201041565 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及其表面處理的方 法，且特別是有關於一種表面型態為大凹洞裡具有小凹洞 的金屬植入物及其表面處理的方法。 【先前技術】 f ) 目前，在金屬植入物（implant)表面形成多孔結構的 方法有多種，例如：喷砂法（sand blasting )或酸#法（acid etching )，透過上述方法可使金屬植入物的表面粗糙度增 加，如此可利於金屬植入物植入生物體内後細胞攀附促使 傷口癒合時間縮短。 舉例來說，美國專利號US5456723揭示一種金屬植入 物的表面處理方法，其處理步驟為利用一粒徑大小為 ^ 250〜500 μιη的金剛石砂進行喷砂後，再以高溫的硫酸 (H2S〇4)/鹽酸(HC1)混合液進行酸蝕，以粗糙化金屬植入物 的表面。 然而使用粒徑大小為250〜500μιη的金剛石砂進行喷砂 處理，大顆粒的金剛砂對於金屬植入物的外螺紋型態會有 一定程度的破壞效果。此外，硫酸/鹽酸混合液為兩種強酸 之混合，在配製時會產生劇烈的放熱脫水反應，具對操作 201041565 人員造成灼傷的危險性。 更者，美國專利字號US5603338揭露另一種金屬植入 物的表面處理方法，其表面處理步驟為是先利用喷砂方法 使鈦金屬植入物表面粗糙化後，接著以氫氟酸(HF)進行第 -人s文蝕，用以去除表面自然氧化層（厚度為 Angstroms)，最後再以高溫的硫酸鹽酸(hci)混合 液進行第二次酸餘’形成金屬植人物不規則且均勻的表面。 Γ) 」而上述所使用的酸液為氫i酸，熟知氫氣酸此一化 學品的人都知道氫I酸為一極危險的化學品，如：氮氣酸 可呈由 |眼或皮膚等途徑進入人體’造成低血鮮、 低血鎂、肺水腫、代謝性酸中毒、心室性心律不整、甚至 亡等嚴重的王身性中毒症狀。此外，第二次酸液為使用 硫酸/鹽酸軌合液，此混合液在配料會產生劇烈放熱的 脫水反應’容易使操作人員造成灼傷。 從上述知，目前常見的金屬植入物的表面處理方法， ，，是使用大顆粒的噴砂體’以破壞金屬植人物的螺紋 型態’就是使用多次的酸餘步驟或是採用具有危險性的酸 餘液’以達到增加表面粗糙度’然而，實際上使用上述方 法均暗藏對人體有危險傷 害的機會。 【發明内容】 有釔於此，本發明提供一種金屬植入物，其表面型態 201041565 為大凹洞裡具有小凹洞，透過此表面型態，可達到金屬植. 入物與生物體間的骨整合效果。 另外，本發明另提供一種金屬植入物的表面處理的方 法，係利用喷砂搭配適當的酸蝕液，降低對人體有危險傷 害的機會。 本發明提出一種金屬植入物，其表面具有複數個微米 級凹洞，且微米級凹洞内更具有複數個次微米級凹洞，其 中微米級凹洞之孔徑介於Ιμπι〜ΙΟΟμιη之間，次微米級凹洞 之孔徑介於100nm〜lOOOnm之間，且金屬植入物的表面平 均粗糙度介於0.1 μπι〜5μιη之間。 在本發明一實施例中，其中所述的金屬植入物之材質 為一鈦金屬、一鈦合金或一含欽元素之金屬。 在本發明一實施例中，其中所述的微米級凹洞係藉由 一喷砂'處理所產生。 在本發明一實施例中，其中所述的次微米級凹洞係藉 〇 由一去氧化再氧化處理所產生。 本發明另提出一種金屬植入物的表面處理方法，包 括：首先，以一砂體對一金屬植入物的表面進行一喷砂處 理，以形成複數個微米級凹洞。之後，將喷砂處理後的金 屬植入物浸泡於一含過氧化氫的複合酸中，進行一去氧化 再氧化處理，以形成至少一次微米級凹洞位於該些微米級 凹洞内並形成一氧化層。最後，將該金屬植入物於該酸液 中取出。 5 .201041565 在本發明一實施例中 為一鈦金屬、一鈦合金或 在本發明一實施例中 在本發明一實施例中 酸或一鹽酸。 在本發明一實施例中 或二氧化鈦。 在本發明一實施例中 ，其中所述的金屬植入物之材質 、> #之金屬。 一含妹 ，其中所述的氧化層為一氧化鈦。 丫其中所述的複合酸更包括-硫 其中所述的砂體材質為氧化鋁 其中戶斤述的砂體的粒度為小於 Ο 〇 200μιη 以下。 在本發明一實施例中’ 該金屬植入物之距離為1〜5 在本發明一實施例中’ 為 2〜4 Kg/cm2。 在本發明一實施例中， 20秒至40秒。 在本發明一實施例中’ 之時間為10分鐘至24小時 在本發明一實施例中， 之溫度為20°C至80°C。 在本發明一實施例中， 介於Ιμπι〜ΙΟΟμιη之間。 在本發明一實施例中， 徑介於100nm〜lOOOnm之間 進行该噴砂處理時，該砂體與 公分。 ^ 其中所述的喷砂處理時之壓力 其中所述的喷砂處理之時間為 其中所述的去氧化再氧化處理 〇 其中戶斤述的去氧化再氧化處理 中戶斤述的微米級凹洞之孔徑 其1f 中戶斤述的次微米級凹洞之孔 其1f 6 201041565 綜上所述，本發明首先以粒徑200μιη以下的砂體對金 屬植入物的表面進㈣砂處理，其達_有表面粗链化之 效果，又保留金屬植入物原先設計的表面型態。 接著，在室溫下以温和反應的過氧化氯(Η2〇2)/硫酸 (h2so4)混合液’取代高溫操作產生劇烈反應的硫酸 (h2so·酸(HC1)混合液進行去氧化再氧化處理，如此可 降低對人體有危險傷害的機會。 Ο 因此，透過上述的方法’金屬植人物可以先在嗔砂肩 理後產生微米級寬度。之後再透過去氧化 步驊’在喷砂處理後所產生的微米級（mierG)寬 洞裡，再侧出均勻次微米級（sub_mieron)寬度之:/ 如此可得到大凹洞裡具有小凹洞之 ，1 /同 高金屬植人物表面孔洞結構的變化 :^•樣不僅痴 化亦同樣達到骨整合之效果。 t〗洞結構的養201041565 VI. Description of the Invention: [Technical Field] The present invention relates to a metal implant and a method of surface treatment thereof, and in particular to a metal having a surface type of a small recess having a large recess Implants and methods of surface treatment thereof. [Prior Art] f) At present, there are various methods for forming a porous structure on the surface of a metal implant, for example, sand blasting or acid etching, which can be made by the above method. The surface roughness of the implant is increased, which is advantageous for the cell clinging to shorten the wound healing time after the metal implant is implanted into the living body. For example, U.S. Patent No. 5,456,723 discloses a surface treatment method for a metal implant which is blasted with diamond sand having a particle size of 250 to 500 μm and then subjected to high temperature sulfuric acid (H2S〇). 4) / Hydrochloric acid (HC1) mixture is acid etched to roughen the surface of the metal implant. However, diamond sand having a particle size of 250 to 500 μm is used for sand blasting, and large particles of diamond have a certain degree of damage to the external thread type of the metal implant. In addition, the sulfuric acid/hydrochloric acid mixture is a mixture of two strong acids, which produces a strong exothermic dehydration reaction during preparation, posing a risk of burns to personnel operating in 201041565. In addition, U.S. Patent No. 5,603,338 discloses a surface treatment method for another metal implant. The surface treatment step is to first roughen the surface of the titanium metal implant by sand blasting, followed by hydrofluoric acid (HF). The first human etch is used to remove the surface natural oxide layer (the thickness is Angstroms), and finally the second acid residue is formed with a high temperature sulfuric acid hydrochloric acid (hci) mixture to form an irregular and uniform surface of the metal implant. Γ)) The acid used in the above is hydrogen i acid. Anyone who is familiar with hydrogen acid is aware that hydrogen acid is a very dangerous chemical. For example, nitrogen acid can be formed by eye or skin. Entering the human body's symptoms of severe blood stasis, low blood magnesium, pulmonary edema, metabolic acidosis, ventricular arrhythmia, and even death. In addition, the second acid solution uses a sulfuric acid/hydrochloric acid ore solution, which produces a highly exothermic dehydration reaction in the formulation, which is liable to cause burns to the operator. From the above, the current surface treatment method for metal implants is to use a large particle blasting body to destroy the thread shape of the metal implanted character. The acid residue 'to achieve increased surface roughness' However, in fact, the above methods are used to hide the opportunity for dangerous damage to the human body. SUMMARY OF THE INVENTION Accordingly, the present invention provides a metal implant having a surface pattern of 201041565 having a small recess in a large recess through which a metal implant can be achieved between the implant and the living body. The osseointegration effect. In addition, the present invention further provides a method of surface treatment of a metal implant by using sandblasting in combination with an appropriate acid etching solution to reduce the risk of dangerous injury to the human body. The invention provides a metal implant having a plurality of micrometer-scale pits on its surface, and a plurality of submicron-sized pits in the micron-sized cavity, wherein the pore size of the micron-sized cavity is between Ιμπι~ΙΟΟμιη, The pore size of the sub-micron-sized cavity is between 100 nm and 100 nm, and the surface roughness of the metal implant is between 0.1 μm and 5 μm. In an embodiment of the invention, the metal implant is made of a titanium metal, a titanium alloy or a metal containing a chin element. In an embodiment of the invention, the micron-sized cavity is produced by a sandblasting process. In an embodiment of the invention, the sub-micron-sized cavity is produced by a deoxidation reoxidation process. The invention further provides a surface treatment method for a metal implant, comprising: first, sandblasting a surface of a metal implant with a sand body to form a plurality of micron-sized cavities. Thereafter, the blasted metal implant is immersed in a composite acid containing hydrogen peroxide, and subjected to a deoxidation and reoxidation treatment to form at least one micron-sized cavity in the micron-sized cavity and formed. An oxide layer. Finally, the metal implant is taken out of the acid solution. 5.201041565 In one embodiment of the invention is a titanium metal, a titanium alloy or, in an embodiment of the invention, an acid or monohydrochloric acid in an embodiment of the invention. In an embodiment of the invention or titanium dioxide. In an embodiment of the invention, the metal implant material, ># metal. A sister, wherein the oxide layer is titanium oxide. The composite acid described therein further comprises - sulfur, wherein the sand body material is alumina, wherein the particle size of the sand body is less than Ο 〇 200 μιη. In an embodiment of the invention, the metal implant has a distance of from 1 to 5 in an embodiment of the invention of '2 to 4 Kg/cm2. In an embodiment of the invention, 20 seconds to 40 seconds. In one embodiment of the invention, the time is from 10 minutes to 24 hours. In one embodiment of the invention, the temperature is from 20 ° C to 80 ° C. In an embodiment of the invention, between Ιμπι~ΙΟΟμιη. In an embodiment of the invention, the sand body is divided into centimeters when the diameter is between 100 nm and 100 nm. ^ The pressure during the blasting treatment, wherein the blasting treatment time is the micro-scale cavity in which the deoxidation and reoxidation treatment is carried out in the deoxidation and reoxidation treatment The hole of the sub-micron-sized cavity of the 1f of the 1f 6 201041565. In summary, the present invention firstly treats the surface of the metal implant with a sand body having a particle diameter of 200 μm or less. _The effect of surface thickening, while retaining the surface shape originally designed by metal implants. Then, at room temperature, a mild reaction of sulfuric acid (Η2〇2)/sulfuric acid (h2so4) mixture is used to replace the high-temperature operation of sulfuric acid (h2so·acid (HC1) mixture for deoxidation and reoxidation treatment. This can reduce the chance of dangerous harm to the human body. Ο Therefore, through the above method, the metal implanted person can first produce a micron-scale width after the sand-sanding shoulder, and then pass through the deoxidation step 骅 after the sandblasting process. In the micro-scale (mierG) wide hole, the width of the sub-mieron is evenly distributed: / so that the small hole in the large cavity can be obtained, and the surface structure of the 1/high-metal implant is changed: ^• The sample not only achieves the effect of osseointegration.
為讓本發明之上述特徵和 舉實施例’並配合所附圖式， 優點能更明顯易懂 作詳細說明如下。 下文特 【實施方式】 圖1是本發明金屬植入物表 參閱圖1，金屬措人_面*處 流程圖。請 屬植入物表面處理的方法句妊.芬^ -喷砂處理(步驟S100) ’也就是說，以一砂體’ 入物表面係具有複數個微魏_。 錢的金屬植 7 .201041565 本㈣㈣砂處㈣步㈣將已細動旨、清潔程序 後的金屬植入物以粒徑200μιη以下的陶竟砂體(如氧化銘 砂、二氧化欽砂)進行喷砂，喷砂壓力為2〜4Kg/cm2，喷砂 距離為卜5公分，喷砂時間為20〜40私、，其中金屬植入物 之材質可為-鈦金屬、-鈦合金或一含鈦元素之金屬。 之後，進行一去氧化再氧化處理（步驟S2〇〇)，即將 喷砂處理後的金屬植入物浸泡於一含過氧化氫的複合酸 〇 中，以开>成至少一-人微米級凹洞位於該些微米級凹洞内並 形成一氧化層，氧化層可為一氧化鈦層。須特別說明的是， 上述含過氧化氫的複合酸可為一硫酸與過氧化氫的混合酸 或一鹽酸與過氧化氫的混合酸。 於本實施例’去氧化再氧化處理步驟（步驟S100)為 將已清潔處理、喷砂、清潔處理過的金屬植入物，浸泡於 以等體積比例混合的過氧化氫（30%)/硫酸（98%)混合液 中’在至溫下作用12〜24小時，最後再潤洗、中和、風乾。 €J 上述的室溫溫度範圍較佳為2(TC至35°C。在其他應用上， 去氧化再氧化處理亦可於高溫下作用約10分鐘至1小時， 上述的高溫溫度範圍較佳為60°C至80。(：。 最後’將該金屬植入物於該酸液中取出。如此，透過 喷砂處理與去氧化再氧化處理後，金屬植入物的表面可產 生「大凹洞裡具有小凹洞」之表面型態。也就是說，大凹 洞為微米級凹洞，小凹洞為次微米級凹洞，微米級凹洞之 孔徑介於1μιη〜1〇〇μπι之間，次微米級凹洞之孔徑介於 201041565 lOOnm〜lOOOnm 之間。 请分別參閱圖2A及圖2B，其分別為經上述流程處理 後之金屬植入物的表面SEM圖，其SEm圖倍率分別為 2500倍及5K倍。如圖2A所示，金屬植入物的表面由喷 砂後所形成的微米級（1〜1〇〇 μπι)大凹洞。如圖2B所示，金 屬植入物的表面具有去氧化再氧化處理後所產生的次微米 級（100〜1000 nm)小凹洞。 綜上所述，本發明的方法首先為利用粒徑2 00μ m以下 的砂體進行噴石少處理，藉此可以改進傳統上使用大粒徑 (250〜500μηι)砂體進行喷砂處理所造成金屬植入物表面螺 、、文5L態改邊的缺點，以達到既有表面粗縫化之效果，又保 留金屬植入物原先設計的表面型態。 ^此外’使用過氧化氫(Η202)/硫酸(h2so4)混合液，取代 冋'皿操作產生劇烈反應的硫酸(H2S 04)/鹽酸(HC1)混合液進 "* ""再氣化處理’以產生次微米級(sub-micron)的均勻 mi’$降低對人體有危險傷害的機會。 如此’透過本發明的表面處理方法，最終可在金屬植 入物表面的產生「大凹洞裡具有小凹洞」之表面型態。 ^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’任何熟習相像技藝者，在不脫離本發明之精神 #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。 9 201041565 【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2A與圖2B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The above-described features and embodiments of the present invention are combined with the accompanying drawings, and the advantages can be more clearly understood and described in detail below. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Fig. 1 is a flow chart of a metal implant of the present invention. Please refer to the method of surface treatment of implants. The method of sputum-finishing treatment (step S100) ‘that is, the surface of the body with a sand body has a plurality of micro-weis. Metallic plant of money 7.201041565 This (4) (4) Sand (4) Step (4) The metal implants after the cleaning process and the cleaning procedure are made of ceramic sand bodies (such as oxidized Ming sand and oxidized sand) with a particle size of 200 μm or less. Sandblasting, blasting pressure is 2~4Kg/cm2, sandblasting distance is 5cm, sandblasting time is 20~40 private, and the metal implant material can be -titanium, -titanium alloy or one containing Metal of titanium. Thereafter, a deoxidation and reoxidation treatment (step S2〇〇) is performed, that is, the metal implant after the sandblasting treatment is immersed in a composite acid strontium containing hydrogen peroxide to open at least one-human micron level. The recess is located in the micron-sized recesses and forms an oxide layer, and the oxide layer may be a titanium oxide layer. It should be particularly noted that the above hydrogen peroxide-containing complex acid may be a mixed acid of monosulfuric acid and hydrogen peroxide or a mixed acid of monohydrochloric acid and hydrogen peroxide. In the present embodiment, the deoxidation reoxidation treatment step (step S100) is to soak the metal implant which has been cleaned, sandblasted, and cleaned in a hydrogen peroxide (30%)/sulfuric acid mixed in an equal volume ratio. (98%) in the mixture 'at the temperature for 12 to 24 hours, and finally rinse, neutralize, air dry. The above room temperature range is preferably 2 (TC to 35 ° C. In other applications, the deoxidation and reoxidation treatment can also be carried out at a high temperature for about 10 minutes to 1 hour, and the above high temperature temperature range is preferably 60 ° C to 80. (: Finally, the metal implant is taken out of the acid solution. Thus, after blasting and deoxidation and reoxidation, the surface of the metal implant can produce a "large cavity". The surface shape of the small recessed hole. That is to say, the large concave hole is a micron-sized concave hole, the small concave hole is a sub-micron concave hole, and the micron-sized concave hole has a pore diameter of between 1 μm and 1 μm The aperture of the sub-micron-sized cavity is between 201041565 lOOnm~lOOOnm. Please refer to FIG. 2A and FIG. 2B respectively, which are respectively the surface SEM images of the metal implant processed by the above process, and the SEm magnifications are respectively 2500 times and 5K times. As shown in Fig. 2A, the surface of the metal implant is formed by a micro-scale (1~1〇〇μπι) large cavity formed by sandblasting. As shown in Fig. 2B, the metal implant is Submicron (100~1000 nm) pits produced after deoxidation and reoxidation In summary, the method of the present invention firstly uses a sand body having a particle diameter of 200 μm or less to perform a small amount of blasting, thereby improving the conventional sandblasting treatment using a large particle size (250 to 500 μηι) sand body. The surface of the metal implant has the disadvantages of changing the edge of the 5L state to achieve the effect of roughening the surface of the existing surface, and retaining the surface shape originally designed by the metal implant. ^In addition, using hydrogen peroxide (Η202) / sulfuric acid (h2so4) mixture, replacing the sulphuric acid (H2S 04) / hydrochloric acid (HC1) mixture that produces a violent reaction into the "* """regasification treatment to produce sub-micron (sub- The uniform mi'$ of micron) reduces the chance of dangerous harm to the human body. Thus, through the surface treatment method of the present invention, the surface pattern of "small pits in large cavities" can be finally produced on the surface of the metal implant. Although the present invention has been disclosed above in the foregoing embodiments, it is not intended to limit the invention to any skilled artisan, and the equivalents of the modifiers and retouchings are still within the scope of the spirit of the present invention. Invention patent protection 9 201041565 [Simplified Schematic] FIG. 1 is a flow chart of a surface treatment method for a metal implant of the present invention; and FIGS. 2A and 2B are SEM images of a surface of a metal implant. , S200 step process