TW593786B - Aluminum product with film with variable colors corresponding to variable view angles, and method for forming a film with variable colors corresponding to variable view angles on an aluminum substrate - Google Patents

Abstract

An aluminum product with a film with variable colors corresponding to variable view angles includes: an aluminum substrate; an aluminum anode oxide film having a thickness less than 10 mum on the surface of the metal substrate, the oxide film including a porous layer and a barrier layer, and a metal deposition formed in the voids of the porous layer, in which the metal deposition is formed by a d.c./a.c. alternating or a combined d.c./a.c. alternating electrolysis process. The aluminum product further includes a roughened layer above the anode oxide film, and/or a multilayered film above the roughened layer and alternatively formed of a high reflective oxide and a low reflective oxide. The present invention further relates to a method for forming a film with variable colors corresponding to variable view angles on an aluminum substrate, which comprises: performing an anode oxidization treatment on an aluminum substrate for providing an aluminum anode oxide film having a porous layer and a barrier layer and with a thickness less than 10 mum on the substrate; and using a d.c./a.c. alternating or a combined d.c./a.c. alternating electrolysis process to deposit a metal deposition in the voids of the porous layer for electrolysis coloring of the aluminum anode oxide film, in which the aluminum substrate receives a roughening treatment prior to receiving the anode oxidation treatment in order to form a roughened layer on the surface of the substrate, and the subsequent anode oxidation treatment forms an anode oxide film between the substrate surface and the roughened layer, and/or a multilayered film consisting of a high reflective oxide and a low reflective oxide are alternatively grown on the anode oxide film after an electrolysis coloring on the aluminum substrate.

Description

593786 A7 __________B7 V. Description of Invention (i)

Invention Back I In recent years, 'the rapid development of 3C industries such as computers, communications, and consumer electronics has made the base metal substrate a decorative shell < 3C products (for example: notebook computers, mobile phones, walkmans, CD players) Devices, MP3s, cameras, and personal digital assistants (pDA) temples) have increasing market demand. Aluminum-based metal substrates are not only lightweight and have a metallic texture, so they have gradually replaced the appearance of painted parts. ^ The coloring of aluminum-based metal substrates has traditionally been achieved by performing anode and protonization treatments and electrolytic coloring with inorganic metal particles. This not only protects aluminum-based metal substrates from corrosion and scratches, but also provides aesthetics. Decorative effect, thus improving the economic value of aluminum-based metal substrates. The anodizing treatment and electrolytic coloring of aluminum-based metal substrates are currently mature technologies. They are generally used in electrolytic baths (such as sulfuric acid bath or phosphoric acid bath) using alternating DC / AC power or using DC or AC power alone. The base metal substrate forms a layer of anodic oxide film, which includes a porous layer (that is, an outer layer) and a barrier layer (that is, an inner layer), and then machine metal particles are deposited in the pores of the porous layer. In order to give the aluminum base metal substrate a colored appearance. However, the appearance color of the products obtained by conventional techniques is still mainly a single color, and there are not many types of colors, mainly bronze, black and red. For the two conventional coloring methods of base metal substrates, please refer to, for example, Eliseo Benitez-Garriga awarded to December 5th, 1995--6-This paper size applies Chinese National Standard (CNS) A4 (210 χ 297 mm) —-

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Line 593786 A7 B7 V. Description of the United States Patent No. 5,472,78 No. 8 of the Invention Description (2), this U.S. Patent discloses colored anodized aluminum products and a method for electrolytically coloring anodized aluminum products. A conventional sulphuric acid bath / DC method is used to form a layer of anodic oxide film on the surface of an aluminum-based metal substrate. The oxide film includes a porous layer (ie, an outer layer) and a barrier layer (ie, an inner layer). Direct current, alternating current, direct current-> The alternating current of alternating current and direct current is used to perform electrolytic coloring of aluminum-based metal substrates in an alternating current of 5 times. According to the examples provided in this U.S. patent specification, the thickness of the anodic oxide film formed of aluminum is more than 15 μm. At this thickness, the colored anodic oxide film can only show the effect of interference effects. The single color produced cannot express the effect of color change with the change of viewing angle. In addition, although this US patent additionally seals the surface of the product, when a finger touches the surface, it is easy to stain fingerprints and not easy to remove. At present, in response to the needs of the market and consumers, the industry is actively researching and developing aluminum products with a film that can change color depending on the viewing angle change, and can form a film that can change color depending on the viewing angle on the surface of the aluminum base metal substrate. method. Preferably, the aluminum product having a film capable of producing a color change according to a change in viewing angle can simultaneously avoid fingerprint contamination. Brief description of the invention: The present invention provides an aluminum product with a film that can produce significant color changes depending on the viewing angle change, and the paper is formed on an aluminum-based metal substrate. The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) ) 593786 A7 B7 V. Description of the invention (Method of film that can produce significant color changes with changes in viewing angle. In the preferred embodiment of the present invention, the film is produced with a film that can change color depending on the viewing angle. The problem of fingerprint contamination of aluminum products can be improved at the same time. Brief description of the figure Figure 1 represents the alternating growth of aluminum roughened surface, anodized film, and high-refractive index oxide and low-refractive index oxide formed by the method of the present invention. A specific embodiment of the interference effect between the multilayer films, wherein the anodic oxide film of aluminum is formed by anodizing in a sulfuric acid bath, and the total thickness is less than 10 μm. Figure 2 represents the method formed by the method of the present invention. Another embodiment of the interference effect between the roughened aluminum surface, the anodic oxide film, and the alternating growth multilayer films of high refractive index oxides and low refractive index oxides The aluminum anodic oxide film is formed through the anodic oxidation treatment sequence of sulfuric acid bath-phosphoric acid bath-sulfuric acid bath. Figure 3 represents the roughened surface of aluminum, anodized film, high-refractive index oxide, and low refractive index formed by the method of the present invention. Another specific embodiment of the interference effect of the alternate growth of multi-layered thin films, the anodic oxide film is formed by the anodic oxidation treatment sequence of the sulfuric acid bath-the acid bath. Figure 4 represents the method of the present invention. The formed rough surface, anodized film, and high-refractive-index oxide and low-refractive-index oxide are alternately formed, and another embodiment of the interference effect between long multilayer films is implemented. The anodized film of aluminum is adjusted. Under voltage conditions at -8- This paper size applies to China National Standard (CNS) Α4 size (210 X 297 mm)

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Line 593786 A7 B7 V. Description of the invention (4) It is formed by anodic oxidation treatment in sulfuric acid bath. Description of the main elements of the figure 4 Symbol 1 represents the base metal substrate; 2 represents the metal deposit layer; 3 represents the micropores of the porous layer of the anodized aluminum film; 4 represents the barrier layer of the anodized aluminum film; y represents The surface of the metal deposit; 6 represents the surface of the base metal substrate; 7 represents the porous layer of the anodized film of aluminum, 8 represents the roughened surface; 9 represents the alternating growth of high refractive index oxides and low refractive index oxides. Thin film; 10 represents small pores A, B, C, D in the micropores of the porous layer; and d represents the total thickness of the anodized film of aluminum. DETAILED DESCRIPTION OF THE INVENTION The object of the present invention is to provide Aluminum products that produce a color-changing film, and the formation of a color that changes with the viewing angle on a metal substrate with a change in viewing angle: a method of changing the film. In addition, by controlling the anodization of aluminum on the surface of the metal substrate The thickness of the film (ie, the interference layer) Scope > The present invention can provide a base metal substrate with different appearance colors as the observer's viewing angle changes. In addition, by subjecting the substrate to a roughening treatment before the substrate is anodized, the product can be made to have different viewing angles. -9- This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) 593786 A7 B7 V. Description of the invention (5) The effect of changing color is more obvious. The present invention also provides a method for improving fingerprint contamination problems. The aluminum anodic oxide film is electrolytically colored, and a multilayer film of high-refractive index oxide and low-refractive index oxide is alternately grown thereon. The reflection color of the material, this treatment can make the appearance color of aluminum products more diversified. In particular, the present invention provides an aluminum product with a film that can produce color as the viewing angle changes. The film comprises:-a base metal substrate,-an aluminum covering the surface of the metal substrate and having a thickness of less than 10 μm An anodic oxide film, the oxide film includes a porous layer and a barrier layer, and-metal deposits in the pores of the porous layer, wherein the metal deposits are performed by alternating current or alternating current or both Obtained by electrolytic coloring, the aluminum product further includes a roughened layer above the anodized film, and / or an alternating-growth multilayer film of high refractive index oxide and low refractive index oxide located above the roughened layer. The present invention further provides a method for forming a film that can change color as the viewing angle changes on an aluminum-based metal substrate, including:-anodizing an aluminum-based metal substrate to provide a Contains a porous layer and a barrier layer with a small thickness, anodized film of aluminum at 10 μιη, and-by alternating current or alternating current or both simultaneously-This paper size applies to Chinese National Standard (CNS) Α4 Specifications (210 X 297 mm) 593786 A7 B7 ___ V. Description of the invention (6) Formula: deposit metal deposits in the pores of the porous layer to perform aluminum anode and polarized film electrolytic coloring, where Before the aluminum base metal substrate is anodized, a roughening treatment is performed to form a roughened layer on the surface of the substrate, and then an anodizing treatment is performed to form a layer between the substrate surface and the roughened layer. Anodized films and / or multilayer films of high-refractive-index oxides and low-refractive-index oxides are alternately grown on the anodized films after the aluminum-based metal substrate is electrolytically colored. In the present invention, the "film that can change color with the change of viewing angle" means that under incident light, the surface of the metal deposits contained in the film can interfere with the surface of the aluminum-based metal substrate. When the observer's perspective changes, they will show different colors. In a preferred embodiment of the present invention, a multilayer film of high-refractive index oxide and low-refractive index oxide is alternately grown on the substrate, which can improve the fingerprint contamination problem on the surface of aluminum products and can provide different The interference effect makes the surface of the substrate show another color change. In the present invention, the roughening treatment is a process before anodizing, and can be a chemical etching treatment or a physical sandblasting treatment. It has the functions of paint removal, etching, stress relief, surface treatment, matting, pear field, etc. The purpose is Refinish the appearance and texture of aluminum products. Any conventional etching technique can be used for chemical etching. -11-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 593786

Management. Generally speaking, chemical etching is mostly alkaline, but depending on the product, an acidic etching solution is also used as needed to produce different retouching effects. Traditional alkali .. Etching is mainly caustic soda, concentration H) wt%; acidic etching is nitric acid, gasification, hydrofluoric acid, etc., ▲ degree is 1 ~ 5% 'for Yu Qinian κ,' The soil spreads to an average roughness of about 1.2 on the surface of the substrate. Any conventional technique can be used for physical blasting. Suitable blasting materials can be changed according to different requirements. Commonly used blasting materials include, but are not limited to, glass beads, oxidation boats, sands, plastic pellets, silicon carbide, steel balls, and steel gravel. In the present invention, the blasting conditions may be, but are not limited to, the use of glass-breaking bead sand with a particle size of 12 to 25 is carried out under a gas pressure of 2 kg / cm2, and the distance between the nozzle and the workpiece is about 150 mm. The average roughness is about ο. For the present invention, the most important thing is that the thickness of the aluminum anodized film on the surface of the aluminum-based metal substrate < aluminum must be controlled to be less than, and at this thickness, the porous layer and the barrier layer are translucent or transparent, so It can easily absorb and scatter light to produce desired interference colors. The aluminum-based metal substrate can be any person skilled in this art. The aluminum alloy is an aluminum alloy. It is known that aluminum alloys often contain at least one metal element other than aluminum, such as silicon, magnesium, copper, zinc, and iron. In addition to the thickness, the purity of the aluminum alloy is also an important factor that can affect the anodization of the aluminum and whether the film can be translucent or transparent. Milk, example ^ If the far-away alloy contains a large amount of scrap and iron,

593786 A7 B7 V. Description of the invention (8) An intermediate metal phase is formed, which is combined with the aluminum anodic oxide film to produce a mist film, which cannot produce the desired interference effect. Therefore, in the present invention, the aluminum purity of the aluminum alloy used is preferably between 90.0 and 99.9%, and most preferably between 95.0 and 99 9%. In the present invention, any technique known in the art can be used to perform an anodic oxidation treatment on an aluminum-based metal substrate to form an anodic oxide film. The oxide film includes a porous layer (outer layer) and a barrier layer (inner layer). ). For example, 'a sulfuric acid bath / DC method not taught in U.S. Patent No. 5,472,788 may be used, and the sulfuric acid bath may have a concentration of from 5 to 40%', preferably having a concentration of from 10 to 20%. If necessary, other acid baths (eg, 5 to 40% concentration of transacid) can also be used or combined to form oxide films with different porous layer structures. The temperature of the anode oxidation treatment may be between 5 and 100 t, more preferably between 15 and 25 C. By controlling the voltage and processing time of the anodizing process, the thickness of the anodized film of aluminum can be controlled. For example, in the present invention, the anodizing treatment can be performed using a voltage between 0.5 and 50 volts for 0.5 to 30 minutes, preferably using a voltage treatment between 3 and 20 volts. To 15 minutes. In addition, the voltage used in the anodizing process also affects the structure of the anodized film formed. Generally, when τ is larger, the number of pores formed in the porous layer is smaller and the thickness of the pore wall is larger, so the thickness of the barrier layer will increase accordingly. Conversely, when the voltage is smaller, the number of pores of the porous layer formed is larger and the thickness of the pore wall is smaller. Therefore, in the normal anodizing process, if the -13- ^ paper size is applicable to the CNS A4 specification (21〇297297)

593786 A7

If the pressure drops suddenly, it will make the pores of the porous layer become pores with several smaller pores. The bonding force between the anodic oxide film and the substrate of the Qi Deming becomes weaker, which makes the invention Zhong 'anodized on Ming base gold: The thickness of the anode's vaporized film made of aluminum is V-emulsion 1 ^. The thickness is less than 10 μm, and relatively, the thickness of the pore layer is greater than the barrier. Any of the electrolytic coloring techniques known in the art can be used for the month of _Jiajia. The prerequisite is that it must be AC / DC. For examples, see, for example, US Patent No. 5,472,788. For example, it can be used in the present invention with the following Group ΐ :: Fun bath: Concentration from 1…. G / L of H2SO4 from 10 to 40 g / L of magnesium sulfate, a concentration of 15 to 5: 2 liters ... and a concentration of 5 to 30 g / L of ammonium sulphate, using parent galvanic / DC alternating current Or a combination of both, using 2 to 50 volts of electrons (preferably from 5 to 20 volts) to deposit metal deposits in the pores of the porous layer. In the present invention, depending on the applied voltage, the time for electrolytic coloring may be from 05 to 30 minutes (preferably i to 10 minutes). Appropriate metal deposits are known and can be selected from, for example, groups consisting of steel, iron, nickel, nickel, tin, gold, silver, shipping, copper, copper, M, and molybdenum. The thickness of the metal deposit also affects the type of interference color formed. Therefore, in the present invention, the thickness of the metal deposit may be from 0 to 1 and μm, preferably from 0.1 to 2 μm. In the present invention, the applicant has found that the anodic oxidation film of Dang Ming's __ ^-14- This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm)

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593786 Α7 Β7 V. Description of the invention (1 ()) When the thickness is less than 10 μm (that is, when the porous layer and the barrier layer are translucent or transparent and in a state), it is used in combination with alternating current or alternating current or both. Electro / decolorization can cause at least two directional optical interference effects. In another preferred embodiment of the present invention, the substrate is an electrolytically colored aluminum oxide layer surface j of the substrate, and grows a high-refractive index emulsion film and a low-refractive index oxide film. The high refractive index oxide film and the low refractive index oxide film can be grown using any known technique. For example, but not limited to, it can be carried out by means of sputtering. For example, in the present invention, a radio-frequency method can be used, with a high purity (for example, 99.9%) of TiO 2 or Si〇2 as a target, using a maximum power of 600 watts (w) of energy, respectively, Ti02 or Si02 targets were deposited on the roughened layer _ alumina and Metal layer-the sandblasted surface of the aluminum substrate, where the thickness of each layer is measured separately with a quartz vibrating film thickness meter, and the thickness of each layer is controlled between 500 and ιοοοΑ by an automatic shutter. By adjusting the number and thickness of these high refractive index and low refractive index oxide films, different optical interference effects can be caused. Among them, it is preferable to alternately grow 3 layers of high refractive index oxide films and 3 layers of low refractive index oxide films, and more preferably to grow 5 layers of high refractive index oxide films and 5 layers of low refractive index oxide films in each case. The layer thickness is preferably controlled within a few tens and hundreds of nanometers in the stem. The applicant found that the multilayers of high refractive index oxides and low refractive index oxides were alternately grown on the substrate -15-593786 A7 B7

V. Description of the invention (U film can further improve the fingerprint contamination problem on the surface of the product. In addition, it can provide different interference effects to make the surface of the substrate appear different color changes. / In the use of the present invention, Preferably, the high-refractive index oxide has a refractive index ranging from 2 to 2.5, and the low-refractive index oxide has a refractive index between 1.3 and 1. 7. Any suitable high-refractive index can be used Oxides and low-refractive-index oxides, among which examples of suitable south-refractive-index oxides can be, but are not limited to, Ti〇2. Or Zr〇2, and examples of suitable low-refractive-index oxides can be, but Not limited to Si02 and Al203. The optical interference effect is mainly the result of interference and absorption caused by the reflection of light between the following surfaces: (丨) the surface of the metal deposits deposited in the pores of the porous layer, and (2) located at the barrier The surface of the base metal substrate under the layer, and (3) the surface of the multilayer film with alternating growth of the refractive index oxide and the low refractive index oxide above the anodized surface. Due to the difference between the incident light path and the metal deposit, There are also differences in the interference colors. Figures 1 to 4 represent different embodiments of the present invention, in which the relationship between the structure of the interference layer and the type of electrolyte, the formation method, and the use voltage are discussed. See Figure 1, Among them, the aluminum-based metal substrate 1 is firstly subjected to a sand blasting treatment to generate a textured metal atomized surface 8 ′. Then, it is subjected to a pretreatment, and then anodized using a sulfuric acid bath / DC method to apply the aluminum substrate. A metal substrate 1 is produced containing -16- this paper size applies to Chinese National Standard (CNS) A4 specifications (210 X 297 mm) 593786 A7 B7 V. Description of the invention (12) Inscription of porous layer 7 and barrier layer 4 The anodic oxide film, the anode of the aluminum. The thickness d of the anodic oxide film (that is, the total thickness of the porous layer 7 and the barrier layer 4) is less than 10 μm. At this thickness, the porous layer and the barrier layer are translucent or Transparent state. The metal 2 is deposited on the bottom of the hole 'gap 3 for alternating color by alternating current or alternating current or both at the same time. On the surface of aluminum anodized film, a multi-layer thin film of high refractive index oxide and low refractive index oxide is alternately grown. The incident light A is reflected on the aluminum base. The surface of the base metal substrate 6 reflects, and the incident light B is on the metal. The surface 5 of the deposit is reflected, and the incident light C and D are reflected on the surface of the multilayer film 9 of the high refractive index oxide and the low refractive index oxide. The reflecting surface and optical path of this structure can show the interference effect of at least two color changes. And, it can improve the fingerprint contamination on the surface of aluminum products. FIG. 2 shows another preferred embodiment of the present invention. In this embodiment, the aluminum-based metal substrate 1 is firstly subjected to a sandblasting treatment to produce a metal atomized surface 8 having a texture and feel, and then subjected to a pretreatment and a sulfuric acid bath / DC method for the first time. Sub-anodizing treatment to form an aluminum anodized film on the base metal substrate 1 and then performing a second anodizing treatment using a phosphoric acid bath / DC method, which can increase the surface area of the bottom of the pores in the porous layer. Therefore, the pore structure with narrow upper and lower width (similar to the bottleneck) is formed. \ Electrolytic coloring is performed by alternating DC / AC current or both. Both metals such as nickel are deposited in the pores. -17 Chinese National Standard (CNS) A4 specification (210 X 297 mm) 593786 A7 B7 5. Description of the invention (13) At the bottom, metal deposits are formed. Subsequently, the third anodizing V ^ treatment is performed, and the aforementioned metal deposits are semi-transparent, so that the electricity can be passed through the third anodizing treatment to decompose them. Next, on the surface of the anodized film of aluminum, a multilayer film 9 of high-refractive index oxide and low-refractive index oxide is alternately grown. In this way, the surface area of the surface 5 of the metal deposit is increased, and at least two different interference colors can be expressed, and the thickness of the anodized film of aluminum formed by the third anodizing treatment will also affect the result of the interference effect. ,-Can improve fingerprint contamination on the surface of aluminum products. FIG. 3 shows another preferred embodiment of the present invention. Specific here

V In the implementation aspect, the aluminum-based metal substrate 1 is firstly subjected to a sandblasting treatment to generate a textured metal atomized surface 8 and then subjected to a pretreatment, and then a sulfuric acid bath / DC method is used for the first anodizing treatment. An aluminum anodized film is formed on the aluminum-based metal substrate 1, and then a second anodizing treatment is performed by a phosphoric acid bath / DC method. Wide (similar to bottleneck) pore structure. After that, electrolytic coloring is performed by alternating DC current or alternating current or both, and a metal such as nickel is deposited on the bottom of the pore to form a metal deposit. After that, a multilayer film 9 of high refractive index oxide and low refractive index oxide is alternately grown on the surface of the anodized film of the electrolytically colored Ming. With this structure, the emission surface and optical path can show the interference effect of at least two color changes, and can improve the fingerprint contamination on the surface of aluminum products. -18- This paper size applies to China National Standard (CNS) A4 (210 X 297) (Centimeter)

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Line 593786 A7 B7 V. Description of Invention (14) Problem. As mentioned above, in the normal anodizing process, if the applied voltage is suddenly reduced, the bottom of the pores of the porous layer will form a branch 10, becoming a pore with several smaller pores, which makes aluminum The bonding force between the anodized film and the substrate becomes weak. Fig. 4 shows the situation where the voltage structure is used to partially separate the completed structure to change the color. In FIG. 4, the aluminum-based metal substrate 1 is firstly subjected to a sandblasting treatment to generate a textured metal atomized surface 8, and then subjected to a pretreatment, and then anodized using a sulfuric acid bath / DC method to generate During the formation of the anodic oxide film of aluminum, the voltage is gradually reduced to 0 volts. As a result, many small pores 10 are formed at the bottom of each pore of the porous layer, and the barrier layer 4 is also thin. This causes the barrier layer 4 and aluminum The bonding force between the base metal substrates 1 becomes weak, and the phenomenon of peeling of the interference layer is easily formed. Thereafter, electrolytic coloring is performed by alternating DC current or alternating current or both, and a metal such as nickel is deposited on the bottom of the pore to form a metal deposit. Then, on the surface of the electrolytically colored aluminum anodized film, a multilayer film 9 of high refractive index oxide and low refractive index oxide is alternately grown. The reflective surface and optical path of this structure can show the interference effect of at least two color changes, and can improve the problem of fingerprint contamination on the surface of aluminum products. By studying the following examples, you can further understand the purpose, features and advantages of the present invention. -19- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 593786 A7

Example 1 The Ming alloy with a purity of 99 · 5% is entered in the following steps. Green: First, sandblast the surface of the aluminum material, and then run the degreasing treatment at 60 ° C for 3 minutes. After washing with water, I used ultrasound to see it in the above solution: two_ degreasing treatment for 3 minutes, and then washed with water, concentrated to 3 〇:

Charge with acid solution and neutralize for 30 seconds. This can be applied to aluminum alloys. The anodic oxide film of aluminum having a degree of 5 μηη includes a pre-layer. The porous layer and the screen have been subjected to the above-mentioned pre-treated aluminum alloy at a concentration of 1 and less than 1. It was sulphuric acid at 12% in the cold at 15 C and anodizing at 7 C for 0 minutes. Afterwards, order by reputation ^ ^ ^ Ar.

Line 仃 ～ 耆 色 · Pre-prepared electroplating ^ ^ T (plating bath set includes 25 g / L nickel sulfate, 20 g / L magnesium sulfate, 25 L boric acid and 15 g / L ammonium sulfate), Using 4 volts at the same time, Xia Liudian and 9 watts of alternating current are used simultaneously to perform electrical deposition for 5 minutes and 4 miles' to deposit metallic nickel on the pore bottom of the porous layer, 〃, 仏 沣. After the electrolytic coloring element is formed, the TiO2 (high-refractive, high-refractive film, and Si 0 2 (low-refractive-index oxide) film are each grown alternately on the surface of the polar oxide film by means of SpUttering. '—) Thickness 500 ~ 1000A. The results are shown in Figure]. 1 layer, each layer, as a result of the thickness' less than ΙΟμηι | interference |, when the observer is located in different views, the aluminum alloy surface will be at least 2 kinds due to interference effects -20. 593786 A7 B7 five, Description of the invention (16) Color change. In addition, the problem of fingerprint contamination of the produced aluminum products has been improved. Example 2 An aluminum alloy having a purity of 99.5% was pretreated in the same manner as in Example 1. The anodized aluminum alloy was subjected to anodization treatment at a temperature of 15 ° C and a DC voltage of 7 volts for 10 minutes in a sulfuric acid bath with a concentration of 12%. After washing with water, a second anodic oxidation treatment was performed in a phosphoric acid bath having a concentration of 12% at a temperature of 15 ° C for 5 minutes using a DC voltage of 7 volts. After that, the electrolytic coloring was performed in the following way: in a pre-prepared electroplating bath (the composition of the electroplating bath is the same as that in Example 1), the electrolytic deposition was performed by alternating current of 4 volts DC-4 volts AC 4 volts DC five times, using 12 volts 5 minutes to deposit metallic nickel on the bottom of the pores of the porous layer. Then washed again. Then, a third anodizing treatment was performed in a sulfuric acid bath under the same conditions as described above. Then, using a method of sputtering, five layers of Ti02 (high-refractive-index oxide) and Si02 (low-refractive-index oxide) films are grown alternately over the surface of the aluminum anodized film, each with a thickness of 500 ~ 1000 A. This can form an anodized film of aluminum with a thickness of 5 μm on the aluminum alloy, which includes a porous layer and a barrier layer. The results are shown in Figure 2. An interference layer with a thickness of less than 10 μm is formed. When the observer is located at different viewing angles, the surface of the alloy will produce -21 due to interference effects.-This paper size applies to Chinese National Standard (CNS) A4 specifications (210 X 297 mm) 593786 A7 B7 V. Description of the invention (17) At least 2 kinds of color changes are produced. In addition, the problem of fingerprint contamination of the produced aluminum products has been improved. Example 3 / An aluminum alloy having an aluminum purity of 99.5% was processed in the same manner as in Example 1. The pre-treated aluminum alloy was anodized in a sulfuric acid bath with a concentration of 12% at a temperature of 15 ° C and a direct voltage of 7 volts for 10 minutes. After washing with water, a second anodic oxidation treatment was performed in a phosphoric acid bath having a concentration of 12% at a temperature of 15 ° C for 12 minutes using a DC voltage of 12 volts. After that, electrolytic coloring was performed in the following way: in a pre-prepared electroplating bath (the composition of the electroplating bath is the same as that in Example 1), electrolytic deposition was performed using a voltage of 12 volts in a manner of alternating alternating current of 4 direct current-direct current 4 direct current and direct current 5 times. Minutes to deposit metallic nickel on the bottom of the pores of the porous layer. Then, 5 layers of long Ti02 (high refractive index oxide) film and Si02 (low refractive index oxide) film were replaced on the surface of aluminum's anodized film by sputtering, and the thickness of each layer was 500 ~ 1000 A. This can form an anodic oxide film with a thickness of 5 μm on the aluminum alloy. The results are shown in FIG. 3. Since the meso system forms an interference layer with a thickness of less than 10 μm, when the observer is at different viewing angles, the aluminum alloy surface will produce at least two color changes due to interference effects. In addition, the fingerprint contamination of the aluminum products has been improved. -22-This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 593786 A7 B7 V. Description of the invention (18) Example 4 An aluminum alloy with a purity of 99.5% aluminum according to Example 1 Pre-processing. > Anodize the pre-treated aluminum alloy in a sulfuric acid bath with a concentration of 12% at a temperature of 15 ° C using a DC voltage of 7 volts. During the process, _ 0 1 volt / second voltage drop rate, gradually reduce the voltage to 0.5 volts and stay for 5 seconds, then lower the voltage to 0 volts, stay for 5 seconds, and then increase the voltage to 20 volts and stay for 20 seconds To obtain a branched pore structure. Then perform the electrolytic coloring in the following way: in a pre-prepared electroplating bath (the composition of the electroplating bath is the same as in Example 1), the electrolysis is performed by alternating current of 5 times with direct current 4 alternating current-> direct current 4 alternating current direct current 5 times Deposit for 5 minutes to deposit metallic nickel on the bottom of the pores of the porous layer. Then, by sputtering, Ti02 (high-refractive-index oxide) film and Si02 (low-refractive-index oxide) film are grown on the surface of aluminum's anodized film alternately in five layers, each with a thickness of 500 ~ 1000 A. This can form an anodized film with a thickness of 5 μm on the alloy. The results are shown in Figure 4. Due to the formation of an interference layer with a thickness of less than 10 μm, when the observer is at different viewing angles, at least two kinds of color changes will occur on the aluminum alloy surface due to interference effects. In addition, the fingerprints of the aluminum products produced have been improved. Example 5 -23- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 593786 A7 __________ B7. _ 5. Description of the invention (19) Aluminum alloy with a purity of 9 9 · 5% The following steps are carried out in the previous step V. 1 First, the Ming material is degreased with 20% sodium pyrophosphate at 60 ° C for 3 minutes, washed with water, and then ultrasonicated in the above solution. After being degreased for 3 minutes, it was washed with water and then neutralized with a 30% nitric acid aqueous solution for 30 seconds. After being washed with water, it was placed in a 5% caustic soda aqueous solution and etched for 1 minute. This can form a 5 μm thick anodized film on the aluminum alloy, which includes a porous layer and a barrier layer. The pre-treated aluminum alloy was subjected to extreme oxidation treatment at a concentration of 12% sulfuric acid at 15 ° C and a DC voltage of 7 volts for 10 minutes. After that, electrolytic coloring was performed in the following manner: In a previously prepared electroplating bath (the composition of the electroplating bath includes 25 g / L of nickel sulfate, 20 g / L of magnesium sulfate, 25 g / L of boric acid, and 15 g / L of ammonium sulfate) The electrolytic deposition was performed for 5 minutes by using a direct current of 4 volts and an alternating current of 9 volts simultaneously to deposit metallic nickel on the bottom of the pores of the porous layer. After the electrolytic coloring is completed, successively, titanium oxide (Ti refractive index oxide) films and 3 丨 〇2 (low refractive index oxide) films are grown on the surface of aluminum anodized film by sputtering. Layers, each with a thickness of 500 ~ 1000a. The results are comparable to Example 1. Because the interference layer is formed with a thickness of less than 10 μm, when the observer is located at different viewing angles, the aluminum alloy surface will produce at least two kinds of color changes due to interference effects. In addition, the fingerprint contamination of Deming products has been improved. • 24- This paper size applies to China i? ^ CNS) Α4 size (21GX 297 male ~

Claims (1)

593786 Announcement & r -------- AB c D Range 1. An aluminum product with a film that changes color as the viewing angle changes, comprising:-a baseless metal base / material,- An anodized film covering the surface of the metal substrate and having a thickness of less than 10 μm, the oxide film includes a porous layer and a barrier layer, and a metal deposit in the pores of the porous layer, wherein the metal is deposited The object is obtained by alternating current or alternating current or both. The electrolytic coloring is obtained. The aluminum product further includes a roughened layer on the anodized film and / or a roughened layer on the anodized film. High-refractive-index oxides and low-refractive-index oxides over the layers alternately grow multilayer films. 2. The aluminum product according to item 1 of the scope of the patent application, wherein the aluminum-based metal substrate comprises a roughened layer above the anodized film, and a high-refractive index oxide and Alternate growth of multi-layer thin films with reduced oxides. 3. The aluminum product according to claim 1 of the application, wherein the high refractive index oxide has a refractive index from 2 to 2.5, and the low refractive index oxide has a refractive index from 1.3 to 1.7. rate. 4. The aluminum product according to item 3 of the scope of patent application, wherein the high refractive index oxide is selected from the group consisting of Ti02 and Zr02, and the low refractive index oxide is selected from the group consisting of si02 and ai2o3, Slaves. 5 · Aluminum products according to item 1 of the scope of patent application, in which the aluminum base-25- This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 593786 A8 B8 C8 D8 The metal base material is a galvanic alloy containing an inscription of 90 to 99: 9%. v ^ 6 · The inscription product according to item 1 of the patent application scope, wherein the metal of the metal deposit is selected from copper, iron, germanium, nickel, tin, gold, silver, platinum, cadmium, lead, manganese, and molybdenum Group of people. 7 · —A method for forming a film that can change color with the change of viewing angle on an aluminum-based metal substrate, comprising:-anodizing the Yiming-based metal substrate to provide a layer over the substrate An anodized film including a porous layer and a barrier layer with a thickness of less than 10 μm, and-by depositing metal deposits in the pores of the porous layer by alternating current or alternating current or both, to form a chain The electrolytic coloring of the anodized film is based on the roughening treatment of the aluminum base metal substrate before the anodizing treatment to form a roughened layer on the surface of the substrate, and then anodizing treatment. An anodic oxide film is formed on the surface of the substrate and between the roughened layers, and / or after the aluminum base metal substrate is electrolytically colored, high-refractive-index oxides and low-folds are alternately grown over the anodic oxide film. Rate oxide multilayer film. 8. The method according to item 7 of the scope of patent application, wherein the # aluminum-based metal substrate is subjected to a roughening treatment before anodizing treatment, so as to form a roughened layer on the surface of the substrate, and then an anode is performed. Oxidation treatment 'to form an anodic oxide film between the surface of the substrate and the roughened layer, and on the aluminum-based metal base-26- This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 593786 ABCD 々, after the patent application material is electrolytically colored, a multilayer film of high refractive index oxide and low refractive index oxide is alternately grown on the anodized film. 9. The method according to the scope of patent application / item 7, wherein the roughening treatment is a chemical surname treatment. 10. The method according to item 7 of the scope of patent application, wherein the roughening treatment is sandblasting. — R 11. The method according to item 7 of the scope of patent application, wherein the anodic oxidation treatment is performed by a sulfuric acid bath / DC method, and the sulfuric acid bath has a concentration of from 10 to 20% by weight. 12. The method according to item 11 of the scope of patent application, wherein the sulfuric acid bath contains nickel sulfate with a concentration of 15 to 50 g / L, magnesium sulfate with a concentration of 10 to 40 g / L, and a concentration of 15 to 50. G / L of boric acid and ammonium sulfate at a concentration from 5 to 30 g / L. 13. The method according to item 7 of the scope of patent application, wherein the anodic oxidation treatment is performed at a temperature from 5 to 100 ° C and a voltage from 0.5 to 50 volts for 0.5 to 30 minutes. 14. The method according to item 13 of the patent application, wherein the anodizing treatment is performed at a temperature from 15 to 25 ° C and a voltage from 3 to 20 volts for 1 to 15 minutes. 15. The method according to item 7 of the scope of patent application, wherein the metal of the metal deposit is a group selected from the group consisting of copper, iron, nickel, nickel, tin, gold, silver, platinum, cadmium, lead, manganese, and molybdenum . 16: The method according to item 8 of the scope of patent application, wherein the high refractive index oxide has a refractive index ranging from 2 to 2.5, and the low -27- This paper size is applicable to the Chinese National Standard (CNS) A4 specification ( 210 X 297 mm) 593786 A BCD 々, the patent application range refractive index oxides have a refractive index from 1.3 to 1.7. 17. The method according to item 16 of the patent claim 7, wherein the high refractive index oxide is selected from the group consisting of Ti02 and Zr02, and the low refractive index oxide is selected from the group consisting of Si02 and Al203. group. 18. The method according to item 11 of the scope of patent application, further comprising performing additional anodizing treatment with a phosphoric acid bath / DC method to form a pore structure with a narrow upper and a lower width in the porous layer. 19. The method according to item 11 of the scope of patent application, further comprising performing an additional smooth oxidation treatment * by a phosphoric acid bath / DC method to form a pore structure with a narrow upper and a lower width in the porous layer, and then, in After electrolytic coloring, another anodizing treatment was performed by a sulfuric acid bath / DC method. 20. The method according to item 11 of the scope of patent application, wherein, after the anodic oxide film of aluminum is formed by a sulfuric acid bath / DC method, the voltage is gradually decreased to 0 volts to form 'many branches' in the bottom of the pores in the porous layer. Small hole. 21. The method according to item 7 of the scope of patent application, wherein the electroplating bath for electrolytic coloring contains the following composition: nickel sulfate with a concentration of 15 to 50 g / L, magnesium sulfate with a concentration of 10 to 40 g / L, Boric acid with a concentration of 15 to 50 g / L and ammonium sulfate with a concentration of 5 to 30 g / L, using alternating current / direct current or the same method as' B, etc., using a voltage from 2 to 50 volts for 0.5 To 30 minutes. -28- This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 593786 A8 B8 C8 D8, patent application scope 22. The method according to item 21 of the patent application scope, where the electrolytic coloring is used The voltage is from 5 to 20 volts for 1 to 10 minutes. -29- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)