WO2006106716A1

WO2006106716A1 - Surface treated metal product

Info

Publication number: WO2006106716A1
Application number: PCT/JP2006/306436
Authority: WO
Inventors: Akira Izumi; Yutaka Kadotani
Original assignee: Kyushu Institute Of Technology; Toyo Stainless Polish Industry Co., Ltd.
Priority date: 2005-03-31
Filing date: 2006-03-29
Publication date: 2006-10-12
Also published as: JP5091667B2; JPWO2006106716A1

Abstract

This invention provides a surface treated metal product comprising a metal product having a surface covered with a see-through carbide, nitride, or carbonitride inorganic material, for example, with a silicon carbonitride film. The surface treated metal product can see beautiful gloss on the metal surface through the film. The surface treated metal product can be colored, and contact marks such as fingerprints are not left even when a finger comes into contact with the surface. Further, even when scratches are formed, they are inconspicuous. Furthermore, the surface treated metal product has excellent corrosion resistance, weathering resistance, antifouling properties and other properties.

Description

Specification

Surface-treated metal products

Technical field

[0001] The present invention relates to a surface-treated metal product obtained by coating a metal product surface with an inorganic material.

More specifically, the present invention covers the surface with a transparent inorganic material film, so that the metal background can be seen through the inorganic material or colored by light interference, In addition, the present invention relates to a surface-treated metal product characterized in that its surface condition is excellent in weather resistance and has anticorrosion and antifouling properties.

Background art

[0002] In recent years, paints have been applied to household appliances such as refrigerators, office equipment such as cabinets, housing equipment such as system kitchens, and outer walls and frames of buildings, and metal products such as stainless steel plates and steel plates. Attempts have been made to make full use of the beautiful luster of metal products without the use of such materials. However, when touching the surface of a metal product with a finger, contact marks such as fingerprints remain, and even if there is a slight pulling flaw, it is noticeable, especially in the case of building materials. It has the disadvantage that metal materials corrode due to the effects of acid rain. For this reason, a protective layer such as a resin film is provided on the surface of a metal product, and attempts are being made to prevent contact traces such as fingers, scratches and the like, and corrosion. However, there is no example of providing an inorganic material as a protective film that can be seen through and has sufficient weather resistance on the surface of metal products. Examples of forming a protective film or an outer surface coating through which the metal background can be seen through are formed on the metal background.

[0003] In JP-A-6-57178, a transparent anticorrosive thick film paint is applied to the metal ground surface of an aluminum alloy road wheel, which is an automotive part, so that the transparency of the metal background before application is improved. There has been disclosed a method for forming a coating film that can prevent corrosion of metal without impairing it and prevent inhibition of adhesion due to external impact (Patent Document 1). In this method, since the surface of the mouth wheel is a three-dimensional curved surface, it is possible to form a protective film by painting, but the anticorrosion effect can be maintained for a long time by the occurrence of pinholes. It is difficult. Patent Document 1: JP-A-6-57178

[0004] Further, Japanese Patent Application Laid-Open No. 9-277476 has excellent formability when used for coating the outer surface of a deep-drawn metal can, and it is important to perform printing on the outer surface of the metal can. Disclosed is a polyester laminate film that can be used to coat the outer surface of deep-drawn metal cans, where the metal surface can be seen through the heel, and when the metal product is sterilized by retort, there is no whitening on the outer coating. (Patent Document 2). The polyester film used for coating the outer surface of this deep-drawn metal can has a crystallization temperature of 100 to 160 ° C in order to ensure moldability and prevent the occurrence of whitening spots during retort sterilization. In addition, a special polyester film containing 0.01 to 1% by weight of a lubricant having an average particle size of 0.01 to 2.5 111 must be used, and a general-purpose inexpensive resin film can be used. Nah ...

Patent Document 2: Japanese Patent Laid-Open No. 9-277476

[0005] The technology as described above provides a metal product in a state in which a metallic glaze is maintained by coating a transparent resin film. In addition, a resin laminated steel sheet coated with a transparent resin film is also known, and a steel sheet coated with a transparent resin such as fluorine or acrylic is also known. However, it is considered that the long-lasting anti-corrosion effect cannot be maintained with the resin film obtained by the current painting method or laminating method due to the occurrence of pinholes. In addition, the surface coating of a resin film has many limitations due to workability that only a specific shape can be coated. In addition, there is a problem that metal coated with rosin cannot be recycled.

[0006] Conventionally, a technique for forming a coating of an inorganic material on the surface of a metal member to impart wear resistance, corrosion resistance, heat resistance, etc. has been known (for example, see Patent Documents 3 and 4 below). As far as the present inventor is aware, there is an idea that the surface of a metal product is coated with a film of a carbide, nitride, or carbonitride-based inorganic material that is transparent and is provided with wear resistance, corrosion resistance, and heat resistance. There has never been a proposal before.

Patent Document 3: Japanese Patent Laid-Open No. 4-165087

Patent Document 4: JP-A-9-125229

Disclosure of the invention

Problems to be solved by the invention [0007] An object of the present invention is to provide a metal product excellent in cosmetics, corrosion resistance, weather resistance, and the like without impairing the transparency of the surface of the metal product.

Means for solving the problem

[0008] The invention according to claim 1 of the present invention is a surface-treated metal product obtained by coating the surface of a metal product with a carbide, nitride, or carbonitride-based inorganic material having transparency.

[0009] The invention according to claim 2 is the surface-treated metal product according to claim 1, wherein the carbide, nitride, or carbonitride-based inorganic material has an interference color with the surface of the metal product. It is.

[0010] The invention according to claim 3 is the surface-treated metal product according to claim 1 or 2, wherein the inorganic material strength material having transparency has a Martens hardness of 25 GPa or more.

[0011] The invention according to claim 4 is the surface-treated metal product according to any one of claims 1 to 3, wherein the transparent inorganic material is a silicon carbonitride film.

[0012] The invention according to claim 5 is any one of claims 1 to 4, wherein the design and the Z or functionality are imparted to the metal surface in advance by physical and Z or chemical treatment. It is a surface-treated metal product described in the section.

[0013] The invention according to claim 6 is characterized in that the physical and Z or chemical treatments are surface polishing force, embossing, punching, etching, thin film forming or anodizing. 6. The surface-treated metal product according to claim 5, wherein the surface-treated metal product is any of the above.

[0014] In the invention according to claim 7, the metal product before coating is stainless steel, aluminum alloy, surface-treated steel, plated steel, aluminum, titanium, magnesium, copper, hastelloy steel, -kel steel, or these 7. The surface-treated metal product according to any one of claims 1 to 6, which is selected from the group consisting of a combination of metals and a product consisting of them and other materials.

[0015] The invention according to claim 8 is a surface-treated titanium product obtained by coating the surface of a titanium color product with a silicon carbonitride film.

[0016] The invention according to claim 9 is a surface-treated magnesium or magnesium alloy product obtained by coating the surface of magnesium or a magnesium alloy having an anodized film with a silicon carbonitride film. In the present invention, the film is a thin film that covers the surface of a metal product. The

The invention's effect

[0017] The surface-treated metal product of the present invention is formed by coating a metal product with an inorganic material film, in particular, a metal product with a transparent film, and the metal background penetrates the inorganic material film. It looks strong or colored due to light interference, and is excellent in weather resistance, corrosion resistance, antifouling property, and the like.

Brief Description of Drawings

[0018] FIG. 1 is a view showing a measurement result of a contact angle of a silicon carbonitride film (SiCN film) formed at each substrate (stainless steel plate) temperature.

FIG. 2 is a diagram showing measurement results of Martens hardness of silicon carbonitride films formed at each substrate temperature.

FIG. 3 is a graph showing changes in contact angle over time of silicon carbonitride films formed on various substrates.

FIG. 4 is a graph showing a change in refractive index with time of a silicon carbonitride film formed on a silicon plate.

FIG. 5 is a diagram showing the change over time of the film thickness of a silicon carbonitride film formed on a silicon plate. BEST MODE FOR CARRYING OUT THE INVENTION

In the present invention, the metal product includes intermediate products and power products of all shapes such as metal plates, pipes and coils. Depending on the application, it may include other combinations such as plastics, glass, ceramics. For metal products, it is an interesting use to take advantage of the beautiful luster of the metal product surface without painting, but the surface of the metal product surface may leave contact marks such as fingerprints when touching the surface. Even if there are slight pulling creases, it is noticeable, and dirt is likely to occur due to wind and rain. Accordingly, the present invention provides a metal product in which these problems are solved, that is, a metal product obtained by coating the surface of a metal product with a carbide, nitride, or carbonitride-based inorganic material. Is. “Transparent” means a state in which the surface of the metal product surface appears to be transparent, or a state in which the metal product surface appears colored in various colors due to light interference with the metal surface. As long as you can feel the beauty of the background even if it is completely transparent It can be a semi-transparent one that looks like it is, or it can be a colored one.

[0020] The carbide, nitride or carbonitride-based inorganic material of the present invention covers a part of the surface of the metal product as needed only by covering the entire surface of the metal product with a film. It may be something that you swear. In addition, an inorganic material that can be colored or printed with an organic or inorganic pigment or the like can also be used. Furthermore, the same kind or different kinds of inorganic materials may be laminated and coated in multiple layers (same thickness or different thickness).

The carbide, nitride or carbonitride-based inorganic material of the present invention preferably has a material hardness of 25 GPa (Martens hardness) or more. Specific examples include silicon carbonitride film, carbonitride film, diamond-like carbon, diamond, silicon diamond, and silicon nitrogen. Particularly preferred in the present invention is a silicon carbonitride film, which means a thin film generally represented by SiCxNy. However, in SiCxNy, X and y mean numerical values satisfying 0 <x <l and 0 <y <4/3, respectively, and 4x + 3y = 4.

[0022] As the metal product before coating, it is necessary to have a metal sheet that can be easily processed, such as a folding casing, which does not generate dirt on the surface for a long period of time. Stainless steel, aluminum alloy , Surface-treated steel, plated steel, aluminum, titanium, magnesium, copper, hastelloy steel, nickel steel or combinations of these metals (e.g. alloys, plywood), and other materials such as plastics, A group power consisting of products made of glass and ceramics.

[0023] The metal product before coating may be one in which design and Z or functionality are imparted to the metal surface in advance by physical and Z or chemical treatment. Any method may be used as the physical treatment.For example, as a surface treatment after hot rolling or cold rolling, after hot rolling, annealing and descaling are performed to obtain a silver-white matte surface finish. After cold rolling, finish the silver white glossy surface by annealing pickling, smooth glossy surface finish by lightly polishing the glossy surface with a polishing roll, and mirror finish by removing bright heat treatment after cold rolling There is a near glossy surface finish. In addition, surface treatment by surface polishing includes various types of surface polishing ranging from relatively rough polishing of about # 100 to precise polishing by puffs. Can do.

[0024] In addition, as a special finish, when a long continuous polish like a hair is applied with an abrasive belt of moderate particle size, a non-directional hairline polishing finish by multi-axis horizontal polishing There are also vibration finishing, shot blasting when alumina or other shots are blown with high-pressure air, and glass bead blasting when glass beads are blown with high-pressure air. In addition, there is a punching machine embossing with a press machine.

[0025] In addition, grinding is performed according to the rotation direction by bringing the abrasive particles into contact with a metal product while rotating the polishing roll using an abrasive roll fixed to paper. In this case, a linear pattern along the traveling direction is formed on the surface of the metal product. In addition, non-directional grinding is performed by bringing a horizontal polishing machine into contact with a metal product while applying eccentricity / vibration using a paper or unclothed cloth with polished particles fixed. In this case, a non-directional random pattern is formed on the metal surface. In addition, by spraying glass beads or alumina onto metal products with high-pressure air, a textured pattern is formed on the metal products. All of these are preferred as physical treatment methods for metal products before coating in the present invention.

[0026] Examples of the chemical treatment include etching, thin film formation, or anodization (oxide film formation by anodization). As the thin film forming process, for example, a thin film made of TiN, TiO, TiCN or the like may be formed on a metal surface by physical vapor deposition (PVD) ion plating technology. When these are combined with the present invention, gold

2

The wear resistance, corrosion resistance, heat resistance, etc. of the product are further improved.

[0027] The surface or surface pattern of a metal product that has been subjected to physical and Z or chemical treatment is a typical surface appearance of the metal product, and is a surface or pattern that is also beautiful in design. The strength of this pattern and the like can be selectively given according to the application and preference by changing or adjusting the physical and Z or chemical treatment method conditions. In addition, if a finger touches a bare metal product, the trace will remain, resulting in a dirty appearance. Therefore, after applying a desired surface pattern to the surface of the metal product as described above, the metal product surface is coated with a transparent inorganic material of the present invention, such as carbide, nitride or carbonitride. Even though the surface of the metal product can be seen through, the surface is not noticeable even if the surface is wrinkled. However, no trace remains, and the cosmetic (surface treatment) metal product of the present invention can be obtained without damaging the beautiful surface.

[0028] Further, the mirror surface of a metal product formed by a physical method or an ionic method may be coated with the transparent inorganic material of the carbide, nitride or carbonitride type of the present invention. Even if the surface is wrinkled, the cosmetic metal product of the present invention can be obtained without damaging the beautiful surface that does not stand out even if a finger or the like is touched. Further, the carbide, nitride or carbonitride-based inorganic material of the present invention may be coated on the metal surface coated with the thin film forming caloe. In either case, an interference color can be emitted depending on the film thickness of the coated inorganic material.

[0029] In the present invention, a known method 'means for coating a metal product surface with a carbide, nitride or carbonitride-based inorganic material having transparency is not particularly limited. Can be adopted. Preferable examples include chemical vapor deposition, anodic oxidation, sputtering, and ion plating.

In the present invention, a characteristic surface-treated titanium product having a very robust interference color can be obtained by coating the surface of the titanium color product with a silicon carbonitride film. When electrolysis is performed using titanium as an anode in an aqueous solution using a positive oxidation system, the titanium surface of the anode reacts with oxygen to form a thin film (acid-soluble film, TiO 2) on the surface. This acid

2

The film itself is colorless and transparent, but appears colored due to interference of visible light due to its thickness. Although the color looks different depending on the thickness of the coating, the thickness of the coating is determined by the anodizing voltage, so the desired titanium color product can be obtained by adjusting the voltage.

[0031] When this is coated with the inorganic material of the present invention, particularly a silicon carbonitride film, a characteristic surface-treated titanium product having a very robust interference color can be obtained. A surface-treated titanium product with a desired color can be obtained by designing with the force that changes the interference color of the original titanium slightly due to the thickness of the silicon carbonitride film. For example, when the titanium color product is used outdoors, the surface of the titanium is acidified due to acid rain, and a film of hydroxide is formed on the surface, causing the light interference color to change completely. Will occur. The harsh phenomenon cannot be solved by ordinary protective coating, but if it is coated with the thin and transparent silicon carbonitride of the present invention, it becomes possible to sufficiently prevent discoloration of interference colors. The

[0032] Magnesium alloys are also increasingly used for portable electronic equipment due to their light weight! However, since it is a metal that is easily oxidized, it is important to protect the surface with an oxidation-resistant film, and it relies on anodic acid resin coating. However, magnesium anodic oxide coatings are porous with larger voids than aluminum oxide coatings, and the coatings have poor acid resistance performance, and limited color development and power cannot be obtained. For this reason, a resin coating is further performed on the anodized film, but the metallic luster at the corners is impaired and the discrimination from the plastic casing is impaired. Also, the resin coating film becomes a problem when recycling magnesium.

[0033] When the silicon carbonitride film (SiCxNy film) of the present invention is formed directly on magnesium or a magnesium alloy or after anodized on the surface of magnesium or a magnesium alloy, the corrosion resistance performance There are advantages such as improvement in surface hardness, improvement in surface hardness, difficulty in attaching fingerprints or generation of metal color, and no obstruction to recycling.

Example 1

[0034] Using hexamethyldisilazane (HMDS) and ammonia (NH 3) as raw materials,

Three

A silicon carbonitride film was deposited and coated on a stainless steel plate that had been mirror-polished by a wire-wire chemical vapor deposition method. When the film thickness of the silicon carbonitride film (SiCxNy film) was changed, the color developed due to interference between the underlying stainless steel substrate and the transparent SiCxNy film, and brown (50 nm) as the film thickness increased. ), Purple (75 nm), blue (90 nm), yellowish green (130 °), gold (150 nm), orange (170 nm), green (190 nm), red purple (200 °). The numbers in parentheses indicate the film thickness of the SiCxNy film measured by ellipsometry. Example 2

FIG. 1 shows the contact angle measurement results of a silicon carbonitride film (SiCxNy film) having a film thickness of 50 nm formed at each substrate (stainless steel plate) temperature. White circles use HMDS and NH (50

The results using 3 sccm) and black circles show the results using only HMDS as the raw material. The contact angle before film formation was 89 degrees, but after the silicon carbonitride film was formed, it can be seen that the value of the contact angle became smaller under any conditions. Since the contact angle is small, Improved wettability and improved antifouling properties.

[0036] Fig. 2 shows the Martens hardness measurement results of the silicon carbonitride film formed at each substrate temperature. Martens hardness measurement was performed using an ultra-fine indentation hardness tester. It can be seen that a silicon carbonitride film having a hardness of 28.7 GPa can be obtained by setting the substrate temperature during deposition to 250 ° C. This is particularly excellent in strength.

[0037] When the stainless steel plate coated with the silicon carbonitride film obtained in this example was immersed in hydrogen fluoride, sulfuric acid, nitric acid, hydrochloric acid, sodium chloride aqueous solution, and sodium hydroxide aqueous solution, interference was caused. No color change, film peeling, or pinholes were observed.

Example 3

[0038] Fig. 3 shows the water of a lOOnm-thick silicon carbonitride film (SiCxNy film) formed on the surface of aluminum (A1), copper (Cu), stainless steel (SUS), and titanium (Ti). The results of contact angle measurement with are shown. Deposition conditions are: HMDS flow rate of raw material 1. lsccm, NH flow rate 5

Three

The substrate temperature was 250 ° C, and the tungsten filament temperature was 1,750 ° C. Although any metal material has a large contact angle in the range of 90 to 140 degrees before film formation, the contact angle value S has decreased after the formation of the silicon carbonitride film, and it has been in a 10% sulfuric acid solution for a long time. Even when immersed, the contact angle was almost unchanged.

Example 4

[0039] FIGS. 4 and 5 show that when a silicon carbonitride film (SiCxNy film) having a film thickness of lOOnm is formed on the surface of the silicon plate and treated with sulfuric acid, nitric acid, hydrochloric acid, or saline at a concentration of 10%. Changes in refractive index (Fig. 4) and film thickness (Fig. 5) are shown. Deposition conditions are as follows: HMDS flow rate of raw material is 1. lsccm, NH flow rate is 50 sccm, substrate temperature is 250 ° C, tungsten filament temperature is 1,750

Three

It was. Since both the refractive index and the film thickness have hardly changed, it can be seen that the quality of the film has changed and the etching has occurred.

Example 5

In this example, the surface of a titanium color plate obtained by anodizing a pure titanium plate was covered with a silicon carbonitride film, and the change in interference color was observed. First, according to a conventional method, the anodic oxidation voltage is set to 13V and 30V, and colored in gold (13V) and blue (30V) respectively. A visible titanium color plate was obtained. Next, hot wire chemical vapor deposition using hexamethyldisilazane (HMDS) and ammonia (NH 3) as the same raw materials as in Example 1.

Three

By this method, a silicon carbonitride film (SiCxNy film) was formed on the surface of the titanium color plate.

[0041] The film thickness was 60 nm for the gold (13V) titanium color plate and 80 nm for the blue (30V) titanium color plate. Depending on the film thickness, the gold color was colored blue and the blue color was colored gold due to interference between the underlying titanium color plate and the transparent SiC xNy film. In addition, the surface-treated titanium plate whose surface obtained by striking the surface was covered with a silicon carbonitride film was very excellent in the weather resistance of the interference color.

Industrial applicability

[0042] The surface-treated metal product of the present invention is coated with an inorganic material having transparency, so that the background and gloss of the metal product are maintained, and the optical interference effect between the inorganic material and the base is utilized. Thus, a beautiful color tone is also given. In addition, the coating film has excellent fingerprint resistance and weather resistance that does not stand out even if the surface is scratched. For this reason, the metal product of the present invention is suitably applied to household appliances such as refrigerators where the metal surface can be seen, office equipment such as cabinets, housing equipment such as system kitchens, and construction materials such as outer and inner walls. can do.

Claims

The scope of the claims

[1] A surface-treated metal product obtained by coating a metal surface with a carbide, nitride, or carbonitride-based inorganic material having transparency.

[2] The surface-treated metal product according to [1], wherein the transparent inorganic material generates an interference color with the metal surface.

[3] The surface-treated metal product according to claim 1 or 2, wherein the transparent inorganic material has a Martens hardness of 25 GPa or more.

4. The surface-treated metal product according to any one of claims 1 to 3, wherein the transparent inorganic material is a silicon carbonitride film.

[5] The surface-treated metal product according to any one of claims 1 to 4, wherein the metal surface is preliminarily provided with designability and Z or functionality by physical and Z or chemical treatment.

[6] Physical and Z or chemical treatments are used for surface polishing force, embossing force, punching caroe

6. The surface-treated metal product according to claim 5, wherein the surface-treated metal product is any one of etching processing, thin film forming processing, and anodizing processing.

[7] Metal products before coating are stainless steel, aluminum alloy, surface-treated steel, plated steel, aluminum, titanium, magnesium, copper, hastelloy steel, nickel steel, or a combination of these metals, The surface-treated metal product according to any one of claims 1 to 6, wherein a group force composed of a product composed of these and other materials is also selected.

[8] Surface-treated titanium products with titanium color products coated with silicon carbonitride film

[9] A surface-treated magnesium or magnesium alloy product obtained by coating the surface of magnesium or a magnesium alloy having an anodized film with a silicon carbonitride film.