201217581 六、發明說明： 【發明所屬之技術領域】 [0001] 本發明涉及一種鍍膜件及該鍍膜件的製備方法。 【先前技術】 [0002] 有害細菌的傳播和感染嚴重威脅著人類的健康，尤其近 年來SARS病毒、禽流感等的傳播和感染，使抗菌材料在 曰常生活中的應用迅速發展起來。將抗菌金屬（Cu、Zn、 Ag等）塗覆於基材上形成抗菌鍍膜件在目前市場上有著廣 泛的應用。該抗菌鍍膜件的殺菌機理為：鍍膜件在使用 過程中，抗菌金屬塗層會緩慢釋放出金屬離子如Cu2+、 Zn2+，當微量的具有殺菌性的金屬離子與細菌等微生物 接觸時，該金屬離子依靠庫倫力與帶有負電荷的微生物 牢固吸附，金屬離子穿透細胞壁與細菌體内蛋白質上的 酼基、氨基發生反應，使蛋白質活性破壞，使細胞喪失 分裂增殖能力而死亡，從而達到殺菌的目的。 [0003] 然該類金屬抗菌塗層厚度通常比較薄，且表面硬度較低 容易磨損，從而降低了金屬抗菌塗層的抗菌持久性。 【發明内容】 [0004] 有鑒於此，有必要提供一種抗菌效果較為持久的鍍膜件 〇 [0005] 另外，還有必要提供一種上述鍍膜件的製備方法。 [0006] —種鍍膜件，其包括基材、形成於基材表面的打底層， 該打底層為Cr層，該鍍膜件還包括形成於打底層表面的 複數CrN層和複數Cu-Zn合金層，該複數CrN層和複數Cu- 099136031 表單編號A0101 第4頁/共12頁 0992062996-0 201217581201217581 VI. Description of the Invention: [Technical Field of the Invention] [0001] The present invention relates to a coated member and a method of preparing the coated member. [Prior Art] [0002] The spread and infection of harmful bacteria is a serious threat to human health. Especially in recent years, the spread and infection of SARS virus, avian flu, etc., have rapidly developed the application of antibacterial materials in normal life. The application of antibacterial metals (Cu, Zn, Ag, etc.) on substrates to form antibacterial coated parts has a wide range of applications on the market. The sterilization mechanism of the antibacterial coating member is: during the use of the coating member, the antibacterial metal coating will slowly release metal ions such as Cu2+ and Zn2+, and when a trace amount of bactericidal metal ions are in contact with microorganisms such as bacteria, the metal ion Relying on Coulomb force and negatively charged microorganisms, the metal ions penetrate the cell wall and react with the sulfhydryl groups and amino groups on the proteins in the bacteria, destroying the activity of the protein, causing the cells to lose their ability to divide and proliferate and die, thereby achieving sterilization. purpose. [0003] However, such metal antibacterial coatings are generally thin in thickness and have a low surface hardness and are prone to wear, thereby reducing the antibacterial durability of the metal antibacterial coating. SUMMARY OF THE INVENTION [0004] In view of the above, it is necessary to provide a coating member having a relatively long-lasting antibacterial effect. [0005] In addition, it is also necessary to provide a method for preparing the above-mentioned coated member. [0006] A coated member comprising a substrate, a primer layer formed on a surface of the substrate, the primer layer being a Cr layer, the coating member further comprising a plurality of CrN layers and a plurality of Cu-Zn alloy layers formed on the surface of the primer layer , the complex CrN layer and the plural Cu- 099136031 Form No. A0101 Page 4 / Total 12 Page 0992062996-0 201217581
Zn合金層交替排布。 [0007] —種鍍膜件的製備方法，其包括如下步驟： [0008] 提供一基材； [0009] 在該基材的表面形成打底層，該打底層為Cr層； [0010] 在該打底層的表面形成CrN層； [0011] 在該CrN層的表面形成Cu-Zn合金層； [0012] 重複交替形成CrN層和Cu-Zn合金層以形成最外層為CrN 層的鍍膜件。 [0013] 所述鍍膜件在基材表面交替濺鍍CrN層和Cu-Zn合金層， CrN層形成為疏鬆多孔的結構，而使Cu-Zn合金層的部分 後入到CrN層中，對Cu-Zn合金層中Cu-Zn金屬離子的快 速溶出起到阻礙作用，從而可緩釋Cu-Zn金屬離子的溶出 ，使Cu-Zn合金層具有長效的抗菌效果。 【實施方式】 [0014] 請參閱圖1，本發明一較佳實施方式的鍍膜件100包括基 材10、形成於基材10表面的打底層20，形成於打底層20 表面的複數CrN層30和複數Cu-Zn合金層40，該複數CrN 層30和複數Cu-Zn合金層40交替排布，其中與所述打底 層20直接相結合的為CrN層30，最外層為CrN層30。所述 複數CrN層30和複數Cu-Zn合金層40的總厚度可為1〜8以 m。本實施例中，所述複數CrN層30和複數Cu-Zn合金層 40的層數可分別為5〜20層。 0992062996-0 [0015] 該基材10的材質可為不銹鋼或含Cr的合金。 099136031 表單編號A0101 第5頁/共12頁 201217581 [0016] 該打底層2 0可以磁控濺射的方式形成。該打底層為一 Cr 層。該打底層20的厚度可為100〜200nm。 [0017] 該複數CrN層30可以磁控濺射的方式形成。所述每一CrN 層30的厚度可為50〜100nm。該CrN層30具有疏鬆多孔的 結構，可使所述C u - Ζ η合金層4 0的部分後入到該C r N層3 0 中。滅鍍該C r N層3 0時採用較低的沉積溫度和沉積偏壓， 使CrN層30具有更好的疏鬆多孔的結構，可使所述Cu-Zn 合金層40的部分嵌入到該CrN層30中。 [0018] 該複數Cu-Zn合金層40可以磁控濺射的方式形成。所述每 一Cu-Zn合金層40的厚度可為200〜300n.m。在每一Cu-Zn合金層40與相鄰的每一 CrN層30的介面處，有部分Cu-Zn合金層40欲入到CrN層30中，從而對Cu-Zn合金層40 起到固持的作用，並可緩釋Cu-Zn金屬離子的溶出，使 Cu-Zn合金層40具有長效的抗菌效果。 [0019] 本發明一較佳實施方式的鍍膜件100的製備方法，其包括 如下步驟： [0020] 提供一基材10，該基材10的材質可為不銹鋼或含Cr的合 金。 [0021] 對該基材10進行表面預處理。該表面預處理可包括常規 的對基材10進行拋光、無水乙醇超聲波清洗及烘乾等步 驟。 [0022] 對經上述處理後的基材10的表面進行氬氣電漿清洗，以 進一步去除基材10表面殘留的雜質，以及改善基材10表 面與後續鍍層的結合力。具體操作及工藝參數為：將基 099136031 表單編號A0101 第6頁/共12頁 0992062996-0 201217581 [0023] Ο [0024] Ο 材10放入一磁控濺射鍍膜機（圖未示）的鍍膜室内，將該 鑛膜室抽真空至3x10 —5torr，然後向鍍膜室内通入流量 為1 00〜30 0sccm(標準狀態毫升/分鐘）的氬氣（純度為 99. 999%)，並施加-200〜-800V的偏壓於基材1〇，對基 材10表面進行氬氣電漿清洗，清洗時間為3〜l〇min。 採用磁控濺射法在經氬氣電漿清洗後的基材1〇的表面濺 鍍一打底層20 ’該打底層20可為一Cr層。濺鍍該打底層 20在所述磁控濺射鍍膜機中進行。使用金屬鉻靶，所述 鉻靶採用直流磁控電源。濺鍍時，開啟鉻靶，通入工作 氣體氬氣，氬氣流量可為100〜300sccm，對基材1〇施加 ~5〇〜-15〇¥的％壓，鍍膜室的溫度可為8〇〜i5(rc，鍵 膜時間可為5〜lOmin。該打底層20的厚度可為1〇〇〜 200nm。 繼續採用磁控濺射法在所述打底層20的表面錢鑛一crN層 30。使用金屬鉻靶，所述銀餐樓再哀流磁控電源。滅鍍 時，開啟鉻靶’通入反應氣截氮氣，氮氣流量可為1〇〜 20sccm ’通入工作氣體氬氣，氬氣流量可為2〇〜50sccm ’對基材10施加直流偏壓，直流偏壓大小可為_ 5 〇〜- 150V，基材10的溫度可為70〜130°C，鍍膜時間可為2〜 3min。該CrN層30的厚度可為50〜ΐ〇〇ηιη。賤鍍該crN層 30採用較低的沉積溫度和較低的沉積偏壓，可使[γν層30 達到較好的疏鬆多孔的結構。 [0025] 繼續採用磁控濺射法在所述CrN層30的表面濺鍵一cu-Zn 合金層40。使用銅鋅合金把’所述鋼鋅合金乾中銅的質 量百分含量為80%〜90%，所述銅鋅合金靶採用射頻磁控 099136031 表單編號A0101 第7頁/共12頁 0992062996-0 201217581 電源。濺鍍時，開啟銅鋅合金靶，通入工作氣體氬氣， 氬氣流量可為20〜50sccm，對基材10施加輕合脈衝偏壓 ，耦合脈衝偏壓大小可為-180〜-350V，脈衝頻率為 ΙΟΚΗζ，脈衝寬度為20/zs，基材10的溫度可為70〜130 °C，鑛膜時間可為2〜3min。該Cu-Zn合金層40的厚度可 為200〜300nm。 [0026] 參照上述步驟，重複交替濺鐘CrN層30和Cu-Ζη合金層40 ，且最外層為CrN層30。交替賤鑛的次數總共可為5〜20 次。所述複數CrN層30和複數Cu-Zn合金層40的總厚度可 為1〜8 # m。 [0027] 所述鍍膜件100在基材10表面交替濺鍍CrN層30和Cu-Zn 合金層40，CrN層30形成為疏鬆多孔的結構，而使Cu-Zn 合金層40的部分嵌入到CrN層30中，對Cu-Zn合金層40中 Cu-Zn金屬離子的快速溶出起到阻礙作用，從而可緩釋 Cu-Zn金屬離子的溶出，使Cu-Zn合金層40具有長效的抗 菌效果。同時CrN層30具有良好的财磨性、耐腐蝕性能以 及色澤美觀等特點，因而在整個膜層的最外層鍍上CrN層 30有助於提升鍍膜件100的耐磨性及美觀性，可延長鍍膜 件100的使用壽命。 【圖式簡單說明】 [0028] 圖1為本發明一較佳實施例鍍膜件的剖視圖。 【主要元件符號說明】 [0029] 鍍膜件：100 [0030] 基材：10 099136031 表單編號A0101 第8頁/共12頁 0992062996-0 :40 201217581 ‘ [0031]打底層：20 [0032] CrN層：30 [0033] Cu-Zn 合金層The Zn alloy layers are alternately arranged. [0007] A method for preparing a coated member, comprising the steps of: [0008] providing a substrate; [0009] forming a primer layer on a surface of the substrate, the primer layer being a Cr layer; A surface of the underlayer forms a CrN layer; [0011] a Cu-Zn alloy layer is formed on the surface of the CrN layer; [0012] The CrN layer and the Cu-Zn alloy layer are alternately formed to form a plated member having the outermost layer of the CrN layer. [0013] The coating member alternately sputters a CrN layer and a Cu-Zn alloy layer on the surface of the substrate, and the CrN layer is formed into a loose porous structure, and a portion of the Cu-Zn alloy layer is later introduced into the CrN layer to Cu The rapid dissolution of Cu-Zn metal ions in the -Zn alloy layer acts as a hindrance, so that the dissolution of Cu-Zn metal ions can be sustained, and the Cu-Zn alloy layer has a long-lasting antibacterial effect. [0014] Referring to FIG. 1, a coated article 100 according to a preferred embodiment of the present invention includes a substrate 10, a primer layer 20 formed on the surface of the substrate 10, and a plurality of CrN layers 30 formed on the surface of the primer layer 20. And a plurality of Cu-Zn alloy layers 40, the plurality of CrN layers 30 and the plurality of Cu-Zn alloy layers 40 are alternately arranged, wherein the underlayer 20 is directly bonded to the CrN layer 30, and the outermost layer is the CrN layer 30. The total thickness of the plurality of CrN layers 30 and the plurality of Cu-Zn alloy layers 40 may be from 1 to 8 m. In this embodiment, the number of layers of the plurality of CrN layers 30 and the plurality of Cu-Zn alloy layers 40 may be 5 to 20 layers, respectively. 0992062996-0 [0015] The material of the substrate 10 may be stainless steel or an alloy containing Cr. 099136031 Form No. A0101 Page 5 of 12 201217581 [0016] The underlying layer 20 can be formed by magnetron sputtering. The underlayer is a Cr layer. The underlayer 20 may have a thickness of 100 to 200 nm. [0017] The plurality of CrN layers 30 may be formed by magnetron sputtering. Each of the CrN layers 30 may have a thickness of 50 to 100 nm. The CrN layer 30 has a loose porous structure, and a portion of the Cu- Ζ η alloy layer 40 is allowed to enter the C r N layer 30. When the C r N layer 30 is deplated, a lower deposition temperature and a deposition bias are used, so that the CrN layer 30 has a better porous structure, and a part of the Cu-Zn alloy layer 40 can be embedded in the CrN. In layer 30. [0018] The plurality of Cu-Zn alloy layers 40 may be formed by magnetron sputtering. Each of the Cu-Zn alloy layers 40 may have a thickness of 200 to 300 n.m. At the interface of each Cu-Zn alloy layer 40 and each adjacent CrN layer 30, a portion of the Cu-Zn alloy layer 40 is intended to be incorporated into the CrN layer 30, thereby holding the Cu-Zn alloy layer 40. The action and the slow release of Cu-Zn metal ions are eluted, so that the Cu-Zn alloy layer 40 has a long-lasting antibacterial effect. A method for preparing a coated member 100 according to a preferred embodiment of the present invention includes the following steps: [0020] A substrate 10 is provided, which may be made of stainless steel or a Cr-containing alloy. [0021] The substrate 10 is subjected to surface pretreatment. The surface pretreatment may include conventional steps of polishing the substrate 10, ultrasonic cleaning with anhydrous ethanol, and drying. [0022] The surface of the substrate 10 subjected to the above treatment is subjected to argon plasma cleaning to further remove impurities remaining on the surface of the substrate 10, and to improve the bonding force between the surface of the substrate 10 and the subsequent plating layer. The specific operation and process parameters are: base 099136031 Form No. A0101 Page 6 / Total 12 Page 0992062996-0 201217581 [0023] 00 [0024] The material 10 is placed in a magnetron sputtering coating machine (not shown) Indoor, the membrane chamber was evacuated to 3x10 - 5 torr, and then argon gas (purity of 99.999%) was flowed into the coating chamber at a flow rate of 100 to 30 0 sccm (standard state ml/min), and -200 was applied. The surface of the substrate 10 was subjected to argon plasma cleaning at a bias of ~-800 V to the substrate, and the cleaning time was 3 to 1 min. The surface of the substrate 1 after the argon plasma cleaning is sputtered by a magnetron sputtering method. The underlayer 20' may be a Cr layer. Sputtering the underlayer 20 is carried out in the magnetron sputtering coater. A metallic chromium target is used, which uses a DC magnetron power supply. During sputtering, the chromium target is turned on, and the working gas argon gas is introduced. The flow rate of the argon gas may be 100 to 300 sccm, and the pressure of the substrate 1 ~ is applied to the pressure of ~5 〇 to -15 〇, and the temperature of the coating chamber may be 8 〇. ~i5(rc, the bonding film time may be 5 to 10 min. The thickness of the underlying layer 20 may be 1 〇〇 to 200 nm. The magnetron sputtering method is continued on the surface of the underlying layer 20 with a crN layer 30. The metal chrome target is used, and the silver dining room sorrows the magnetic control power source. When the plating is off, the chromium target is turned on, and the reaction gas is introduced into the nitrogen gas, and the nitrogen flow rate can be 1 〇 20 20 cm. The flow rate can be 2〇~50sccm 'The DC bias is applied to the substrate 10, the DC bias voltage can be _ 5 〇~-150V, the temperature of the substrate 10 can be 70~130 ° C, and the coating time can be 2~3min. The thickness of the CrN layer 30 may be 50 to ΐ〇〇ηιη. The ruthenium plating of the CrN layer 30 uses a lower deposition temperature and a lower deposition bias, so that the [γ ν layer 30 can achieve a better porous structure. [0025] The cu-Zn alloy layer 40 is continuously sputter-bonded on the surface of the CrN layer 30 by magnetron sputtering. The steel-zinc alloy is dried using a copper-zinc alloy. The mass percentage of copper is 80%~90%, and the copper-zinc alloy target adopts RF magnetic control 099136031 Form No. A0101 Page 7 / Total 12 Page 0992062996-0 201217581 Power supply. When sputtering, the copper-zinc alloy target is turned on. The working gas argon gas is introduced, the flow rate of the argon gas may be 20 to 50 sccm, and the light pulse pulse bias is applied to the substrate 10. The coupling pulse bias voltage may be -180 to -350 V, the pulse frequency is ΙΟΚΗζ, and the pulse width is 20/. Zs, the temperature of the substrate 10 may be 70 to 130 ° C, and the film time may be 2 to 3 min. The thickness of the Cu-Zn alloy layer 40 may be 200 to 300 nm. [0026] Referring to the above steps, repeating the alternating splash clock The CrN layer 30 and the Cu-Ζη alloy layer 40, and the outermost layer is the CrN layer 30. The number of alternate tantalum ore may be 5 to 20 times in total. The total thickness of the plurality of CrN layers 30 and the plurality of Cu-Zn alloy layers 40 may be The coating member 100 alternately sputters the CrN layer 30 and the Cu-Zn alloy layer 40 on the surface of the substrate 10, and the CrN layer 30 is formed into a loose porous structure, and the Cu-Zn alloy is formed. Part of the layer 40 is embedded in the CrN layer 30, which hinders rapid dissolution of Cu-Zn metal ions in the Cu-Zn alloy layer 40, thereby The slow release of Cu-Zn metal ions causes the Cu-Zn alloy layer 40 to have a long-lasting antibacterial effect. At the same time, the CrN layer 30 has good properties such as good grindability, corrosion resistance and beautiful color, and thus is in the entire film layer. The outermost layer of the CrN layer 30 helps to improve the wear resistance and aesthetics of the coated member 100, and can extend the service life of the coated member 100. BRIEF DESCRIPTION OF THE DRAWINGS [0028] FIG. 1 is a cross-sectional view of a coated member according to a preferred embodiment of the present invention. [Main component symbol description] [0029] Coating member: 100 [0030] Substrate: 10 099136031 Form No. A0101 Page 8 / Total 12 Page 0992062996-0 : 40 201217581 ' [0031] Underlayer: 20 [0032] CrN layer :30 [0033] Cu-Zn alloy layer
I': ❹ 099136031 表單編號A0101 第9頁/共12頁 0992062996-0I': ❹ 099136031 Form No. A0101 Page 9 of 12 0992062996-0