KR101741011B1 - Metal materials and manufacturing methods having various colored metal oxide film - Google Patents

Abstract

The present invention provides a method of manufacturing a metal oxide film by introducing a complex oxide solution containing a metal-based self-oxide and other metal oxide on the surface of a Group 11 metal based on copper (Cu). In the above manufacturing method, in addition to the general copper oxidation color, there is provided a metal base having a variety of colors capable of distinguishing a total of 10 kinds or more in total from the composite oxide. Furthermore. The present invention provides a method of manufacturing an oxide film having a unique texture according to the kind of additives added to the complex oxide solution.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal substrate having a metal oxide film of various colors,

TECHNICAL FIELD The present invention relates to a metal surface treatment technique, and more particularly, to a method of manufacturing an oxide film and an oxide film of a metal material having various colors and textures by oxidizing a metal surface using an oxidizing solution.

The metallic material to be used as a sheath is painted or painted, and a color steel sheet is typically used. Conventional color steel sheets are used as construction materials, home appliances materials and automotive steel sheets by combining the electroplated galvanized steel sheet and the hot-dip galvanized steel sheet with the process of painting or bonding the film, but the color is monotonous, There is a limit to the feeling and aesthetic desire. In addition, suppliers of existing markets supply color steel sheets based on the mass production system through continuous production, and are not able to meet the demands of the metal materials of various colors in the market.

Korean Patent No. 10-1508970 (a street lamp with a high-strength and high-corrosion-resistant brass film) is coated with a composite film-forming agent to form a high corrosion-resistant base rust-preventive film, and a protective paint film , And then applying a brass powder to a transparent paint over a protective paint film, applying and heating the brass powder to provide a street lamp that provides the durability by utilizing the inherent color of the brass.

However, since the method of forming the film by mixing the powder brass with the transparent paint and then applying the heat treatment is difficult to realize various colors depending on the type of the coating material and the oxidation reaction, There was a limitation that it could not follow the tendency of the industry.

{Patent Document 0001} Korean Patent No. 10-1508970, 'Street Lamp with High Strength and Corrosion Resistant Brass Coating'

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SUMMARY OF THE INVENTION The present invention provides a method for forming an oxide film on a Group 11 metal substrate by chemical treatment (such as oxidation) and supplying a film-forming material (copper oxide, titanium oxide, or chromium oxide). The present invention provides a coating film having various kinds of colors, chroma, brightness, and texture that are settled by controlling the thickness of the oxide film and acting the film-forming material at a predetermined ratio.

Further, according to the present invention, the metal oxide and the film-forming target material, which are supplied while the metal substrate is subjected to the chemical treatment, are supplied instead of the simple heat treatment or the anodizing method in which the film is formed using the anode electrode, It is possible to stabilize the thin film and to change the color, saturation, lightness, texture, etc. over time in the use environment in which the oxide film exposed to the outside is given, so that natural color can be derived.

In addition, whenever the additives to be added to the film-forming material are different, an oxide film having a unique texture and color can be provided.

In particular, the metal substrate treated with the oxide film can be applied to the field of automobiles in the field of automobiles in the construction field, and the present invention can be applied to the buildings related to exhibitions and cultures related to the demands of the users.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are not intended to limit the invention to the precise form disclosed. There will be.

According to an aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: (a) contacting a complex oxide solution on at least one surface of a surface of a metal substrate; And (b) depositing an oxide film on the surface of the metal substrate in contact with the composite oxide solution while removing impurities on the surface of the metal substrate.

In an embodiment of the present invention, the method for forming an oxide film may further include, after step (b), injecting ammonia vapor onto the surface to which the complex oxide solution is contacted.

According to another aspect of the present invention, there is provided an oxide film forming method, wherein the step of forming the oxide film in the step (c) further comprises a step of heating the surface to be contacted do.

In the embodiment of the present invention, in the method for forming an oxide film, the metal-based metal may be any one of a Group 11 metal or an alloy obtained by adding at least one Group 11 metal.

According to another embodiment of the present invention, the Group 11 metal may be copper.

In an embodiment of the present invention, the alloy obtained by adding at least one Group 11 metal may be at least one selected from the group consisting of Cu-Ag alloys, Cu-Cd alloys, Cu-Cr alloys, Cu- Cu alloys, Cu-Te alloys, Cu-Si alloys, Cu-Pb alloys, Cu-Zn alloys (brass), Cu-Sn alloys (bronze and copper alloys) And a Cu-Ni-based alloy (white copper).

In order to achieve the above object, the composite oxide solution is characterized by being an oxidizer and an oxide of a metal constituting the metal base.

In an embodiment of the present invention, the oxide of the metal constituting the metal substrate includes at least one of Cu _x O and Cu ₂ (OH) Cl.

Further, the Cu _x O may be any one of CuO and Cu ₂ O.

In another embodiment of the present invention, the composite oxide solution may further include at least one of Ti 2 O, CrO 3, and NixOy.

In yet another embodiment of the present invention, NixOy may be any of NiO, NiO2, and Ni2O3.

In order to achieve the above aspect, wherein the oxidizing agent comprises any one of perchloric acid (HClO _4), hydrochloric acid (HCl), nitric acid (HNO _3), sulfuric acid (H ₂ SO _4), phosphoric acid (H ₃ PO ₄₎ Thereby forming an oxide film.

In one embodiment of the present invention, the oxidant may be a mixed solution of nitric acid (HNO ₃ ) and sulfuric acid (H ₂ SO ₄ ).

In another embodiment of the present invention, the mass ratio of nitric acid (HNO ₃ ) and sulfuric acid (H ₂ SO ₄ ) in the complex oxidation solution may be nitric acid: sulfuric acid = 0.1: 99.9 to 50:50.

In order to accomplish the above object, the complex oxide solution may further include an activator to uniformly perform the reaction.

In another embodiment of the present invention, the activator is selected from cerium sulfate (Ce ₂ (SO ₄ ) ₃ ), selenium dioxide (SeO ₂ ), antimony oxide (SbO ₂ , Sb ₂ O ₄ ), vanadium oxide ₂ ). ≪ / RTI >

In the embodiment of the present invention, the composite oxidizing solution further includes an additive capable of changing the color or texture of the surface of the metal base.

In order to achieve the above object, the additive of the present invention is characterized in that the additive is composed of any one or combination of two or more of salt, sulfur, peanut oil, wood chips, sawdust, vinegar and sugar frost.

In an embodiment of the present invention, the steam injection time in the step of spraying the ammonia vapor is 1 to 40 hours.

In order to achieve the above object, the heating temperature of the contact surface is in the range of 100 ° C. to 300 ° C., and the heating time is 5 minutes to 60 minutes. ≪ / RTI >

In an embodiment of the present invention, there is provided a method for manufacturing a metal substrate having an oxide film, comprising the steps of: contacting a composite oxide solution to remove impurities on the surface of the metal substrate and simultaneously depositing an oxide film on the surface of the metal substrate Lt; / RTI >

In order to achieve the above object, the present invention provides a metal base material, wherein the metal base metal is any one of a Group 11 metal or an alloy obtained by adding at least one Group 11 metal.

In another embodiment of the present invention, there is provided a metal substrate characterized in that the Group 11 metal is copper.

In an embodiment of the present invention, the alloy obtained by adding at least one Group 11 metal may be at least one selected from the group consisting of Cu-Ag alloys, Cu-Cd alloys, Cu-Cr alloys, Cu- Cu alloys, Cu-Te alloys, Cu-Si alloys, Cu-Pb alloys, Cu-Zn alloys (brass), Cu-Sn alloys (bronze and copper alloys) And a Cu-Ni-based alloy (Baikdong), or a combination of two or more thereof.

In an embodiment of the present invention, there is provided a complex oxide solution comprising an oxidant and an oxide of a metal constituting the metal base.

In another embodiment of the present invention, the oxide of the metal constituting the metal member is a _{Cu x O, Cu 2 (OH} ) Cl, Cu (CH 3 CO 2) 2, CuSO 4, Cu 2 (OH) 2 CO 3 Or a mixture thereof.

In order to achieve the above object, the present invention provides a complex oxide solution, wherein the Cu _x O is any one of CuO and Cu ₂ O.

In the embodiment of the present invention, the complex oxide solution further includes at least one of Ti ₂ O, CrO ₃ , and NixOy.

In another embodiment of the present invention, the Ni _x O _y comprises NiO, NiO ₂ , and Ni ₂ O ₃ .

In another embodiment of the present invention, the oxidant comprises one of a perchloric acid (HClO _4), hydrochloric acid (HCl), nitric acid (HNO _3), sulfuric acid (H ₂ SO _4), phosphoric acid (H ₃ PO ₄₎ And a complex oxidation solution.

In order to achieve the above object, the oxidizing agent is a mixed solution of nitric acid (HNO ₃ ) and sulfuric acid (H ₂ SO ₄ ).

In another embodiment of the present invention, the mass ratio of nitric acid (HNO ₃ ) and sulfuric acid (H ₂ SO ₄ ) in the complex oxidation solution is nitric acid: sulfuric acid = 0.1: 99.9 to 50:50. Solution.

According to an embodiment of the present invention, there is provided a complex oxide solution, which further comprises an activator that allows the reaction to be performed uniformly in the complex oxide solution.

In another embodiment of the present invention the activator is selected from the group consisting of cerium sulfate (Ce ₂ (SO ₄ ) ₃ ), selenium dioxide (SeO ₂ ), antimony (III) oxide (SbO ₂ , Sb ₂ O ₄ ), vanadium oxide VO ₂ ). The present invention also provides a complex oxide solution comprising at least one of the following compounds:

In one embodiment of the present invention, there is provided a composite oxide solution having a mass ratio of 0.1 to 30 wt% of the metal oxide, 20 to 40 wt% of the oxidizer, 0.1 to 5 wt% of the activator, and 30 to 70 wt% of distilled water do.

In another embodiment of the present invention, the oxide of the metal includes at least one of Cu (CH ₃ CO ₂ ) ₂ ), CuSO ₄ , and Cu ₂ (OH) ₂ CO ₃ , And the antimony (III) oxide (Sb ₂ O ₃ ).

In order to accomplish the above object, there is provided a composite oxide solution further comprising an additive capable of changing the color or texture of the surface of the metal substrate.

In another embodiment of the present invention, the additive is a composite oxide (a) selected from the group consisting of salt, sulfur, peanut oil, wood chips, sawdust, vinegar, sugar frost, Solution.

According to the embodiment of the present invention, it is possible to secure a technique capable of realizing a metal substrate of various colors without using an organic pigment on the surface of a Group 11 metal.

Further, since the composite oxide solution containing the additive can realize a metal substrate having a unique texture, it is possible to provide a metallic shell that increases the appearance aesthetic of the conventional unlike a metal having a uniform color or an oxide film .

It should be understood that the effects of the present invention are not limited to the above effects and include all effects that can be deduced from the detailed description of the present invention or the configuration of the invention described in the claims.

1 is a view showing an oxide film production process according to an embodiment of the present invention.
FIG. 2 is a view showing a kind of an oxide film according to an embodiment of the present invention. FIG.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In order to clearly illustrate the present invention, parts not related to the description are omitted, and similar parts are denoted by like reference characters throughout the specification.

Throughout the specification, when a part is referred to as being "connected" (connected, connected, coupled) with another part, it is not only the case where it is "directly connected" "Is included. Also, when a part is referred to as "comprising ", it means that it can include other components as well, without excluding other components unless specifically stated otherwise.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, the terms "comprises" or "having" and the like refer to the presence of stated features, integers, steps, operations, elements, components, or combinations thereof, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

1 is a view showing an oxide film production process according to an embodiment of the present invention. First, in order to form a unique shell of the metal substrate itself, a complex oxidation solution is contacted to cause an oxidation reaction (S100). The present invention is characterized in that an oxide of a metal base constituting a metal base in a composite oxidation solution is deposited on a metal surface to form an oxide film without using an electrochemical reaction to form an oxide film.

After S100, the impurities present on the surface of the metal substrate should be removed (S110). In the case of a metal substrate, since oxygen exists in the atmosphere, it is naturally oxidized even if it is not subjected to a separate oxidation process, and has an uneven metal oxide layer. In the case of the oxidation layer by natural oxidation, the color is not likely to cause a unique aesthetic feeling, and since the thickness and oxidation degree of the oxide layer can not be uniformly adjusted by the process, it is generally desired A step of removing impurities other than the oxide layer existing on the surface of the metal substrate and the oxide layer of the metal itself is performed to form a film.

The composite oxidizing solution is an oxidizing agent that helps form an oxide film so that the surface to be oxidized of the metal substrate can be utilized as a shell of a so-called sensitive material having various colors and textures.

Conventionally, in order to manufacture a color steel sheet, an anodizing process, which is a method of forming an oxide film electrochemically using a metal to be plated as an anode, is used, or an organic solvent is used. However, the conventional processes have to implement uniform color and texture, and thus there has been a limit in that it can not follow the business flow of a small quantity production type of multi-product according to the recent increase in emotional consumption. Further, if an organic solvent is used, the volatile organic solvent is inevitably left in the produced metal sheath, which may cause environmental pollution. Therefore, when an oxide film is deposited by using a complex oxide solution, a multicolor alloy having a wave length in the range of 400 to 700 nanometers (nm) is developed, and unlike the existing color steel sheet manufacturing process, It can be implemented. Furthermore, since there is no use of organic solvents, environmentally friendly oxidation films are formed and harmful substances such as building materials used in the construction of new houses and buildings, and the like, cause headaches, dermatitis, fatigue, difficulty in breathing and asthma Environmental problems such as sick house syndrome do not occur.

Further, when a complex oxidation solution is used, since the oxidizing agent and the oxide of the metal constituting the metal base to form the oxide film are included and the reaction progress of the oxide film can be controlled, the thickness, the components, etc. of the oxide film are uniform The function of the envelope can be performed well.

Wherein the composite oxide includes an oxide of a metal constituting the metal base, wherein the oxide of the metal constituting the metal base is Cu _x O, Cu ₂ (OH) Cl, Cu (CH ₃ CO ₂ ) ₂ , CuSO ₄ , And Cu ₂ (OH) ₂ CO ₃ . Furthermore, the Cu _x O may be any one of CuO and Cu 2 O.

The complex oxide solution may further include at least one of Ti 2 O, CrO 3, and NixOy.

In order to achieve the above object, the Ni _x O _y is one of NiO, NiO 2, and Ni 2 O 3.

In another embodiment of the present invention, the oxidizing agent contained in the composite oxide solution of perchloric acid (HClO _4), hydrochloric acid (HCl), nitric acid (HNO _3), sulfuric acid (H ₂ SO _4), phosphoric acid (H ₃ PO ₄₎ Quot;

In one embodiment of the present invention, the mass ratio of nitric acid (HNO ₃ ) and sulfuric acid (H ₂ SO ₄ ) in the oxidizing agent is 0.1 to 40 wt%.

In another embodiment of the present invention, there is provided a complex oxidation solution characterized in that it further comprises an activator which allows the reaction to be uniformly performed in the complex oxidation solution.

Of the active agent is sulfuric acid, cerium _{(Ce 2 (SO 4) 3} ), selenium dioxide (SeO _2), antimony (Ⅲ) oxide (SbO _2, Sb2O _4), vanadium oxide (VO ₂₎ to an aspect And a complex oxidation solution comprising at least one of the foregoing components.

In one embodiment of the present invention, there is provided a composite oxide solution having a mass ratio of 0.1 to 30 wt% of the metal oxide, 20 to 40 wt% of the oxidizer, 0.1 to 5 wt% of the activator, and 30 to 70 wt% of distilled water do.

In another embodiment of the present invention, the oxide of the metal includes at least one of Cu (CH ₃ CO ₂ ) ₂ ), CuSO ₄ , and Cu ₂ (OH) ₂ CO ₃ , And the antimony (III) oxide (Sb ₂ O ₃ ).

In one embodiment of the present invention, there is provided a composite oxide solution further comprising an additive capable of changing the color or texture of the metal base surface.

In another embodiment of the present invention, the additive comprises a complex oxide (a) selected from the group consisting of salt, sulfur, peanut oil, nuts, sawdust, vinegar, sugar frost, Solution. Vinegar is one of the Western vinegar, and it is a typical seasoning with sour taste. Sugar frost is powdered sugar. By the additive, not only the original texture of the metal substrate but also various textures can be realized.

Further, even after the oxide film is formed primarily on the basis of the complex oxide solution, the additional oxidation reaction can proceed by the natural oxidation. The natural oxidation oxidizes the appearance or inner appearance of the building, etc., Can cause.

After forming the oxide film by contacting with the complex oxide solution, ammonia vapor is sprayed to increase the diversity of the oxidation reaction (S120). At this time, the time for spraying the ammonia vapor is 1 to 40 hours. Depending on the time during which the ammonia vapor is sprayed, the color or pattern of the oxide film may vary.

After S120, the surface of the portion of the formed oxide film can be heated. The heating temperature at the time of heating the surface is 100 ° C. (° C.) to 300 ° C. (° C.), and the heating time is 5 to 60 minutes. Depending on the change in the heating temperature and the change in the heating time, the color or pattern of the oxide film may vary variously.

After S130, an oxide film is formed (S140).

It is possible to form an oxide film having a specific texture on the surface of the metal substrate when ammonia vapor is sprayed after contacting the metal substrate with the additive mixed with various kinds of the complex oxidation solution.

2 is a view showing kinds of various types of oxide films produced according to an embodiment of the present invention.

(1) is the result of spraying ammonia vapor after contacting a surface of a brass metal base with a sugar frost as an additive to a Cu-Zn based alloy (brass).

(2) is the result of spraying ammonia vapor after contacting a surface of a brass metal base with a salt of Cu-Zn based alloy (brass) as an additive to the complex oxidation solution.

(3) is the result of spraying ammonia vapor after contacting the surface of the brass metal base with the sawdust to the Cu-Zn alloy (brass) as an additive for the composite oxidation solution for 12 to 36 hours.

(4) is the result of contacting the surface of the brass metal base with the Cu-Zn based alloy (brass) using peanut oil as an additive for the composite oxidation solution.

It will be understood by those skilled in the art that the foregoing description of the present invention is for illustrative purposes only and that those of ordinary skill in the art can readily understand that various changes and modifications may be made without departing from the spirit or essential characteristics of the present invention. will be. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included within the scope of the present invention.

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Claims (37)

In the method for forming an oxide film of a metal base,
(a) contacting the composite oxide solution on at least one surface of the metal substrate surface; And
(b) removing the impurities on the surface of the metal substrate and simultaneously depositing the oxide film on the surface of the metal substrate that has been contacted; And
(c) after the step (b), injecting ammonia vapor onto the surface to which the complex oxide solution is contacted; Lt; / RTI >
Wherein the composite oxide solution comprises an oxidizing agent and an oxide of a metal constituting the metal substrate.
delete The method according to claim 1,
Wherein the step (c) further comprises a step of heating the contacted surface.
The method according to claim 1,
Wherein the metal of the metal base is any one of a group 11 metal or an alloy obtained by adding at least one group 11 metal.
The method of claim 4,
Lt; RTI ID = 0.0 > 11 < / RTI > metal is copper.
The method of claim 5,
The alloy obtained by adding at least one of the Group 11 metals may be at least one selected from the group consisting of a Cu-Ag alloy, a Cu-Cd alloy, a Cu-Cr alloy, a Cu-Be alloy, a Cu- Cu alloys such as Cu-Si alloys, Cu-Pb alloys, Cu-Zn alloys (brass), Cu-Sn alloys (bronze and palladium), Cu-Al alloys (aluminum bronze) Or a combination of two or more thereof.
delete The method according to claim 1,
The oxide of the metal constituting the metal substrate may include at least one of Cu _x O, Cu ₂ (OH) Cl, Cu (CH ₃ CO ₂ ) ₂ , CuSO ₄ and Cu ₂ (OH) ₂ CO ₃ To form an oxide film.
The method of claim 8,
Wherein the Cu _x O is any one of CuO and Cu ₂ O.
The method according to claim 1,
Wherein the composite oxide solution further comprises at least one of Ti ₂ O, CrO ₃ , and Ni _x O _y .
The method of claim 10,
Wherein the Ni _x O _y is one of NiO, NiO ₂ , and Ni ₂ O ₃ .
The method according to claim 1,
Wherein the oxidizing agent comprises at least one of perchloric acid (HClO ₄ ), hydrochloric acid (HCl), nitric acid (HNO ₃ ), sulfuric acid (H ₂ SO ₄ ) and phosphoric acid (H ₃ PO ₄ ) .
The method of claim 12,
Wherein the oxidizing agent is a mixed solution of nitric acid (HNO ₃ ) and sulfuric acid (H ₂ SO ₄ ).
14. The method of claim 13,
Wherein the mass ratio of nitric acid (HNO ₃ ) and sulfuric acid (H ₂ SO ₄ ) in the complex oxidation solution is nitric acid: sulfuric acid = 0.1: 99.9 to 50:50.
The method according to claim 1,
Wherein the composite oxide solution further comprises an activator that allows the reaction to be performed uniformly.
16. The method of claim 15,
Wherein the active agents comprises at least one of sulfuric acid cerium _{(Ce 2 (SO 4) 3} ), selenium dioxide (SeO _2), antimony (Ⅲ) oxide (SbO _2, Sb2O _4), vanadium oxide (VO ₂₎ Wherein the oxide film is formed on the substrate.
The method according to claim 1,
Wherein the composite oxide solution further comprises an additive capable of changing the color or texture of the surface of the metal substrate.
18. The method of claim 17,
Wherein the additive is one or more of a combination of at least one of salt, sulfur, peanut oil, wood chips, sawdust, vinegar, sugar frost, or a combination of two or more thereof.
The method according to claim 1,
Wherein the steam injection time in the step of spraying the ammonia vapor is 1 to 40 hours.
The method of claim 3,
Wherein the heating temperature of the step of heating the contacted surface is 100 to 300 占 폚 and the heating time is 5 to 60 minutes.
Removing the impurities on the surface of the metal substrate by contacting the composite oxide solution and placing the oxide film on the surface of the metal substrate that has been contacted, and then spraying ammonia vapor onto the surface to which the composite oxide solution is contacted,
Wherein the composite oxide solution comprises an oxidizing agent and an oxide of a metal constituting the metal base.
23. The method of claim 21,
Wherein the metal of the metal base is any one of a Group 11 metal or an alloy obtained by adding at least one Group 11 metal.
23. The method of claim 22,
Wherein the Group 11 metal is copper.
24. The method of claim 23,
The alloy obtained by adding at least one of the Group 11 metals may be at least one selected from the group consisting of a Cu-Ag alloy, a Cu-Cd alloy, a Cu-Cr alloy, a Cu-Be alloy, a Cu- Cu alloys such as Cu-Si alloys, Cu-Pb alloys, Cu-Zn alloys (brass), Cu-Sn alloys (bronze and palladium), Cu-Al alloys (aluminum bronze) Or a combination of two or more thereof. delete delete delete delete delete delete delete delete delete delete delete delete delete

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