KR20210151612A - Surface treating method for internal/external metal material, and internal/external metal material treated by the same - Google Patents

Abstract

The present invention relates to a method for surface treatment of a metal interior and exterior material and a surface-treated metal interior and exterior material, and more particularly to the method for surface treatment of metal interior and exterior materials, the method comprising steps of: forming a barrier layer with valve metal on the surface of metal interior and exterior materials, anodizing the surface and performing dyeing and sealing after forming a surface layer with an aluminum (Al)-based metal thereon. According to the present invention, anodizing, coloring, and sealing technology are applied to the surface of various metal interior and exterior materials such as zinc, stainless steel, and magnesium, thereby capable of realizing the surface color of various, beautiful and uniform metal interior and exterior materials.

Description

Method of surface treatment of metal interior and exterior materials and surface-treated metal interior and exterior materials

The present invention relates to a method for surface treatment of metal interior and exterior materials and to a surface-treated metal interior and exterior material, and more particularly, after forming a barrier layer made of valve metal and a surface layer made of aluminum-based metal on the surface of various metal interior and exterior materials It relates to a surface treatment technology for metal interior and exterior materials that realizes a beautiful and uniform surface color by applying anodizing technology.

Anodizing is one of the electrochemical film forming methods. It uses a solution of sulfuric acid, oxalic acid, chromic acid, etc. as an electrolyte to form an anodized film on the surface of a metal such as aluminum, resulting in mechanical, electrical, and chemical properties. It means the technology for forming this excellent film. The film formed by this anodization film treatment method is very hard, has great corrosion resistance, and can be dyed in various colors. Accordingly, it is used in various industrial fields. In particular, it is in the spotlight in product-related industries such as mobile phone cases, where demand is rapidly increasing. there is a technique

However, in the case of aluminum, only the method of anodizing after machining the aluminum alloy plate is actually applied. This is because a uniform anodized film cannot be formed due to non-uniform precipitation.

On the other hand, the machining method is applicable only to a simple form in consideration of productivity, is difficult to apply to a complex form due to economic feasibility according to the manufacturing price, and also consumes a lot of effort and cost in the subsequent assembly process.

Accordingly, a method of vacuum-depositing aluminum and anodizing the deposited aluminum on aluminum die-casting products, which is easy to mass-produce complex shapes, has also been recently developed, but there is a problem in the adhesion of the thin film of the vacuum deposition method.

In order to solve this problem, in Korean Patent Application Laid-Open No. 10-2012-0116558 (High-speed film forming apparatus and film forming method using the same, published on October 23, 2012), a method combining the vacuum vapor deposition method and the arc method solves the adhesion problem of the vacuum vapor deposition method. A method has been suggested, and in Korean Patent Application Laid-Open No. 10-2012-0116557 (a method for surface treatment of a die-casting alloy and a die-casting alloy material having a surface structure prepared thereby, published on October 23, 2012), an oxide of less than stoichiometry, Methods using nitrides or oxynitrides have also been proposed.

In addition, in Korean Patent Laid-Open Publication No. 10-2013-0115475 (Method for surface treatment of metal interior and exterior materials and metal interior and exterior materials having a surface structure manufactured thereby, published on October 22, 2013), contact with a jig with a thin deposition film during aluminum deposition A method that can be applied to a magnesium alloy material other than an aluminum material by applying a method of reinforcing the thickness by a cold spray method to the area has been proposed, but there is a problem that a separate process is required rather than a continuous process.

In the case of interior and exterior materials made of aluminum, if the aluminum deposition thickness in the visible area is sufficient, there is no problem in use even if the color is not uniformly formed in the invisible hidden area during the subsequent coloring sealing process, so the method using deposition is applied. There is no great difficulty in doing this, but in the case of metal interior and exterior materials such as magnesium alloy, stainless steel, and zinc alloy, if there is a thin part of aluminum, there is a problem that the part bursts during the anodizing process.

In addition, if a portion where the aluminum layer is formed too thinly occurs during the aluminum formation process, or if some aluminum layer becomes too thin by a polishing process by electrolytic polishing, chemical polishing, or mechanical polishing, or a hairline forming process, this part also The same problem occurred in the anodization process.

Therefore, the surface of metal interior and exterior materials other than aluminum can also be stably anodized, and accordingly, there is a need for a technology capable of implementing various exterior colors on the surface of these metal interior and exterior materials.

The present invention was devised to solve the above problems, and an object of the present invention is to form a barrier layer made of a valve metal and a surface layer made of an aluminum-based metal on the surface of various metal interior and exterior materials, and then anodize it It is to provide a surface treatment technology for metal interior and exterior materials that realizes a beautiful and uniform surface color by applying technology.

In order to achieve the object as described above, according to an embodiment of the present invention, i) forming a barrier layer 10 with a valve metal on the surface of the metal interior and exterior material 1; ii) a surface layer of an aluminum (Al)-based metal on the barrier layer 10

forming (20); iii) anodizing the surface on which the surface layer 20 is formed; and iv) coloring the anodized surface with a dye and sealing the surface.

At this time, the valve metal is titanium (Ti), niobium (Nb), tantalum (Ta), zirconium (Zr), vanadium (V), tungsten (W), hafnium (Hf), aluminum (Al) and yttrium (Y) It may be one single metal or an alloy of two or more selected from the group consisting of, preferably, the valve metal is an alloy of titanium (Ti), aluminum (Al) and vanadium (V), or titanium (Ti), aluminum (Al) and an alloy of niobium (Nb), and more preferably, the valve metal may be Ti6Al4V or Ti6Al7Nb.

In addition, the surface layer 20 is preferably a single layer formed of one selected from the group consisting of aluminum, aluminum alloy, and aluminum oxide, nitride, and oxynitride having less than a stoichiometric composition ratio, or a composite layer in which two or more are laminated.

Between steps ii) and iii), the method further comprises a step of sanding the surface of the product or a hairline treatment, or at least one selected from the group consisting of chemical polishing, electrolytic polishing and mechanical polishing. It may further include a polishing step of performing the above.

Meanwhile, it is preferable that the barrier layer 10 has a thickness of 0.03 to 5 μm and the surface layer 20 has a thickness of 5 to 100 μm, and the barrier layer 10 and the surface layer 20 are PVD (Physical Vapor Deposition). ) method, more preferably vacuum evaporation, sputtering, and at least one selected from the group consisting of cathodic vacuum arc method.

In addition, before step i), it may further include the step of pre-treating the surface of the metal interior and exterior material (1) through ultrasonic cleaning or ion collision, in step iv), the group consisting of organic material coloring, inorganic material coloring and electrolytic coloring It is preferable to color the dye on the anodized surface by at least one method selected from .

In order to achieve the above object, according to another embodiment of the present invention, a barrier layer 10 made of a valve metal is formed on the surface of the metal interior and exterior material 1, and is made of an aluminum (Al)-based metal. Provided is a surface-treated metal interior and exterior material in which a surface layer 20 having an anodized surface is formed on the barrier layer 10 .

In this case, it is preferable that the surface of the anodized surface layer 20 is sealed after coloring the dye.

In addition, the valve metal is titanium (Ti), niobium (Nb), tantalum (Ta), zirconium (Zr), vanadium (V), tungsten (W), hafnium (Hf), aluminum (Al) and yttrium (Y) It may be one single metal or an alloy of two or more selected from the group consisting of, preferably, the valve metal is an alloy of titanium (Ti), aluminum (Al) and vanadium (V), or titanium (Ti), aluminum (Al) ) and an alloy of niobium (Nb), and more preferably, the valve metal may be Ti6Al4V or Ti6Al7Nb.

In addition, the surface layer 20 is preferably a single layer formed of one selected from the group consisting of aluminum, aluminum alloy, and aluminum oxide, nitride, and oxynitride having less than a stoichiometric composition ratio, or a composite layer in which two or more are laminated.

Meanwhile, it is preferable that the barrier layer 10 has a thickness of 0.03 to 5 μm and the surface layer 20 has a thickness of 5 to 100 μm, and the barrier layer 10 and the surface layer 20 are PVD (Physical Vapor Deposition). ), and more preferably, at least one selected from the group consisting of Evaporation, Sputtering, and Cathodic Vacuum Arc.

As described above, the surface treatment method and surface-treated metal interior and exterior material of the present invention as described above apply anodizing, coloring, and sealing technology to the surface of various commonly used metal interior and exterior materials such as zinc, stainless steel, and magnesium. It has the effect of realizing the surface color of various, beautiful and uniform metal interior and exterior materials.

1 is a view showing a flow chart of a method for surface treatment of a metal interior and exterior material according to an embodiment of the present invention.
2 is a schematic view showing a laminated structure of a surface-treated metal interior and exterior material according to another embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. Prior to this, the terms or words used in the present specification and claims should not be construed as being limited to conventional or dictionary meanings, but should be interpreted as meanings and concepts consistent with the technical spirit of the present invention.

First, according to a preferred embodiment, the present invention provides a method for surface treatment of a metal interior and exterior material comprising a barrier layer forming step, a surface layer forming step, anodizing step, and dye coloring/sealing treatment step. A flow chart for this is shown in FIG. 1 . Hereinafter, each step in the time series will be described in detail.

First, in the barrier layer forming step, a metal interior and exterior material 1 as a workpiece is prepared. Metal interior and exterior material (1) means a metal that can be used as interior and exterior materials for products, and includes zinc, stainless steel, magnesium, aluminum alloy, die-casting alloy (depending on the type, silicon (Si), iron (Fe), copper (Cu), manganese (Mn) ), zinc (Zn), nickel (Ni), titanium (Ti), lead (Pb), tin (Sn) or chromium (Cr)) The invention can be applied.

In particular, in the present invention, the metal interior and exterior material 1 may be a metal that does not contain an aluminum component, and even if it does not contain aluminum, the anodizing process can be stably performed by the process according to the present invention.

In the barrier layer forming step, the barrier layer 10 is formed with a valve metal on the surface of the metal interior and exterior material 1 described above. Valve metal refers to a metal that exhibits a valve effect, and the valve effect refers to a phenomenon in which current flows in a solution from a solution to a metal but hardly flows from a metal to a solution. .

Among valve metals, titanium and niobium are used to produce various colors through an anodizing process in the decoration industry dealing with jewelry. In more detail, when these valve metals are anodized, interference colors such as blue, yellow, pink or green are expressed depending on the applied voltage, and the anodizing depth is adjusted according to the size of the applied voltage, so that the you will see different colors.

Meanwhile, in the present invention, the barrier layer 10 may be formed of a single metal such as titanium, niobium, tantalum, vanadium, zirconium, tungsten, hafnium, and yttrium, or an alloy of two or more of these metals. In addition, the single metal or alloy can be formed by adding aluminum to each other, and it is more preferable to form the barrier layer 10 with Ti6Al4V or Ti6Al7Nb, which are titanium aluminum alloys that have been supplied in various compositions in recent years.

As used herein, each number in the term "Ti6Al4V" or "Ti6Al7Nb" does not mean the stoichiometric ratio of the compound, but the weight ratio in the alloy. More specifically, in the case of "Ti6Al4V", it means a titanium-aluminum-vanadium alloy containing 6 wt% of aluminum (Al) and 4 wt% of vanadium (V) based on the total weight, and in the case of "Ti6Al7Nb", the total It means a titanium-aluminum-niobium alloy containing 6 wt% of aluminum (Al) and 7 wt% of niobium (Nb) based on weight.

When the barrier layer 10 is first formed on the surface of the metal interior and exterior material 1 with such a valve metal, the surface bursting phenomenon is prevented as described above when the anodizing process and the coloring/sealing process are performed on the metal interior and exterior material 1 can do.

More specifically, when the aluminum-based material on the barrier layer 10 is anodized, the thick portion remains unoxidized while the thin portion is all anodized so that the barrier layer 10 is anodized. come into contact with the easing solution.

At this time, when the barrier layer 10 is made of valve metals, this effect can be obtained because it is oxidized only at a maximum of 1 μm or less and acts as a barrier layer. If the barrier layer 10 does not exist, a phenomenon in which the surface bursts occurs while an excessive current flows in the portion.

The method of forming the barrier layer 10 is not appropriate because, in the case of the CVD (Chemical Vapor Deposition) method, the process temperature is usually high at 500° C. or higher, which may cause problems such as deformation of the material, so PVD (Physical Vapor Deposition) Deposition) method is preferred. In more detail, the barrier layer 10 may be formed on the surface by adopting at least one method selected from the group consisting of vacuum evaporation, sputtering, and cathodic vacuum arc. It is most preferable to use sputtering or cathodic vacuum arc method in consideration of the adhesion of the formed material.

Before forming the barrier layer 10, an ultrasonic cleaning process is performed to remove oil components or foreign substances remaining on the surface of the metal interior and exterior material 1, which is a workpiece, or argon gas ion collision or metal ion collision in a vacuum chamber. It is preferable to perform a process of removing surface impurities or oxides as a method of collision.

On the other hand, the thickness of the barrier layer 10 may vary depending on the process conditions during anodization and the thickness of the surface layer 20 to be described later, but when the thickness of the surface layer 20 is sufficiently thick, it is possible to be 0.03 μm or more. However, it takes a lot of time and money to uniformly and thickly form all parts of the metal interior and exterior material 1 with PVD coating, and the process is not easy. Accordingly, a problem may occur, such as a certain portion being formed thinner than other portions, or being formed thinner in a portion in contact with a jig or the like, a rear portion, a hidden portion, or the like.

In this region, since the barrier layer 10 and the surface layer 20 are thinner than the thickest region, in the anodization step, not only the outermost surface layer 20 but also the barrier layer 10 is anodized. If there is no barrier layer 10 made of a valve metal under the surface layer 20 made of an aluminum-based metal, a problem occurs because the metal interior and exterior material 1 directly reacts with the anodizing solution in this part, but the barrier layer 10 ) is present, the barrier layer 10 is anodized and acts as a barrier of a certain thickness. That is, when commonly known titanium or niobium is colored, a phenomenon occurs in which the surface is colored according to an applied voltage. On the other hand, although the oxidation pore depth in this part is insufficient, it is not possible to show a uniform coloring effect, but this part does not impair the value of the product because there is no problem in appearance.

Since the oxidation depth is about 30 to 300 nm and similar to other metal layers, the thickness of the barrier layer 10 may be 0.03 μm or more, preferably 0.1 μm or more, and more preferably 0.3 μm or more, the metal interior and exterior material. The surface of (1) can be sufficiently protected.

On the other hand, tantalum is oxidized to about 1.6 nm per 1 V and oxidized to 160 nm when anodized at 100 V, and niobium is anodized to 300 to 400 nm. The minimum thickness should be changed appropriately.

Although there is no particular limitation on the upper limit of the thickness of the barrier layer 10 , it is preferably 5 μm or less in consideration of the rate of formation of the barrier layer 10 and economic feasibility according to price.

Next, step ii) of forming the surface layer 20 is a step of forming the surface layer 20 of the aluminum-based metal on the barrier layer 10 formed on the surface of the metal interior and exterior material 1 as described above. As for the formation method, it is most preferable to use a sputtering method or a cathode vacuum arc method as in the above-described barrier layer 10, and in the case of the CVD method, since the process temperature is usually high at 500° C. or more, there is a problem such as deformation of the material. not appropriate

The surface layer 20 may be formed of various materials including an aluminum component, such as pure aluminum, an aluminum alloy, etc., and preferably may be formed of an aluminum oxide, nitride or oxynitride layer having a stoichiometric composition ratio less than the aluminum oxide, nitride or oxynitride layer. In the case of an aluminum compound layer of less than this stoichiometric composition ratio, it has superior hardness and excellent adhesion and strong bonding force compared to materials such as pure aluminum or aluminum alloy. This is because strong adhesion and adhesion can be imparted between the anodized film layers to be formed.

Next, the anodization step, which is step iii), is a process of oxidizing a part of the above-mentioned surface layer 20 to an anodization film layer by anodizing treatment. It is in the range of 5 to 100 μm depending on the required thickness of the anodization film layer. A surface layer 20 must be formed.

In order to obtain a required film layer thickness according to product requirements, the surface layer 20 in an appropriate thickness range can be formed in various ways, but as described above, the thickness range is limited as described above. Since the easing depth is too thin, there is a problem in that various colors cannot be made in the subsequent coloring process, which is a subsequent process. This is because the object to be processed is deformed or thickened as it ages, causing problems in assembling with other assemblies.

Anodizing treatment, that is, anodizing treatment, is a process of forming a film such as aluminum oxide (Al2O3) by using a metal product such as aluminum as an anode and polarizing it under appropriate conditions in a certain electrolyte solution. This film is very light and has great corrosion resistance, and since a porous layer is formed and can be dyed in various colors, it is a process that can increase the commercial value by imparting a beautiful and profound color to the surface as well as practicality such as corrosion resistance and abrasion resistance to be.

Here, for the anodization, any one of conventional sulfuric acid, oxalic acid, chromic acid, or a mixed acid thereof can be used, and the thickness of the film is adjusted according to the required color, so preferably, the surface layer 20 is preliminarily 5 as described above. It can be formed in ~100 μm.

Meanwhile, the method may further include a step of sanding or hairline treatment of the surface prior to step iii) of anodizing the surface in order to improve the required properties or hallmarks of the product. Sanding is an operation of polishing the undercoat surface with a prescribed abrasive paper in order to achieve a required surface treatment purpose, and is an operation for removing surface defects and improving smoothness and adhesion. Hairline is an operation used for the purpose of improving the quality of a product by giving a hair-like line to the surface.

In addition, if the final product is matt, it is okay to oxidize it as it is, but in the case of manufacturing a glossy product, if the thickness of the thin film increases, the gloss of the thin film decreases. It is preferable to further add a polishing step, more specifically, a step of performing chemical polishing, electrolytic polishing or mechanical polishing before the step. Chemical polishing is a method of performing gloss polishing without using an external electric current, and refers to a process of chemically smoothing the surface of a metal. In general, the main raw material of chemical polishing is phosphoric acid, and the process of forming a phosphate film is performed. Electrolytic polishing refers to a polishing method that makes a smooth surface by electrolysis under predetermined conditions when a higher gloss is required by overcoming the limitation of surface gloss formation caused by chemical polishing.

Next, in step iv), the dye coloring and sealing treatment step, when a porous film layer is formed through anodization, a dye is colored on the anodized surface through a dye coloring method such as organic material coloring, inorganic material coloring, or electrolytic coloring. and finally performing a sealing process to block the pores of the anodized film by a method such as hydration sealing, metallic sealing, organic sealing, low temperature sealing, or the like. Through the dye coloring process, the product value can be improved by adding an aesthetic feeling to the product surface, and the weather resistance and durability of the coloring and the corrosion resistance of the film can be improved through the sealing process.

Hereinafter, examples of the surface treatment method of the metal interior and exterior material and the surface-treated metal interior and exterior material of the present invention will be described. However, since this is only the most preferred embodiment of the present invention and does not represent all of the technical spirit of the present invention, it is understood that there may be various equivalents and modifications that can be substituted for them at the time of filing the present invention. shall.

1: Metal interior and exterior materials
10: barrier layer
20: surface layer

Claims (17)

i) forming a barrier layer 10 with a valve metal on the surface of the metal interior and exterior material 1;
ii) forming a surface layer 20 of an aluminum (Al)-based metal on the barrier layer 10;
iii) anodizing the surface on which the surface layer 20 is formed; and
iv) coloring the anodized surface with a dye and sealing;
includes,
The valve metal is a surface treatment method of a metal interior and exterior material, characterized in that Ti6Al4V or Ti6Al7Nb.
The method according to claim 1, wherein the surface layer 20 is a single layer formed of one selected from the group consisting of aluminum, aluminum alloy, and aluminum oxide, nitride, and oxynitride having less than a stoichiometric composition ratio, or a composite layer in which two or more are laminated. A method for surface treatment of metal interior and exterior materials, characterized in that The method of claim 1, further comprising, between steps ii) and iii), sanding or hairline treatment of the product surface. The method of claim 1, further comprising a polishing step of performing at least one selected from the group consisting of chemical polishing, electrolytic polishing, and mechanical polishing between steps ii) and iii). The method of claim 1, wherein the barrier layer (10) has a thickness of 0.03 to 5 µm. The method according to claim 1, wherein the surface layer (20) has a thickness of 5 to 100 µm. The method of claim 1, wherein the barrier layer (10) and the surface layer (20) are formed by a PVD (Physical Vapor Deposition) method. The method of claim 10, wherein the PVD method is at least one selected from the group consisting of vacuum evaporation, sputtering, and cathodic vacuum arc method. The method of claim 1, further comprising the step of pretreating the surface of the metal interior and exterior material (1) through ultrasonic cleaning or ion collision before step i). According to claim 1, wherein in step iv), the dye is colored on the anodized surface by at least one method selected from the group consisting of organic material coloring, inorganic material coloring and electrolytic coloring, and hydration sealing, metallic sealing, organic sealing and A method for surface treatment of metal interior and exterior materials, characterized in that sealing the colored surface by at least one method selected from the group consisting of low-temperature sealing. The barrier layer 10 made of valve metal is formed on the surface of the metal interior and exterior material 1, and the surface layer 20 made of an aluminum (Al)-based metal and the surface of which is anodized is the barrier layer 10 Formed above, the valve metal is a surface-treated metal interior and exterior material, characterized in that Ti6Al4V or Ti6Al7Nb. [15] The surface-treated metal interior and exterior material according to claim 14, wherein the surface of the anodized surface layer (20) is sealed after coloring the dye. The method according to claim 14, wherein the surface layer 20 is a single layer formed of one selected from the group consisting of aluminum, aluminum alloy, and aluminum oxide, nitride, and oxynitride having less than a stoichiometric composition ratio, or a composite layer in which two or more are laminated. Surface-treated metal interior and exterior materials, characterized in that. 15. The surface-treated metal interior and exterior material according to claim 14, wherein the barrier layer (10) has a thickness of 0.03 to 5 μm. The surface-treated metal interior and exterior material according to claim 14, wherein the surface layer (20) has a thickness of 5 to 100 µm. [15] The surface-treated metal interior and exterior material according to claim 14, wherein the barrier layer (10) and the surface layer (20) are formed by a PVD (Physical Vapor Deposition) method. The surface-treated metal interior and exterior material according to claim 22, wherein the PVD method is at least one selected from the group consisting of vacuum evaporation, sputtering, and cathodic vacuum arc method.

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