588124 A7588124 A7
發明背景 近年來，由於電腦、通訊與消費性電器等3c產業之蓬 勃發展，使得以鋁基底金屬基材為裝飾外殼 =逄 L座(例 如：聿記型電腦、行動電話、隨身聽、光碟播放哭 MP3、照相機及個人數位助器（pDA)等）的市場需^有 曰漸增加之趨勢，銘基底金屬基材不僅重量輕且具有:屬 ^感’故已逐漸取代拷漆的外觀部件。BACKGROUND OF THE INVENTION In recent years, due to the vigorous development of 3c industries such as computers, communications and consumer appliances, aluminum-based metal substrates are used as decorative shells = 逄 L blocks (for example: 聿 note computers, mobile phones, walkmans, CD players) The market for MP3s, cameras, and personal digital assistants (pDAs) needs to gradually increase. Ming-based metal substrates are not only light in weight but also have a sense of belonging, so they have gradually replaced the appearance of painted parts.
裝 銘基底金屬基材之著色，傳統上係藉由進行陽極氧化處 理以於减底金屬|材上形成_層多孔性之銘的陽極氧化 月旲後，接著將無機金屬粒子加以電解沉積於該多孔性之鋁 的陽極氧化膜足孔隙中、或以有機染料吸附於該多孔性之 銘的陽極氧化膜之孔隙中而達成，此二種不僅可保護銘基 底金屬基材免於腐蝕及刮傷，且可提供美觀之裝飾效果。 然而，此二習知技術獲得之鋁製品的外觀仍以單一顏色為 主，且顏色不會隨視角不同而產生變化。 t 一種習知之光學基材著色方法可參見例如1 984年7月 3 1號公開之日本專利第59_ 1 3 3 5 〇1號之描述，其利用電 子鎗4鍍法於一透明之非金屬基材（如玻璃）上依序鍍上由 中折射率氧化物層、高折射率氧化物層及低折射率氧化物 層組成之抗反射多層膜。此日本專利主要著眼於調整高折 射率氧化物層的成份比例，以藉由光學干涉效應獲得反射 率降低的鐘膜’然’该專利係著眼於透明基材之教示，且 根本未述及任何多孔層的使用，更無法提供任何可隨視角 改變而產生顏色變化之製品。另外，美國專利第 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐)5 五、發明説明（ 4，6 2 6，4 4 5號揭示利用兩私 J用田射沉積法於基材上鍍予多層膜， 此多層膜為交替成長之高把 足阿折射率氧化物層及低折射率氧化 物層 < 組合。此吴國專利# 」使用足基材亦為透明之非金屬基 材（主要為聚酉旨），且其並夫摇― ^, 龙未揭不其製品可隨視角改變而產 生顏色變化，亦未述及任何多孔層之使用。 為因應市場及消費者 > 兩+、 而求，目前業界正積極研發且有 可依視角改變而產生顏色變 八 、 巴夂化又膜的鋁製品，及可於鋁基 底金屬基材表面形成可依葙备 侬視角改變而產生顏色變化之膜的 方法。 > 發明簡诚 本發明提供具有可依視角改變而產生顏色變化之膜的銘 製品’以及於銘基底金屬基材上形成可隨視角改變而產生 顏色變化之膜的方法。 显示簡單說明 圖1係本發明之一種鋁基材之結構圖。 圖2係根據本發明於㈣材上形成銘之陽極氧化膜之高 解析電子顯微鏡相片。 *圖3係本發明於陽極氧化膜上方交替成長高折射率Ti〇2 薄膜與低折射率Si〇2薄膜之多層薄膜的高解析電子顯微 鏡相片。 圖示主要元件符號敘述： 1代表鋁基底金屬基材； 2代表銘之陽極氧化膜的屏障層； 3代表鋁之陽極氧化膜之多孔層的微孔，· ----- G張尺度適财® s家襟準T^A4規格—7公爱 4代表鋁基底金屬基材之表面； 5代表低折射率氧化物薄膜； 6代表高折射率氧化物薄膜； 7代表鋁之陽極氧化膜的障壁層厚度； 8代表鋁之陽極氧化膜的多孔層厚度； 9代表又替成長之而折射率氧化物薄膜及低折射率氧化物薄 膜之總厚度。 發明詳诫 本發明之目的在於提供具有可依視角改變而產生顏色變 化之膜的鋁製品，以及於鋁基底金屬基材上形成可隨視角 改變而產生顏色變化之膜的方法。此等目的可藉由控制鋁 基底金屬基材表面上之鋁的陽極氧化膜（即干涉層）之厚度 於一特定範圍，並且於其上交替成長高折射率氧化物薄膜 及低折射率氧化物薄膜之多層薄膜，以於觀察者视角改變 時產生不同干涉效應，造成無基底金屬基材之外觀顏色變 化。. ^ 特定了之，本發明提供一種具有可隨視角改變而產生顏 色變化之膜的鋁製品，其包含·· --鋁基底金屬基材， 一覆蓋於該金屬基材表面且厚度小於之銘的陽 極氧化膜’該氧化膜包含一多孔層及一屏障層，及 -位於該陽極氧化膜上方之交替成長之高折射率氧化物 薄膜及低折射率氧化物薄膜之多層薄膜。 本發明另提供一種於鋁基底金屬基材上形成可隨视角改The coloring of the base metal substrate is traditionally anodized by forming an anodic layer on the reduced metal material by performing anodizing treatment, and then the inorganic metal particles are electrolytically deposited thereon. The anodized film of porous aluminum is achieved in the pores of the anodized film of the porous inscription, or is adsorbed in the pores of the anodized film of the porous inscription. These two types can not only protect the ingot metal substrate from corrosion and scratches. , And can provide beautiful decorative effects. However, the appearance of aluminum products obtained by these two conventional techniques is still dominated by a single color, and the color does not change with different viewing angles. t A conventional optical substrate coloring method can be found in, for example, the description of Japanese Patent No. 59_ 1 3 3 5 001 published on July 31, 1984, which uses an electron gun 4 plating method on a transparent non-metallic substrate. (Such as glass) is sequentially coated with an anti-reflective multilayer film composed of a medium refractive index layer, a high refractive index oxide layer and a low refractive index oxide layer. This Japanese patent mainly focuses on adjusting the composition ratio of the high-refractive index oxide layer to obtain a clock film with reduced reflectance through optical interference effects. 'Ran' This patent focuses on the teaching of transparent substrates, and does not mention any The use of the porous layer can not provide any products that can change color with the change of viewing angle. In addition, the paper size of the U.S. patent applies to the Chinese National Standard (CNS) A4 specification (210X297 mm). A multi-layer film is plated on the material. This multilayer film is a combination of a high-foot and high-refractive-index oxide layer and a low-refractive-index oxide layer that grow alternately. This Wu Guo Patent # "uses a foot substrate that is also a transparent non-metal The base material (mainly for the purpose of polycondensation), and its blending-^, Dragon has not revealed that its products can change color as the viewing angle changes, nor does it mention the use of any porous layer. In response to the market and consumers & gt For two +, for the current, the industry is actively researching and developing aluminum products that can change the color depending on the viewing angle. The aluminum products can be formed on the surface of the aluminum base metal substrate and can be changed according to the angle of view. And a method for producing a film with a color change. ≫ The invention provides an inscription product having a film that can produce a color change according to a change in viewing angle, and a method for forming a color change on the metal substrate of the inscription that can produce a color change with the change in viewing angle. Membrane method. Brief description of the display Figure 1 is a structural diagram of an aluminum substrate of the present invention. Figure 2 is a high-resolution electron microscope photograph of an anodic oxide film formed with an inscription on a base material according to the present invention. * Figure 3 is an anodic oxide film of the present invention The high-resolution electron microscope photographs of the multilayer thin films of high refractive index Ti〇2 film and low refractive index Si〇2 film alternately grown on the top. The main component symbol description in the figure: 1 stands for aluminum base metal substrate; 2 stands for Ming's anodized film Barrier layer; 3 represents the micro-pores of the porous layer of aluminum anodized film, · ----- G-scale Dimensions Choi ® s Jia Jinquan T ^ A4 specifications-7 public love 4 represents the aluminum base metal substrate Surface; 5 represents a low refractive index oxide film; 6 represents a high refractive index oxide film; 7 represents the thickness of the barrier layer of the anodized film of aluminum; 8 represents the thickness of the porous layer of the anodized film of aluminum; The total thickness of the refractive index oxide film and the low refractive index oxide film. DETAILED DESCRIPTION OF THE INVENTION The object of the present invention is to provide an aluminum product with a film that can produce a color change depending on the viewing angle, and an aluminum-based metal substrate. Method for forming a film that changes color with the change of viewing angle. These purposes can be controlled by controlling the thickness of the aluminum anodized film (ie, interference layer) on a surface of an aluminum-based metal substrate to a specific range, and The high-refractive-index oxide film and the low-refractive-index oxide film are alternately grown on top of each other, so that different interference effects occur when the viewer's viewing angle is changed, causing the appearance color of the baseless metal substrate to change. ^ Specifically, this The invention provides an aluminum product with a film that can change color as the viewing angle changes. The aluminum product includes an aluminum-based metal substrate, an anodized film covering the surface of the metal substrate and having a thickness smaller than that of the name. The film includes a porous layer and a barrier layer, and a multilayer thin film of a high-refractive-index oxide film and a low-refractive-index oxide film that alternately grow above the anodized film. The invention also provides a method for forming a metal substrate on an aluminum substrate, which can be changed with the viewing angle.
k而產生顏色變化之膜的方法，其包含： _於鋁基底金屬基材上進行陽極氧化處理，以提供一包 含多孔層及屏障層且厚度小於10μπ1之鋁的陽極氧化膜匕 及 毛▲陽極氧化膜上方交替成長高折射率氧化物薄膜及 低折射率氧化物薄膜之多層薄膜。 本發明中所稱之「可隨視角改變而產生顏色變化的 膜」，係指於入射光下，該膜所含之高折射率氧化物薄膜 及低折射率氧化物薄膜之表面可與鋁基底金屬基材表面產 生干涉效應，因此當觀察者之視角改變時，其會表現不同 之顏色。 對本發明而言，最重要的是位於該鋁基底金屬基材表面 之鋁的陽極氧化膜的厚度必須控制在小於1 〇 ,於此厚 度下’多孔層及屏障層均呈半透明或透明狀態，故可容易 地進行光的吸收與散射，產生所欲之干涉色。 該銘基底金屬基材可為任何此技藝中習用者，較佳係鋁 足合金’已知銘之合金往往含有至少一種另外的金屬元 素，例如矽、鎂、銅、鋅及鐵等，除了厚度以外，鋁合金 足純度亦為可影響該鋁之陽極氧化膜是否可呈半透明或透 明狀態之重要因素。舉例言之，倘若該鋁合金中含有大量 的碎及鐵’則會形成一中間金屬相，並與鋁的陽極氧化膜 結合而產生霧狀膜，其無法產生所欲的干涉效應。因此， 於本發明中’所使用鋁之合金所含的鋁純度較佳係介藉於 9 0 · 0 至 9 9.9 %，最佳介於 9 5.0 至 9 9.9 %。 本紙張尺度適用中國國家標準(CNS) A*規格(21〇χ 297公釐）8 588124 五、發明説明（ 於本發明中，可使用任何此技藝中已知之技術以於鋁基 底金屬基材上進行陽極氧化處理以形成陽極氧化膜，該氧 化膜包含多孔層（外層）與屏障層（内層）。例如，可使用美 國專利第5，4 7 2，7 8 8號中所教示之硫酸浴/直流電法，該 硫酸浴可具有自5至40%之濃度，較佳係具有自1〇至 20%之濃度。視須要亦可使用或搭配使用其他酸浴（如： 5至4 0 %濃度之磷酸）以形成具不同多孔層結構的氧化 膜。該陽極氧化處理之溫度可介於自5至l〇(rc之間，較 佳係介於自15至25。(：之間。藉由控制陽極氧化處理之電 壓大小與處理時間，可控制所形成鋁的陽極氧化膜之厚 度。舉例T之，可於本發明使用介於自〇 · 5至5 〇伏特間 之電壓進行該陽極氧化處理歷〇·5至3〇分鐘，較佳係使 用介於自3至20伏特間之電壓處理！至15分鐘。此外， 陽極氧化處理時使用之電壓對所形成鋁之陽極氧化膜结構 亦具有影響。一般而言，當電壓愈大，所形成多孔層^孔 數少且孔壁厚度大，故屏障層之厚度亦會隨之增加。反 之’當電壓愈小，則所形成多孔層之孔數多且孔壁厚产 二、。因此，於正常陽極氧化處理流程中，偏將施加之電： 遽然下降，則會使多孔層之孔隙底部形成分支，成為 數=小孔徑的孔隙者，此使得銘之陽極氧化膜與基“ 《結合力變得較弱。於本發明中，經陽極氧化 〜 底金屬基材所形成之館的陽極氧化膜厚度係何二:基 且相對來說，多孔層之厚度大於屏障層。 111， 接著，本發明料該_氧化膜表^交替成長高拆射 ^纸張尺度制t開家鮮 裝 訂 娜124 、發明説明（6 率氧化物薄膜及低折射率氧化物薄膜之多層薄膜。可使用 任何已知技術成長該高折射率氧化物薄膜及低折射率氧化 物薄膜。舉例言之，但錢^，可利用㈣（sputtering) 《万式進#。例如，於本發明中可採用射頻(η — · hquency)方式，以高純度（例如99 9%)Ti〇2或以〇2作 為靶材，利用最大功率為6〇〇瓦(w)之能量分別將 丁1〇2或㈣2㈣以原子或離子飛賤之方式，依次沉積於 銘基材4氡化銘層表面上；或者，可採用電子鎗蒸鍵方 式’於例如1χ10-Μχ10、ΟΓΓ之壓力下施加1〇 κν的 屯壓’包子速度可達6xl〇4km/Sec，電子束高速撞擊在膜 材料上轉換成熱能，溫度可達攝氏數千度，如此可使材料 蒸發，依次沉積於鋁基材之氧化鋁層表面上。其中各層之 厚度係以石英震盡膜厚計分別量測，並以自動關閉器 (shutter)控制各層厚度於5〇〇至1〇〇〇人之間。藉由調整 此等高折射率及低折射率氧化物薄膜之層數與厚度，可造 成不同的光學干涉效應。其中’較佳係交替成長各3層之 高折射率氧化物薄膜及低折射率氧化物薄膜，更佳係交替 成長各5層之高折射率氧化物薄膜及低折射率氧化物薄 膜，每層厚度較佳係控制於數十至數百奈米之内。申請人 發現到，於基材上交替成長高折射率氧化物薄膜及低折射 率氧化物薄膜之多層薄膜，可提供不同的干涉效應，使基 材表面可隨視角不同顯現不同顏色變化。 於本發明中，較佳地，#亥南折射率氧化物係具有自2至 2.5間之折射率，其光程差為λ/2，而該低折射率氧化物係 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐） 裝 玎 t 588124 五、發明説明ί 具有自1.3 S 1.7間之折射率，其光程為入/4。可使用任 何合宜之高折射率氧化物與低折射率氧化物，其中，適用 之高折射率氧化物的例子可為，但不限於，Zr〇2、 ΊΆ、Ce02、Cr2〇3及Ta2〇5，而適用之低折射率氧化 物的例子可為，但不限於，Si〇2、MgF2及叫八…。 光學干涉效應主要係因光線在下列表面間發生反射而造 成干涉與吸收之結果：⑴位於屏障層下方的减底金屬底 材之表面，及（2)位於陽極氧化膜上方之交替成長高折射率 氧化物薄膜低折射率氧化物薄膜之多層薄膜表面。由於入 射光之路&與所沈積金屬氧化物之折射率及膜厚有關，故 折射率不同，膜厚不同，則會有不同的光程差（光學膜厚X 折射率），造成產生之干涉色亦有差異。 於本毛月中，申凊人發現到，當陽極氧化膜厚度小於 1 Ο μιη時（即多孔層及屏障層均為半透明或透明狀態時）， 再配合父替成長 < 高折射率氧化物薄膜及低折射率氧化物 薄膜之多層薄膜，可造成至少二個方向性的光學干涉效 應。光學干涉效應主要係因光線在下列數層金屬氧化物表 面發生反射而造成干涉與吸收之結果：（1)位於鋁陽極氧化 層上方之乂替成長之高折射率氧化物薄膜及低折射率氧化 =薄膜之多層薄膜之表面，及⑺位於屏障層下方的铭基底 至屬底材<表面。不同入射光路徑與及/或高（低）折射率氧 化物物種，所產生之干涉色便有所差異。 圖1代表本發明之較佳實施態樣，其中探討干涉層之結 構、干涉層之厚度及氧化物材質間之關係。 Α4規格(210X297公釐） 度適用中國國家冢^^ 588124 A7 B7 五、發明説明（8 )A method for producing a color-changing film includes: _ anodizing an aluminum-based metal substrate to provide an anodized aluminum film and wool comprising aluminum and a porous layer and a barrier layer with a thickness of less than 10 μπ1 ▲ anode A multilayer thin film of a high refractive index oxide film and a low refractive index oxide film is alternately grown on the oxide film. The “film that can change color with the change of viewing angle” in the present invention means that under incident light, the surface of the high-refractive-index oxide film and the low-refractive-index oxide film contained in the film can be compared with the aluminum substrate. The surface of the metal substrate produces an interference effect, so when the viewing angle of the observer changes, it will show different colors. For the present invention, the most important thing is that the thickness of the anodized film of aluminum on the surface of the aluminum base metal substrate must be controlled to less than 10, at which the 'porous layer and the barrier layer are translucent or transparent, Therefore, light can be easily absorbed and scattered to produce a desired interference color. The inscription base metal substrate can be any person skilled in the art, preferably an aluminum foot alloy. Known inscription alloys often contain at least one other metal element, such as silicon, magnesium, copper, zinc, and iron, in addition to the thickness. In addition, the purity of the aluminum alloy is also an important factor that can affect whether the anodized film of the aluminum can be translucent or transparent. For example, if the aluminum alloy contains a large amount of scrap and iron ', an intermediate metal phase will be formed, which will be combined with the aluminum anodic oxide film to produce a misty film, which cannot produce the desired interference effect. Therefore, in the present invention, the aluminum contained in the alloy of aluminum used in the present invention preferably has a purity of 90% to 99.9%, most preferably 95.0% to 99.9%. This paper size applies Chinese National Standard (CNS) A * specification (21〇χ 297 mm) 8 588124 V. Description of the invention (In the present invention, any technique known in the art can be used on aluminum-based metal substrates Anodizing is performed to form an anodized film, which includes a porous layer (outer layer) and a barrier layer (inner layer). For example, a sulfuric acid bath taught in US Patent No. 5,4 7 2, 7 8 8 can be used. In the direct current method, the sulfuric acid bath may have a concentration of from 5 to 40%, preferably a concentration of from 10 to 20%. Other acid baths (such as: 5 to 40% of Phosphoric acid) to form oxide films with different porous layer structures. The temperature of the anodizing treatment may be from 5 to 10 (rc, preferably from 15 to 25. (:.). By controlling The voltage and processing time of the anodizing treatment can control the thickness of the anodized film formed of aluminum. For example, in the present invention, the anodizing treatment can be performed using a voltage between 0.5 and 50 volts in the present invention. 0.5 to 30 minutes, preferably between Voltage treatment between 3 and 20 volts! To 15 minutes. In addition, the voltage used in the anodizing treatment also has an effect on the structure of the anodized film of aluminum formed. Generally speaking, when the voltage is larger, the porous layer is formed. If the number is small and the thickness of the pore wall is large, the thickness of the barrier layer will also increase. Conversely, when the voltage is smaller, the number of pores formed in the porous layer is larger and the thickness of the pore wall is two. Therefore, in the normal anodizing process, The partial electricity will be applied: If it suddenly drops, it will cause the bottom of the pores of the porous layer to branch into pores with a number of small pores, which makes Ming Zhi ’s anodic oxide film and substrate "the binding force becomes weaker. In the invention, what is the thickness of the anodic oxide film in the hall formed by the anodization to the base metal substrate: relatively speaking, the thickness of the porous layer is greater than the barrier layer. 111, Next, the present invention expects the _ oxide film table ^ Alternative growth of high-resolution shots ^ Paper-scale manufacturing of tatami 124, invention description (6-rate oxide film and low-refractive-index oxide film multilayer film. This high-folding can be grown using any known technique Rate oxide film and low-refractive-index oxide film. For example, but ^, you can use sputtering << 万 式 进 #. For example, in the present invention, a radio frequency (η-· hquency) method can be used to High purity (for example, 99 9%) Ti〇2 or 〇2 as the target material, using the maximum power of 600 watts (w) of the energy respectively to Ding 102 or ㈣2㈣ in an atomic or ionic manner, in order, It can be deposited on the surface of the base layer of the substrate. Alternatively, electron gun bonding can be used to 'apply a pressure of 10kv under a pressure of 1x10-Mx10, 0ΓΓ'. The bun speed can reach 6x104km / Sec, The electron beam impinges on the film material and converts it into thermal energy at a temperature of thousands of degrees Celsius. This can cause the material to evaporate and deposit on the surface of the aluminum oxide layer of the aluminum substrate. The thickness of each layer is measured by a quartz shaker film thickness meter, and the thickness of each layer is controlled by an automatic shutter (500 to 10,000 people). By adjusting the number and thickness of these high and low refractive index oxide films, different optical interference effects can be created. Among them, 'preferably, alternately grows three layers of high-refractive-index oxide films and low-refractive-index oxide films, and more preferably, alternately grows five-layer high-refractive-index oxide films and low-refractive-index oxide films, each layer The thickness is preferably controlled within tens to hundreds of nanometers. The applicant has found that multilayer films of high refractive index oxide films and low refractive index oxide films grown alternately on the substrate can provide different interference effects, so that the surface of the substrate can show different color changes with different viewing angles. In the present invention, it is preferable that #HAI 南 refractive index oxide has a refractive index from 2 to 2.5, and the optical path difference is λ / 2, and the low refractive index oxide is suitable for the country of this paper. Standard (CNS) A4 specification (210 X 297 mm) Decoration t 588124 V. Description of the invention ί It has a refractive index between 1.3 S and 1.7, and its optical path is in / 4. Any suitable high-refractive-index oxide and low-refractive-index oxide can be used. Among them, examples of suitable high-refractive-index oxides can be, but are not limited to, ZrO2, Hf, Ce02, Cr203, and Ta205. Examples of suitable low-refractive-index oxides are, but are not limited to, Si02, MgF2, and eight. The optical interference effect is mainly the result of interference and absorption caused by the reflection of light between the following surfaces: 表面 the surface of the reduced-substrate metal substrate located below the barrier layer, and (2) the alternately growing high refractive index above the anodized film Multilayer thin film surface of oxide thin film. The path of incident light is related to the refractive index and film thickness of the deposited metal oxide. Therefore, if the refractive index is different and the film thickness is different, there will be different optical path differences (optical film thickness X refractive index). Interference colors are also different. In the middle of this month, Shen Yanren found that when the thickness of the anodic oxide film is less than 10 μm (that is, when the porous layer and the barrier layer are both translucent or transparent), the growth is accompanied by the growth of the parent < high refractive index oxidation Multilayer thin films of thin films and low refractive index oxide films can cause at least two directional optical interference effects. The optical interference effect is mainly the result of interference and absorption caused by the reflection of light on the surface of the following several metal oxides: (1) a high-refractive-index oxide film and a low-refractive-index oxide that grow on the aluminum anodized layer; = The surface of the multilayer film, and the substrate under the barrier layer to the substrate < surface. The interference color produced by different incident light paths and / or high (low) refractive index oxide species varies. FIG. 1 represents a preferred embodiment of the present invention, in which the relationship between the structure of the interference layer, the thickness of the interference layer, and the oxide material is discussed. Α4 specification (210X297mm) Degree Applicable to Chinese National Mound ^^ 588124 A7 B7 V. Description of Invention (8)
裝 參閱圖1，其中係使用硫酸浴/直流電法進行陽極氧化處 理，以於鋁基底金屬基材1上生成一包含多孔層8及屏障 層7的铭之陽極氧化膜，該铭之陽極氧化膜之厚度（即，多 孔層8及屏障層7之總厚度）係小於1 〇 μ m，於此厚度下， 多孔層及屏障層均呈半透明或透明狀態。然後以電子鎗蒸 鍍設備於該陽極氧化膜上方交替成長各5層之高折射率氧 化物6及低折射率氧化物5薄膜，此薄膜總厚度小於 2000A。入射光A照射到此薄膜表面會產生反射、透射、 偏振及相位變化，進而使此鏡膜形成建設性干涉，此鍍膜 之厚度與光學路徑有關，不同的厚度會產生不同的光程 差，因此顏色變化取決於氧化物材質、材質沉積厚度及陽 極氧化鋁層厚度。 藉由研讀以下實例可進一步了解本發明之目的、特徵及 優點。 實例1 f 將銘純度為9 9 · 5 %之铭合金依下列步驟進行前處理：首 先以2 0 %之焦磷酸鈉，於6 0 °C之溫度下進行脫脂處理3 刀4里’經水洗之後、再藉超音波作用於上述溶液中，進行 脫脂處理3分鐘，再經水洗後，以濃度為3 〇 %之硝酸水溶 液予以中和30秒。此可於铭合金上形成厚度為5 μπι的鋁 之陽極氧化膜，其包含多孔層與屏障層。 將經上述前處理之铭合金’於濃度為1 2 %之硫酸浴中， 於15。(：之溫度下，使用7伏特之直流電壓進行陽極氧化處 理1 〇分鐘，此於鋁基材上形成之鋁之陽極氧化膜之高解 本紙張尺度適用中國國家標準(CNS) Α4規格(210Χ 297公爱)" ---- A7 A7Please refer to FIG. 1, in which an anodic oxidation treatment is performed by using a sulfuric acid bath / DC method to generate an anodized film including a porous layer 8 and a barrier layer 7 on the aluminum-based metal substrate 1. The anodized film of the inscription The thickness (that is, the total thickness of the porous layer 8 and the barrier layer 7) is less than 10 μm. At this thickness, the porous layer and the barrier layer are both translucent or transparent. Then, an electron gun evaporation device is used to alternately grow 5 layers of high refractive index oxide 6 and low refractive index oxide 5 films on the anodized film, and the total thickness of the film is less than 2000A. The incident light A irradiates the surface of the film, which will cause reflection, transmission, polarization, and phase changes, which will cause the mirror film to form constructive interference. The thickness of the coating film is related to the optical path. Different thicknesses will cause different optical path differences, so The color change depends on the oxide material, the thickness of the material deposited, and the thickness of the anodized aluminum layer. The purpose, features, and advantages of the present invention can be further understood by studying the following examples. Example 1f A pretreatment of Ming alloy with a purity of 99.5% was performed according to the following steps: first degreasing with 20% sodium pyrophosphate at 60 ° C 3 knives 4 miles' washed with water Then, the solution was subjected to ultrasonic waves to perform degreasing treatment for 3 minutes, and then washed with water, and then neutralized with a 30% nitric acid aqueous solution for 30 seconds. This can form an anodized film of aluminum with a thickness of 5 μm on the Ming alloy, which includes a porous layer and a barrier layer. The above-prepared Ming alloy 'was placed in a sulfuric acid bath having a concentration of 12% at 15%. (: Anodizing treatment is performed at a temperature of 7 volts DC voltage for 10 minutes. The high resolution of the aluminum anodized film formed on the aluminum substrate is based on Chinese paper standard (CNS) A4 specification (210 × 297 public love) " ---- A7 A7
析電子顯微鏡相片參見圖2。 2 ^ ’利用電子鎗蒸鍍方式 丁.。上方交替成長各5層之高折射率氧化物（即 1 2)薄版與低折射率氧化物（即Si〇2)薄膜 用真空度係之蒸發溫度係_。^ 所形成s1〇2層之厚度為700A，而Ti〇2之墓發溫度係 19〇〇t，所形成之厚度為i咖A。所獲得銘製品之高解 析電子顯微鏡相片可參見圖3。 由於月例1中係於鋁基材上形成鋁之陽極氧化膜，以及交 替成長<高折射率氧化物及低折射率氧化物多層薄膜，此 結構於入射光進入後，會產生反射、透射、偏極及相位變 化’因而當觀祭者位於不同視角下，該铭合金表面因干涉 效應而會產生至少2種之顏色變化。 ---13- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐）Analytical electron micrographs are shown in Figure 2. 2 ^ ’using electron gun evaporation method D .. Five layers of high-refractive-index oxide (ie 12) thin plates and low-refractive-index oxide (ie Si02) thin films are grown alternately on the top. ^ The thickness of the s102 layer is 700A, and the temperature of the tombstone of Ti02 is 1900t, and the thickness of the layer is iCaA. The high resolution electron micrograph of the obtained Ming product can be seen in Figure 3. Since the anodic oxide film of aluminum is formed on the aluminum substrate in the example 1 and the multilayers of <high-refractive-index oxide and low-refractive-index oxide are grown alternately, this structure will cause reflection, transmission, and Polarization and phase change '. Therefore, when the spectator is at different viewing angles, the surface of the Ming alloy will have at least 2 color changes due to interference effects. --- 13- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)