 Hydration treatment hydration treatment time (minutes) s § 1-H 〇 (N _1·5χ treatment temperature +270 (minutes) No hydration treatment VO No hydration treatment 1 rml foot 8 Μ <n il e Ο 〇 film formation electrolytic current density (A / dm2) 〇 CS 〇 - treatment liquid temperature rc) 〇〇 1 anodizing treatment liquid sulfuric acid 150g / L Remarks comparison comparison EXAMPLES Comparative Example Comparative Example Comparative Example Comparative Example Comparative Example Comparative Example (N -18- 201030189 . According to Tables 1 to 4', when the treatment temperature of the hydration treatment is 80 ° C, 90 ° C, and 10 ° C No. 7 to No. 9 and No. No. 7 to No. 9 of the invention example satisfying the requirements of the hydration treatment of the present invention as the processing time for satisfying the condition of "treatment time (minutes) 2_ΐ·5χ treatment temperature (°C) + 2 70 ”) .14~No.16, Νο·21~Νο·23 The crack density obtained in the test becomes high, and the Vickers hardness is satisfied. On the other hand, when the treatment temperature of the hydration treatment is 80 °C, 90 φ °C, 1 ° °C, the processing time (minutes) -1.5 X treatment temperature (°C) is not satisfied.维.2~Ν〇·6, Ν〇·10~Ν〇·13, No.17~Νο.20 of the condition of +270 ” and Vickers hardness of No. 1 as a comparative example without hydration treatment In addition, the hardness becomes small. In addition, whether the treatment temperature of hydration treatment is 70 °C Ν〇·24~Νο·29 satisfies “treatment time (minutes) 2-1·5χ treatment temperature (t) +2 70” The condition is smaller than the Vickers hardness of No. 1 which is a comparative example in which the hydration treatment is not performed. Φ No. 30 or No. 31 is a method using high hardness in the past (low temperature, high current density treatment) An example of forming an anodized film. The Vickers hardness is the same as No. 7, 8, 15, and 16, but the crack density is much higher than that of the film. On the other hand, No. 2, 3, and 10. 11, 17, 18 is equivalent to an anodized film which reproduces the density of the crack in the past, as described above, the Vickers hardness is small. That is, by satisfying it Treatment time (minutes) 2-1.5 X treatment temperature (°C) +2 70" conditions such as hydration treatment can form a hardness higher than that of the anodized film formed by the conventional method and there is no problem in the occurrence of cracks. Anodized film. -19- 201030189 In addition, No. 3 2 to 4 3 are test pieces subjected to heat treatment after hydration treatment. According to Tables 1 to 4, the heat treatment treatment temperature is 120 °C, 300 °C, and 40 °C, as the "treatment time (minutes) 2-0. lx treatment temperature (°C) + 7 1" The processing time of the condition is satisfied. The crack density obtained in the test of the invention examples of the heat treatment requirements of the present invention is much lower than that obtained by the conventional high hardness method. No. 30 or No. 31 of the anode/oxide film is not a problem occurrence density, and the Vickers hardness also satisfies the conformity assessment standard. _ On the other hand, the heat treatment treatment temperature is 120 ° C, 300 ° C, 400 ° C, but does not meet the "treatment time (minutes) 2-0. lx treatment temperature (t) + 71" conditions of the No. Compared with before heat treatment, 35~N〇.37 did not increase the Vickers hardness by more than Hv.25. When the results of the above tests are summarized, it can be confirmed that the surface treatment member for a semiconductor liquid crystal manufacturing apparatus can be manufactured by satisfying the requirements of the present invention, and the hardness can be formed by a simple method higher than that of the anodized film formed by the conventional method and occurring in the crack. In terms of the aspect, there is no problem with the high hardness and low crack balance of the excellent anodized film. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph summarizing the test results of the examples, and is a graph showing the relationship between the hydration treatment time and the hydration treatment temperature and the Vickers hardness. 2 is a graph summarizing the test results of the examples, showing a relationship between the treatment time of the hydration treatment and the treatment temperature and the crack density. FIG. 20 - 201030189 FIG. 3 is a view showing an optical microscope 400 times in the embodiment. Microscopic photograph of the occurrence of cracks in the observation example of the surface of the test piece
-21 --twenty one -