567238 五、發明說明（i) 本案係一種眼鏡架框變色的方法，特別是先將眼鏡 架框應用無電鎳方法做非晶結構之鎳-磷合金為中間層， 而後做真空離子鍍鈦，再將離子鍍鈦眼鏡架框物件置於 矽酸鹽、氫氧化物、硫酸鹽、硫酸、磷酸或其混合之水 溶液施以一定電位之電解發色處理。藉控制電位可得到 離子鍍鈦膜之各種顏色，此等顏色是一種不同氧化狀態 鈦薄膜之非干擾色。近年來離子鍍鈦已逐漸增加被應用 於裝飾及抗腐蝕的材料，然而至今離子鍍鈦變色的方法 人仍有一些困難，例如在真空腔体變色不穩定及色澤有 限的問題，又傳統之鈦發色方法其使用電解液為硫酸、 鉻酸、填酸、删酸、氟化物、過氧化氫、氫氧化納等水 溶液以高電壓或定電流之直流陽極處理，會經由微孔侵 蝕到非鈍性如銀、銅、鋅基合金之焊點、支架或螺絲區 域而無法發色均勻。本案克服上述的問題，其方法如圖 一及圖二所示，含有非鈍性材料所組合之基材（8 )首先應 用電鍍（1)方法做一層光澤鎳為底層（7)，接著應用無電 鎳（2 )方法做一層覆蓋性優越、孔率小、附著性高、硬度 高及耐蝕性佳之非晶結構之鎳-磷合金為中間層（6 )，再 應用真空離子鍍（3 )方法做一層鈦層（5 )，最後應用電解 氧化（4 )方法做變色處理。 因為鈦有優良的機械物理化學特性，例如抗腐蝕 性、抗菌性、抗人體過敏性及除臭功能等，最近年來鈦 及其合金亦被使用於建築及裝飾材料，例如屋頂、牆板 及一些室内裝璜結構等物件，裝飾品例如眼鏡、手錶567238 V. Description of the invention (i) This case is a method for discoloring the spectacle frame frame. In particular, the spectacle frame frame is firstly made of a nickel-phosphorus alloy with an amorphous structure as an intermediate layer by using an electroless nickel method, and then vacuum ion-plated titanium is used. An ion-plated titanium frame frame object is placed on silicate, hydroxide, sulfate, sulfuric acid, phosphoric acid, or a mixed aqueous solution thereof, and subjected to electrolytic electrochromic treatment at a certain potential. Various colors of ion-plated titanium films can be obtained by controlling the potential. These colors are a non-interfering color of titanium films with different oxidation states. In recent years, ion-plated titanium has gradually been applied to decorative and anti-corrosive materials. However, the method of discoloration of ion-plated titanium still has some difficulties, such as the problem of unstable color change and limited color in the vacuum cavity, and the traditional titanium The color development method uses an electrolyte solution such as sulfuric acid, chromic acid, acid filling, acid removal, fluoride, hydrogen peroxide, sodium hydroxide and other high-voltage or constant-current DC anode treatment, which will erode through the pores to non-blunt Properties such as silver, copper, zinc-based alloy solder joints, brackets or screw areas cannot be uniformly colored. This case overcomes the above problems. The method is shown in Figures 1 and 2. The substrate (8) containing a combination of non-passive materials is firstly plated (1) with a layer of glossy nickel as the bottom layer (7), and then applied without electricity. The nickel (2) method is used to form a layer of nickel-phosphorus alloy with an amorphous structure with excellent coverage, small porosity, high adhesion, high hardness and good corrosion resistance as the intermediate layer (6), and then vacuum ion plating (3) is used to make One layer of titanium (5), and finally the electrolytic oxidation (4) method is used for discoloration treatment. Because titanium has excellent mechanical physical and chemical properties, such as corrosion resistance, antibacterial properties, anti-allergic and deodorizing functions, titanium and its alloys have also been used in construction and decoration materials, such as roofs, wall panels and some Interior decoration structures and other items, such as eyewear, watches
567238 五、發明說明（2) 等。鈦及其合金的建築材料及裝飾物，施以陽極氧化處 理來呈現不同的色澤增進美觀但因鈦及鈦合金的價格較 高，尤其是裝飾物如眼鏡其成形加工組裝較困難，需應 用各種不同性質的或成本較低的基材經焊接組合裝配而 成。如圖二所示，本案主要係將含有非鈍性材料所組合 之基材（8)做光澤鎳（7)/鎳磷合金（6) /鈦（5)多層鍍膜之 電解氧化鈦處理變色。 鈦及其合金的發色已有很多的研究，其主要是鈦及 其合金物件於電解液施陽極處理或熱氧化處理使表面上 形成氧化薄膜，由於光線的干涉現象呈現出顏色，此顏 色的變化是依據鈦氧化薄膜厚度而改變。鈦氧化薄膜厚 度可藉陽極氧化處理施加之電壓控制，也就是鈦及其合 金的表面顏色可由陽極氧化處理之電壓來控制。在研究 報告裡，最實用的鈦及其合金的發色方法是將鈦及其合 金作為陽極在電解液通以直流電，此電解液組成為含有 如磷酸、硫酸或硼酸的水溶液，經由電壓的控制可得到 一些不同的顏色。例如使用磷酸電解液，陽極氧化處理 之電壓為25 Volt，鈦及其合金的表面色澤為藍色。若 電壓繼續增加則氧化膜厚度繼續變厚而呈現多種顏色， 例如從黃色到粉紅色、到紫色及到綠色，當電壓至1 2 0 Volt 顏色轉變成紅紫色。因此鈦及其合金的一些顏色可 藉調控電壓來穫得，但是前面所說的傳統發色方法需要 鈦及其合金才可形成各種不同的顏色。傳統直流陽極處 理發色方法處理非鈦基材組合再經離子鍍鈦之物件會經567238 V. Description of the invention (2) and so on. Titanium and its alloy construction materials and decorations are anodized to show different colors and lusters to enhance their beauty. However, due to the higher price of titanium and titanium alloys, especially the decoration and assembly of decorative objects such as glasses are difficult, and various applications are required. Different nature or lower cost substrates are assembled by welding. As shown in Figure 2, this case is mainly based on the electrolytic titanium oxide discoloration of the base material (8) containing non-blunt materials as a glossy nickel (7) / nickel-phosphorus alloy (6) / titanium (5) multilayer coating. There have been many studies on the color development of titanium and its alloys. The main reason is that titanium and its alloys are anodized or thermally oxidized on the electrolyte to form an oxidized film on the surface. Due to the interference of light, the color appears. The change is based on the thickness of the titanium oxide film. The thickness of the titanium oxide film can be controlled by the voltage applied by the anodizing treatment, that is, the surface color of titanium and its alloy can be controlled by the voltage of the anodizing treatment. In the research report, the most practical method for coloring titanium and its alloys is to use titanium and its alloys as anodes to apply direct current to the electrolyte. This electrolyte is composed of an aqueous solution containing phosphoric acid, sulfuric acid or boric acid, which is controlled by voltage. Some different colors are available. For example, using phosphoric acid electrolyte, the voltage of anodizing treatment is 25 Volt, and the surface color of titanium and its alloy is blue. If the voltage continues to increase, the thickness of the oxide film will continue to thicken and present a variety of colors, such as from yellow to pink, to purple, and green. When the voltage reaches 120 Volt, the color changes to red-purple. Therefore, some colors of titanium and its alloys can be obtained by regulating the voltage, but the traditional color development method mentioned above requires titanium and its alloys to form various colors. Traditional DC anode haircut color treatment of non-titanium substrate combination and then ion-plated titanium objects
567238 五、發明說明（3) 由微孔侵蝕到非鈍性基材而無法發色均勻，本發明發現 若先經無電鎳方法做一層覆蓋性優越、孔率小、附著性 高、硬度高及耐蝕性佳之非晶結構之鎳-磷合金為中間層 可形成均勻的顏色，此係本案特點之一。另外，傳統的 直流電陽極發色處理是將工件置於陽極，而本案的電解 發色處理可使用交流將工件置於兩極，因此發色處理的 效率是傳統方法的二倍，且可使用一般的110V或220V交 流電源經變壓器提供定電壓之電源作為高效率之離子鍍 鈦物件的表面發色處理，此為本案特點之二。 含有非鈍性材料所組合之眼鏡架框，首先做光澤鎳 電鍍為底層，接著用無電鎳方法做一層非晶結構之鎳-磷 合金為中間層，而後做真空離子鍍鈦，再將離子鍍鈦眼 鏡架框做交流電解發色。研究其機構和形成的氧化物膜 之結構，發現置於矽酸鹽、氫氧化物、硫酸鹽、硫酸、 磷酸或其混合之水溶液施以一定電位之交流電解發色處 理，藉控制電位可得到各種顏色，此等顏色是一種不同 氧化狀態鈦薄膜之非干擾色。本案以定電壓的交流電解 處理來改變離子鍍鈦物件的表面顏色。由實驗得知使用 交流電解發色處理之電壓為1 4 Vo 11表面色澤變為黃 色，當電壓至28 Vo It顏色轉變成深藍色，當電壓至42 Volt顏色轉變成淺藍色，當電壓至70 Volt顏色轉變成紫 色，當電壓至98 Volt顏色轉變成粉紅色，當電壓至112 V ο 1 t顏色轉變成綠色。交流電解電壓的大小使表面鈦氧 化狀態變化而呈現多種顏色，從黃色到藍色、淺藍色、567238 V. Description of the invention (3) From micropores to non-blunt substrates without uniform color development, the present invention found that if the first layer is made by electroless nickel method, it has superior coverage, small porosity, high adhesion, high hardness and The nickel-phosphorus alloy with an amorphous structure and excellent corrosion resistance can form a uniform color as an intermediate layer, which is one of the characteristics of this case. In addition, the conventional DC anode color treatment is to place the workpiece on the anode, and the electrolytic color treatment in this case can use AC to place the workpiece on the two poles. Therefore, the efficiency of the color development is twice that of the traditional method, and the general method can be used. 110V or 220V AC power is treated by the transformer to provide a constant voltage power supply as the surface color treatment of high-efficiency ion-plated titanium objects. This is the second feature of this case. A spectacle frame containing a combination of non-blunt materials is firstly made of glossy nickel plating as the bottom layer, and then an electroless nickel method is used to form an amorphous nickel-phosphorus alloy as an intermediate layer, and then vacuum ion plating is performed, and then ion plating is performed. Titanium spectacle frames make AC electrolytic hair color. The structure of the formed oxide film was studied, and it was found that the solution was placed on silicate, hydroxide, sulfate, sulfuric acid, phosphoric acid, or a mixed aqueous solution, and subjected to a certain potential of an alternating electrolytic color treatment. Various colors, these colors are a non-interfering color of titanium films with different oxidation states. In this case, a constant voltage AC electrolytic treatment was used to change the surface color of ion-plated titanium objects. It is known from experiments that the voltage applied to the electrolytic electrolytic color treatment is 1 4 Vo 11 and the surface color changes to yellow. When the voltage reaches 28 Vo It, the color changes to dark blue. When the voltage reaches 42 Volt, the color changes to light blue. When the voltage reaches 70 Volt color changes to purple, when voltage reaches 98 Volt color changes to pink, when voltage reaches 112 V ο 1 t color changes to green. The size of the AC electrolytic voltage changes the surface oxidation state of titanium and presents a variety of colors, from yellow to blue, light blue,
567238 五、發明說明（4) 紫色、粉紅色及到綠色。以下實例作為本案較詳細的說 明： 實例一： 含有非鈍性如銀、銅、鋅基合金之焊點、支架或螺 絲區域之不銹鋼為基材之眼鏡架框首先做一層3微米厚度 之光澤鎳電鍍為底層，接著應用無電鎳方法做一層1微米 厚度層覆蓋性優越、孔率小、附著性高、硬度高及耐蝕 性佳之非晶結構之鎳-磷（8wt%P)合金為中間層，再做一 層0.5微米厚度真空離子鍍鈦，最後置入0.05M 矽酸 納、0 . 1 Μ 硫酸鈉及添加氫氧化納至ρ Η值為1 2水溶液作 交流電解處理，施以定電壓1 4 V ο 11約3分鐘，眼鏡架框 表面呈現金黃色澤氧化鈦鍍膜。 實例二： 含有非鈍性如銀、銅、鋅基合金之焊點、支架或螺 絲區域之不銹鋼為基材之眼鏡架框首先做一層3微米厚度 之光澤鎳電鍍為底層，接著應用無電鎳方法做一層1微米 厚度層覆蓋性優越、孔率小、附著性高、硬度高及财I虫 性佳之非晶結構之鎳-磷（8wt%P)合金為中間層，再做一 層0 . 5微米厚度真空離子鍍鈦，最後置入0 . 0 5 Μ 矽酸 鈉、0 . 1 Μ 硫酸鈉及添加氫氧化鈉至pH值為1 2水溶液作 交流電解處理，施以定電壓2 8 V ο 11約4分鐘，眼鏡架框 表面呈現藍色澤氧化鈦鍍膜。567238 V. Description of the invention (4) Purple, pink and green. The following examples serve as a more detailed description of this case: Example 1: A stainless steel-based spectacle frame containing non-blunt stainless steel, such as silver, copper, zinc-based alloy solder joints, brackets or screw regions, is first made of a layer of 3 micron thick nickel Electroplating is used as the bottom layer, and then a nickel-phosphorus (8wt% P) alloy with an amorphous structure having a good coverage, small porosity, high adhesion, high hardness, and good corrosion resistance is used as the intermediate layer. Make another layer of 0.5 micron thickness vacuum ion titanium plating, and finally put 0.05M sodium silicate, 0.1 M sodium sulfate and add sodium hydroxide to ρ Η value 1 2 aqueous solution for AC electrolytic treatment, apply a constant voltage 1 4 V ο 11 for about 3 minutes, the surface of the frame of the spectacle frame presents a golden yellow titanium oxide coating. Example 2: Spectacle frames with non-passive stainless steel such as silver, copper, zinc-based alloy solder joints, brackets, or screw areas as the substrate. First, a layer of 3 micron thick nickel plating is used as the bottom layer, and then electroless nickel is applied. A layer of 1 micron thick nickel-phosphorus (8wt% P) amorphous alloy with excellent coverage, small porosity, high adhesion, high hardness, and good insect properties is used as an intermediate layer, and then a layer of 0.5 micron Thickness vacuum ion-plated titanium, and finally put 0.05 M sodium silicate, 0.1 M sodium sulfate, and add sodium hydroxide to a pH of 12 aqueous solution for alternating current electrolytic treatment, a constant voltage of 2 8 V ο 11 In about 4 minutes, the surface of the frame of the spectacle frame showed a blue titanium oxide coating.
567238 五、發明說明（5) 實例三： 含有非鈍性如銀、銅、鋅基合金之焊點、支架或螺 絲區域之錳鎳合金為基材之眼鏡架框首先做一層5微米厚 度之光澤鎳電鍍為底層，接著應用無電鎳方法做一層2微 米厚度層覆蓋性優越、孔率小、附著性高、硬度高及耐 蝕性佳之非晶結構之鎳-磷（8wt%P)合金為中間層，再做 一層0.5微米厚度真空離子鍍鈦，最後置入0.05M矽酸 納、0 . 1 Μ 硫酸納及添加氬氧化鈉至ρ Η值為1 2水溶液作 交流電解處理，施以定電壓4 2 V ο 11約5分鐘，眼鏡架框 表面呈現淺藍色澤氧化鈦鍍膜。 實例四·· 含有非鈍性如銀、銅、鋅基合金之焊點、支架或螺 絲區域之鈦為基材之眼鏡架框首先做一層1微米厚度之光 澤鎳電鍍為底層，接著應用無電鎳方法做一層0. 5微米厚 度層覆蓋性優越、孔率小、附著性高、硬度高及耐蝕性 佳之非晶結構之鎳-磷（8 w t %P )合金為中間層，再做一層 0.5微米厚度真空離子鍍鈦，最後置入0.05M 矽酸鈉、 0.1 Μ 硫酸納及添加氫氧化鈉至ρ Η值為1 2水溶液作交流 電解處理，施以定電壓7 0 V ο 11約5分鐘，眼鏡架框表面 呈現紫色澤氧化鈦鍍膜。 實例五： 含有非鈍性如銀、銅、鋅基合金之焊點、支架或螺567238 V. Description of the invention (5) Example 3: Spectacle frames with non-passive materials such as silver, copper, zinc-based alloy solder joints, brackets, or manganese-nickel alloys as the base area are first made with a 5 micron thickness of gloss Nickel electroplating is used as the bottom layer, and then a nickel-phosphorus (8wt% P) alloy with an amorphous structure of an amorphous structure having a good coverage, small porosity, high adhesion, and high corrosion resistance is used as the intermediate layer by using a non-electric nickel method to form a 2 micron thickness layer Then, a layer of vacuum ion titanium plating with a thickness of 0.5 micron is made, and finally 0.05M sodium silicate, 0.1 M sodium sulfate and sodium argon oxide are added to ρ 1 to a value of 12 aqueous solution for alternating current electrolytic treatment, and a constant voltage of 4 is applied. 2 V ο 11 for about 5 minutes, the surface of the spectacle frame showed a light blue titanium oxide coating. Example 4: An eyeglass frame containing non-blunt titanium such as silver, copper, zinc-based alloy solder joints, brackets or screws in the titanium frame as the base material. Firstly, a layer of 1 micron thick nickel plating is used as the bottom layer, and then electroless nickel Method A layer of 0.5 micron thick amorphous-nickel-phosphorus (8 wt% P) alloy with amorphous structure, excellent coverage, small porosity, high adhesion, high hardness, and good corrosion resistance was used as an intermediate layer, and then another layer was 0.5 micron Thickness vacuum ion-plated titanium, finally put 0.05M sodium silicate, 0.1M sodium sulfate and add sodium hydroxide to ρ ρ value of 12 aqueous solution for alternating current electrolytic treatment, apply a constant voltage of 70 V ο 11 for about 5 minutes, The surface of the frame of the spectacle frame has a purple-colored titanium oxide coating. Example 5: Solder joints, brackets or screws containing non-blunt materials such as silver, copper, zinc-based alloys
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567238 五、發明說明（6) 絲區域之鈦為基材之眼鏡架框首先做一層1微米厚度之光 澤鎳電鍍為底層，接著應用無電鎳方法做一層0. 5微米厚 度層覆蓋性優越、孔率小、附著性高、硬度高及耐蝕性 佳之非晶結構之鎳-磷（8w t %P )合金為中間層，再做一層 0.5微米厚度真空離子鍍鈦，最後置入0.05M 矽酸鈉、 0.1 Μ 硫酸鈉及添加氫氧化鈉至ρ Η值為1 2水溶液作交流 電解處理，施以定電壓9 8 V ο 11約5分鐘，眼鏡架框表面 呈現粉紅色澤氧化鈦鍍膜。 實例六： 含有非鈍性如銀、銅、鋅基合金之焊點、支架或螺 絲區域之鈦為基材之眼鏡架框首先做一層1微米厚度之光 澤鎳電鍍為底層，接著應用無電鎳方法做一層0. 5微米厚 度層覆蓋性優越、孔率小、附著性高、硬度高及耐蝕性 佳之非晶結構之鎳-磷（8 w t %P )合金為中間層，再做一層 0.5微米厚度真空離子鍍鈦，最後置入0.05M 矽酸鈉、 0 . 1 Μ 硫酸鈉及添加氫氧化鈉至pH值為1 2水溶液作交流 電解處理，施以定電壓11 2 V ο 1 t約5分鐘，眼鏡架框表 面呈現綠色澤氧化鈦鍍膜。 雖然本案已以較佳實例揭露如上，任何熟悉此技藝 者當可作些許變化，然皆不離如附申請保護專利之範 圍。567238 V. Description of the invention (6) The titanium-based spectacle frame in the silk region is firstly made with a layer of 1 micron thick nickel plating as the bottom layer, and then applied an electroless nickel method to make a layer of 0.5 micron thickness with superior coverage and holes A nickel-phosphorus (8w t% P) alloy with an amorphous structure of a small rate, high adhesion, high hardness, and good corrosion resistance is used as an intermediate layer, and then a 0.5 micron thickness vacuum ion titanium plating is performed, and finally 0.05M sodium silicate is placed. , 0.1 M sodium sulfate and adding sodium hydroxide to a pH value of 12 aqueous solution for AC electrolysis treatment, applying a constant voltage of 9 8 V ο 11 for about 5 minutes, the surface of the eyeglass frame frame shows a pinkish titanium oxide coating. Example 6: Glasses frames containing non-blunt titanium, such as silver, copper, zinc-based alloy solder joints, brackets, or titanium in the substrate area, are first coated with a layer of 1-micron glossy nickel as the base layer, followed by the electroless nickel method A layer of 0.5 micron thick nickel-phosphorus (8 wt% P) amorphous layer with excellent coverage, small porosity, high adhesion, high hardness and good corrosion resistance is used as an intermediate layer, and another layer of 0.5 micron thick Vacuum ion-plating titanium, finally put 0.05M sodium silicate, 0.1M sodium sulfate and add sodium hydroxide to pH 12 aqueous solution for AC electrolytic treatment, apply a constant voltage of 11 2 V ο 1 t for about 5 minutes The surface of the frame of the spectacle frame presents a green-colored titanium oxide coating. Although this case has been disclosed above with a good example, any person familiar with this technique can make some changes, but it does not depart from the scope of application for patent protection.
567238 圖式簡單說明 第ίο頁567238 Schematic description