201040317 六、發明說明： 【發明所屬之技術領域】 本發明是有關於一種金屬植入物之表面處理方法，特 別是能於金屬植入物表面形成微米級粗糙孔洞，並生成一 層均勻氧化層之表面處理方法。 【先前技術】 〇 目刖，在金屬植入物（implant)表面形成多孔結構的 方法有多種’如：嘴砂法（sand blasting)或酸餘法（&别 etching)，透過上述方法可使金屬植入物的表面粗糙度增 加產生具有均勻粗链度的植體表面’以促進與植入區域 周圍的骨組織聯結。 舉例來說，美國專利字號US6,491，723揭露一種金屬 植入物的表面處理方法，其表面處理步驟係先利用氫氟萨 O (HF)進行第一次酸蝕，用以去除表面自然氧化層；再以言 溫的硫酸(H2S〇4)/鹽酸(HC1)混合液進行第二次酸蝕，邢成 不規則且均勻的表面。 然而氫氟酸是極危險的化學品，可經由口、急 异、眼或 皮膚等途徑進入人體，造成低血鈣、低血鎂、肺水腫一、 謝性酸中毒、心室性心律不整、甚至死亡等嚴重的全身= 中毒症狀。而硫酸/鹽酸混合液為兩種強酸之混人 ^ σ，在配製 201040317 時會產生劇烈放熱的脫水反應，a ‘令易使操作人員造成灼傷。 【發明内容】 有鑑於此，本發明提供— 法，用以降低表面處理過程中對/植入物的表面處理方 並增加生物相容性之效果。 趙有危險傷害的機會， 本發明另提出一種金屬植入物 ο 植入物之表面具有-第-氧化層，其：驟：方法，金屬 金屬植入物浸泡於一第一酸液中/、乂匕.首先，將 後，將浸泡於第-酸液中之金屬桔M去除第—氧化層。之 入物浸泡於一第二酸液中，第二龄、 冉把金屬植 夜包含一過氧化翁，用 以粗縫化金屬植入物之表面並形成7 將金屬植入物自第二酸液中取出。 氧化層。最後’ 在本發明一實施例中，其中 10mn。 二氧化層之厚度大於 在本發明一實施例中’其中金 金屬、一鈦合金或一含鈦元素之金屬物之材質為一鈦 在本發明一實施例中，其中筮— 一鹽酸。〜料更包括-硫酸或 在本發明一實施例中，其中當第_ * 、 硫酸的混合酸時，其混合酸中的過氣：，液為過氧化氫與 氧與硫酸之體積比 為1 : 1 : 1，其中過氧化氫的濃度為3〇% ’硫酸的濃度 為 95%。 & 201040317 在本發明一實施例中，其中當第二酸液為過氧化氫與 鹽酸的混合酸時’其混合酸中的過氧化氫與鹽酸之體積比 為1 : 1〜6 : 1，其中過氧化氫的濃度為30%，鹽酸的濃度 為 37%。 在本發明一實施例中，其中浸泡於第一酸液之時間為 數分鐘至60分鐘。 在本發明一實施例中，其中浸泡於第二酸液之時間為 數分鐘至24小時。 〇 在本發明一實施例中，其中浸泡於第一酸液時之處理 溫度為60。(：至。 在本發明一實施例中’其中浸泡於第二酸液時之處理 溫度為20。(：至8(rc。 在本發明—實施例中’其中第一酸液係選自由硝酸、 鹽酸與硫酸所組成之群組。 在本發明一實施例中’其中金屬植入物浸泡於該第一 〇 .、時其表面形成複數微米級的粗繞孔洞。 在本發明—實_中，其中形成於該金屬植入物表面 氧化層之表面粗糙度(尺&值)約為0 3〜0 7pm。 综上所述，本發明首先以高溫的鹽酸或硫酸進行鈦金 屬植入物表面粗縫化處理，使其具有微米級的孔洞。此階 段主要是利用鹽酸或硫酸來取代具有高危險性之氫氟酸進 行第—次酸蝕’並同時製造粗糙表面。並以室溫下溫和反 應的過氧化氫(H2〇2)/硫酸（H2S04)混合液’取代高溫操 201040317 作產生劇烈反應的鹽酸/硫酸混合液進行第二次酸蝕，如 此，可降低對人體有危險傷害的機會。 為讓本發明之上述特徵和優點能更明顯易懂，下文特 舉實施例，並配合所附圖式，作詳細說明如下。 【實施方式】 圖1疋本發明一實施例之金屬植入物表面處理方法的 流程圖。其中，金屬植入物之材質可為一鈦金屬、一鈦合 Ο 金或一含鈦元素之金屬，而這些金屬植入物與空氣接觸 後，其表面通常都具有一氧化層，此氧化層可為一氧化鈦 層（Ti02)。 請參閱圖1，金屬植入物表面處理的方法包括以下步 驟：首先，進行一第一次酸蝕處理（步驟S100)，係將金 屬植入物浸泡於重量百分比為37%的鹽酸(HC1)溶液中，其 中金屬植入物可以是完全浸泡或局部浸泡於上述鹽酸(HC1) 〇 溶液，以去除金屬植入物表面氧化層，並於表面形成複數 微米級的粗糙孔洞，而有關第一次酸蝕處理的操作參數， 可以是讓金屬植入物在溫度為60〜8〇。〇的鹽酸溶液中作 用數分鐘至60分鐘，於本實施例，金屬植入物於鹽酸溶液 中之作用時間為1G〜3G分鐘。接著，將金屬植人物依序進 行潤洗與中和的程序，其中潤洗程序可以採用超純水進行 清洗並濕潤。 201040317 第一次酸蝕處理（步驟S100)之後，進行一第二次酸 蝕處理（步驟S200)，即將經過鹽酸酸蝕並中和處理過的 金屬植入物，浸泡於一混合酸當中。其中，混合酸可為過 氧化氫(3 0%)/硫酸(95%)的混合酸或是過氧化氫(3 0%)/鹽酸 (37%)的混合酸。 須特別說明的是’過氧化氫(3〇%)/硫酸(95%)的混合酸 為等體積比例混合或是不同體積比例混合，其中較佳的是 0 過氧化氫與硫酸之體積比為1 : 1〜,6 : 1。同理，過氧化氫 (3 0%)/鹽酸(3 7%)的混合酸為等體積比例混合或是不同體 積比例混合，其中較佳的是過氧化氫與鹽酸之體積比為j : 1 〜6 : 1。 有關第二次酸钱處理的操作參數，可以是讓金屬植入 物在室溫的混合酸溶液中作用數分鐘至24小時，於本實施 例，金屬植入物於混合酸溶液中之作用時間為_1()分鐘，最 ❹後再進行潤洗、中和以及風乾等動作，其中潤洗程序可以 採用超純水進行清洗並濕潤。 經第二次酸蝕處理過後的金屬植入物，其表面會形成 一第二氧化層’此第二氧化層可為—氧化鈦層（Ti〇2)。其 中，須特別說明的是經酸餘處理後所產生的氧化層厚度， .、大】、為大於l〇nm’與金屬植入物經酸蝕處理前所產生的 自然氧化層厚度有明顯差別。 請分別參閱圖2A及圖2B，其分別為經上述流程處理 201040317 後之金屬植入物的表面 ㈣…倍。如圖2二：_:倍率分別為 面是由複數個呈現略尖的錐狀單；現金屬植入物表 粗链表面，各錐狀單體之_略相距 (Ra值）約為〇.3~〇 7叫。 田祖梭度 本圣月之第一階段酸蝕步驟主 第一酸液，如鹽酸，來取袂气恤的 來取代虱鼠酸進行表面自然氧化層的 Ο201040317 VI. Description of the Invention: [Technical Field] The present invention relates to a surface treatment method for a metal implant, in particular, a micron-scale rough hole can be formed on the surface of a metal implant, and a uniform oxide layer is formed. Surface treatment method. [Prior Art] At the same time, there are various methods for forming a porous structure on the surface of a metal implant, such as sand blasting or acid extraction (&etching). The increased surface roughness of the metal implant produces an implant surface with a uniform thick chain to promote bonding with bone tissue surrounding the implanted area. For example, U.S. Patent No. 6,491,723 discloses a surface treatment of a metal implant, the surface treatment step of which is first acid etching using hydrofluoric O (HF) to remove surface oxidation. The layer is further subjected to a second acid etching with a mixture of sulfuric acid (H2S〇4)/hydrochloric acid (HC1), which is an irregular and uniform surface. However, hydrofluoric acid is a very dangerous chemical that can enter the body through mouth, irritability, eye or skin, causing hypocalcemia, hypomagnesemia, pulmonary edema, hallucinogenic acidosis, ventricular arrhythmia, and even Severe systemic death such as death = symptoms of poisoning. The sulfuric acid/hydrochloric acid mixture is a mixture of two strong acids ^ σ, which will produce a vigorous exothermic dehydration reaction when formulated in 201040317, a ‘easy to cause burns to the operator. SUMMARY OF THE INVENTION In view of the above, the present invention provides a method for reducing the surface treatment of an implant/implant during surface treatment and increasing the biocompatibility effect. Zhao has the opportunity to be in danger of injury. The present invention further provides a metal implant. The surface of the implant has a --oxide layer. The method: the metal metal implant is immersed in a first acid solution. First, after that, the metal oxide M immersed in the first acid solution removes the first oxide layer. The material is immersed in a second acid solution, and the second age, strontium metal contains a peroxide, used to roughen the surface of the metal implant and form 7 metal implant from the second acid Remove from the liquid. Oxide layer. Finally, in an embodiment of the invention, 10 nm is therein. The thickness of the dioxide layer is greater than that in the embodiment of the present invention, wherein the metal material, the titanium alloy or the metal material containing a titanium element is a titanium material. In one embodiment of the invention, the hydrazine-hydrochloric acid. The material further includes sulfuric acid or in an embodiment of the present invention, wherein when the mixed acid of the _* and sulfuric acid is mixed with the excess gas in the acid: the liquid is hydrogen peroxide and the volume ratio of oxygen to sulfuric acid is 1 : 1 : 1, wherein the concentration of hydrogen peroxide is 3〇% 'the concentration of sulfuric acid is 95%. & 201040317 In an embodiment of the present invention, wherein when the second acid liquid is a mixed acid of hydrogen peroxide and hydrochloric acid, the volume ratio of hydrogen peroxide to hydrochloric acid in the mixed acid is 1: 1 to 6: 1. The concentration of hydrogen peroxide was 30%, and the concentration of hydrochloric acid was 37%. In an embodiment of the invention, the time during which the first acid is immersed is from several minutes to 60 minutes. In an embodiment of the invention, the time during which the second acid solution is immersed is from several minutes to 24 hours. In one embodiment of the invention, the treatment temperature when immersed in the first acid solution is 60. (Into. In one embodiment of the invention, the treatment temperature in which the second acid solution is immersed is 20. (: to 8 (rc. In the present invention - the embodiment wherein the first acid liquid is selected from the group consisting of nitric acid And a group consisting of hydrochloric acid and sulfuric acid. In an embodiment of the invention, wherein the metal implant is immersed in the first crucible, the surface forms a plurality of micron-sized thick wound holes. In the present invention - the actual The surface roughness (foot & value) formed on the surface oxide layer of the metal implant is about 0 3 to 0 7 pm. In summary, the present invention firstly performs titanium metal implant with high temperature hydrochloric acid or sulfuric acid. The surface is roughened to have micron-sized pores. This stage mainly uses hydrochloric acid or sulfuric acid to replace the high-risk hydrofluoric acid for the first etching and simultaneously produces a rough surface. The mildly reacted hydrogen peroxide (H2〇2)/sulfuric acid (H2S04) mixture replaces the high temperature operation 201040317 for the second reaction of the hydrochloric acid/sulfuric acid mixture which produces a violent reaction, thus reducing the risk of harm to the human body. Opportunity. To make the invention The features and advantages can be more clearly understood. The following detailed description of the embodiments, together with the drawings, will be described in detail below. [Embodiment] FIG. 1 is a flow chart of a metal implant surface treatment method according to an embodiment of the present invention. The metal implant may be made of a titanium metal, a titanium alloy or a titanium-containing metal. When the metal implant is in contact with air, the surface of the metal implant usually has an oxide layer. The layer may be a titanium oxide layer (Ti02). Referring to Figure 1, the metal implant surface treatment method comprises the following steps: First, performing a first acid etching treatment (step S100), soaking the metal implant In a 37% by weight hydrochloric acid (HC1) solution, the metal implant may be completely immersed or partially immersed in the above hydrochloric acid (HC1) hydrazine solution to remove the surface oxide layer of the metal implant and form a plurality of layers on the surface. Micron-scale rough holes, and the operating parameters for the first acid etching treatment may be to allow the metal implant to act for several minutes to 60 minutes in a hydrochloric acid solution at a temperature of 60 to 8 Torr. The action time of the metal implant in the hydrochloric acid solution is 1 G~3 G minutes. Then, the metal planting character is sequentially washed and neutralized, wherein the washing process can be washed and moistened with ultrapure water. After the first acid etching treatment (step S100), a second etching treatment (step S200) is performed, that is, the metal implant which has been subjected to hydrochloric acid etching and neutralization treatment is immersed in a mixed acid. The mixed acid may be a mixed acid of hydrogen peroxide (30%) / sulfuric acid (95%) or a mixed acid of hydrogen peroxide (30%) / hydrochloric acid (37%). The mixed acid of (3〇%)/sulfuric acid (95%) is mixed in an equal volume ratio or mixed in different volume ratios, and preferably 0 is a volume ratio of hydrogen peroxide to sulfuric acid of 1:1~6:1. Similarly, the mixed acid of hydrogen peroxide (30%) / hydrochloric acid (3 7%) is mixed in equal volume ratio or mixed in different volume ratios, wherein the volume ratio of hydrogen peroxide to hydrochloric acid is preferably j: 1 ~6: 1. The operating parameter for the second acid treatment may be that the metal implant is allowed to act in a mixed acid solution at room temperature for several minutes to 24 hours. In this embodiment, the action time of the metal implant in the mixed acid solution For _1 () minutes, the most sputum is followed by washing, neutralization and air drying, etc., where the washing process can be washed and moistened with ultrapure water. After the second etching treatment, the metal implant has a second oxide layer formed on its surface. The second oxide layer may be a titanium oxide layer (Ti〇2). Among them, it should be specially stated that the thickness of the oxide layer produced by the acid residue treatment is significantly different from that of the metal oxide before the acid etching treatment. . Please refer to FIG. 2A and FIG. 2B respectively, which are the surface (4) times of the metal implant after the process of 201040317. As shown in Fig. 2: _: The magnification is a cone-shaped single surface which is slightly pointed by a plurality of faces; the surface of the thick metal chain of the current metal implant is slightly parallel (Ra value) about 〇. 3~〇7 is called. Tian Zusuo This is the first stage of the acid etching step of the holy month. The first acid solution, such as hydrochloric acid, is used to replace the scorpion acid to replace the surface natural oxide layer.
去除，姐表面製造微米級的_孔洞，而第二階段酸姓 步驟主要是以第二酸液’如在室溫下的過氧化氫/硫酸混合 液’進行第二錢域理，進行去氧化崎氧域理，使金 屬植入物表面生成-層均勻純淨的氧化層。如此，不僅可避免 在使用酸液或配製酸液時產生的劇烈反應，減少危險性， 且金屬植人物表面生成-層均勻純淨的氧化層，可用以增加植 入物之生物相容性。雖然本發明以前述實施例揭露如上，然 其並非用以限定本發明，任何熟習相關技藝者，在不脫離 本發明之精神和範圍内，所作更動與潤飾之等效替換，仍 為本發明之專利保護範圍内。 【圖式簡單說明】 圖1是本發明金屬植入物表面處理方法的流程圖；以及 圖2Α及圖2Β是金屬植入物的表面SEM圖。 【主要元件符號說明】 S100、S200步驟流程Removal, the surface of the sister is made of micron-sized holes, and the second stage of the acid surname is mainly based on the second acid solution, such as hydrogen peroxide/sulfuric acid mixture at room temperature, for deoxidation. The surface of the metal implant produces a uniform and pure oxide layer on the surface of the metal implant. In this way, not only the violent reaction generated when using the acid solution or the acid solution is avoided, the risk is reduced, and the surface of the metal implant has a uniform and pure oxide layer, which can be used to increase the biocompatibility of the implant. While the present invention has been described above in the foregoing embodiments, it is not intended to limit the invention, and the equivalents of the modification and retouching are still in the present invention without departing from the spirit and scope of the invention. Within the scope of patent protection. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart showing a surface treatment method of a metal implant of the present invention; and Fig. 2A and Fig. 2B are surface SEM images of a metal implant. [Main component symbol description] S100, S200 step flow