JP2003328112A - Gold-colored lustrous material and manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gold-colored lustrous material suitable for use in automobile exterior parts, etc., and also to provide a method for manufacturing such a gold-colored lustrous material by using a vacuum process. <P>SOLUTION: The gold-colored lustrous material has a base material composed of a metallic material or a resin material, a resin coating film formed on the surface of the base material, a metal thin film deposited onto the resin coating film by sputtering, a compound thin film deposited onto the metal thin film by sputtering and a transparent resin coating film formed as a protective layer on the compound thin film. In the method for manufacturing the gold-colored lustrous material, the films constituting the gold-colored lustrous material are formed in succession from the side of the base material composed of the metallic or resin material. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a golden glitter material suitable for use in automobile exterior parts and the like, and a method for producing the same.

[0002]

2. Description of the Related Art Metallic materials and resin materials (golden luster materials) having a golden metallic luster are used for automobile exterior parts and the like. As a surface treatment method for imparting a golden metallic luster to a metal material and a resin material, there is an electro gold plating method using potassium gold cyanide or the like. However, in this method, since the surface is smoothed with a coating material that is an insulator in order to obtain a metallic luster, the metal material or the resin material cannot be directly electroplated. Therefore, this method requires a step of forming a conductive film on the paint that smoothes the surface. Furthermore, since this method uses a cyanide chemical which is a poison, it requires strict chemical storage management and waste liquid treatment with strict process control.

Another surface treatment method for giving a metallic metallic luster to metallic materials and resin materials is an anodizing method. The anodizing method is industrially used for aluminum, titanium, tantalum and niobium. In particular, when the anodic oxidation method is used for an aluminum alloy, the color of the oxide film changes depending on the alloy component. Among them, oxalic acid is used as the electrolytic solution, and 3000 series, 5000 series, 60 containing magnesium are used.
A gold color is obtained by forming a decorative dyeing coating on a 00 series alloy. However, this method cannot be applied to the surface treatment of the resin material or the applicable metal material is limited. In addition, this method, like the electroplating method,
Waste liquid treatment with strict process control is required. Furthermore, the anodic oxidation method cannot be applied to a material whose surface is smoothed with a paint which is an insulator.

The process of forming a new conductive film on the smoothed coating surface, the strict chemical storage control, and the waste liquid treatment with strict process control are not required, and a wide range of metallic materials and resin materials are provided with a golden metallic luster. There is a vacuum method as a surface treatment method. The vacuum method includes vacuum deposition, ion plating, and sputtering.

By vacuum-depositing gold or a gold alloy on the surface of a resin coating film obtained by smoothing the surface of a metal material or a resin material, a glitter material having a golden metallic luster can be obtained. However, since the gold vapor deposition film and the gold alloy vapor deposition film have weak adhesion to the resin coating film, the obtained gold color glitter material does not have satisfactory performance as an automobile exterior part. Titanium nitride is another material that develops a golden color, but when attempting to evaporate titanium nitride by vacuum vapor deposition, titanium and nitrogen are decomposed and a golden thin film cannot be obtained.

A gold titanium nitride film is obtained by using ion plating. However, since titanium particles having ionization and high energy are reacted with nitrogen gas, the metal material or the resin material whose surface is smoothed by the resin coating film is deformed at a high temperature.

By sputtering, a thin film can be formed at room temperature on the surface of a resin coating film (insulator) obtained by smoothing the surface of a metal material or a resin material. However, when a titanium nitride thin film is formed by sputtering, there is a problem that a golden color cannot be obtained.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above problems and manufacture a golden glitter material suitable for use in automobile exterior parts and the like, and to manufacture such a golden glitter material using a vacuum method. To provide a way to do.

[0009]

The golden glitter material of the present invention comprises a base material made of a metal material or a resin material, a resin coating film (undercoat) formed on the surface of the base material, and the resin coating film. A thin metal film formed by sputtering on the
A compound thin film formed by sputtering on the metal thin film, and a transparent resin coating film (top coat) formed as a protective layer on the compound thin film.

Further, the method for producing a golden luster material of the present invention comprises a step of forming a resin coating film on the surface of a base material made of a metal material or a resin material, and forming a metal thin film on the resin coating film by sputtering. And a step of forming a compound thin film on the metal thin film by sputtering, and a step of forming a transparent resin coating film as a protective layer on the compound thin film.

In the golden glitter material of the present invention and the method for producing the golden glitter material of the present invention, the following items (1) and (2) are preferable.

(1) The metal thin film is made of Al, Ni, Ti, C
r and an alloy containing at least one of these metals as a main component. The film thickness is 10 to 15
It is 0 nm.

(2) The compound thin film is a compound containing Ti and N. The film thickness is 5 to 100 nm.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION In order to achieve the above object, the present inventor has earnestly studied to develop a titanium nitride thin film formed mainly by sputtering into a gold color having metallic luster. As a result, they have found the following matters and arrived at the present invention. That is, a metal thin film of a specific component is previously formed on the surface of a resin coating film obtained by smoothing the surface of a metal material or a resin material by sputtering. Then, it was found that the titanium nitride thin film laminated on the metal thin film by sputtering develops a golden color with metallic luster. .

In the gold glitter material of the present invention, when the base material is a metal material, a chemical conversion treatment film such as chromate may be formed on the surface of the base material from the viewpoint of rust prevention and adhesion of the base material.

The resin coating film is, for example, of polyester type or acrylic type and is formed in order to make the surface of the base material made of a metal material or a resin material smooth. The film thickness is preferably formed to 5 to 40 μm. If it is less than 5 μm, a sufficiently smooth surface cannot be obtained. On the other hand, when it exceeds 40 μm, coating film defects such as sagging and cracking are likely to occur. When the surface roughness of the base material is large, at least one electrostatic coating film of polyester, acrylic and epoxy is formed in advance, and a resin coating film is formed on it. Good.

A metal thin film is formed on the resin coating film by sputtering, and a compound thin film is formed on this metal thin film by sputtering. The thickness of the metal thin film is less than 10 nm,
Alternatively, if the film thickness of the compound thin film is less than 5 nm, gold color is not developed. That is, when the compound thin film having an appropriate film thickness is formed on the metal thin film having an appropriate film thickness, the compound thin film develops a golden color with metallic luster. At the same time, it provides satisfactory performance for automobile exterior parts. Although the reason for these is not clear, it is considered that the metal thin film functions as an adhesive layer between the resin coating film and the compound thin film, and the adhesion is strengthened. When the compound thin film is titanium nitride, a golden color cannot be obtained if there is no metal thin film or if the film is insufficient. On the other hand, when the thickness of the metal thin film exceeds 150 nm, cracks and wrinkles occur in the metal thin film. Further, when the film thickness of the compound thin film exceeds 100 nm, cracks and wrinkles occur in the compound thin film.

A transparent resin coating film is formed as a protective layer on the compound thin film. The transparent resin coating film is, for example, an acrylic melamine type or an acrylic urethane type. The film thickness is 5-4
The thickness is preferably 0 μm. If it is less than 5 μm, scratches caused by scratching, flying stones, etc. reach the compound thin film and the metal thin film. On the other hand, when it exceeds 40 μm, coating film defects such as armpits and sags occur. From the viewpoint of the adhesiveness between the compound thin film and the transparent resin coating film, an epoxy resin coating film may be previously formed on the compound thin film, and the transparent resin coating film may be formed thereon.

The manufacturing method of the present invention is a method of manufacturing the golden luster material of the present invention.

In the production method of the present invention, when the base material is a metal material, a chemical conversion treatment such as chromate may be applied to the base material from the viewpoint of rust prevention and adhesion of the base material.

When a resin coating film is formed on a substrate having a high surface roughness, at least one powder coating material selected from polyester, acrylic and epoxy powders may be electrostatically coated in advance.

Before forming the transparent resin coating film,
From the viewpoint of adhesion between the compound thin film and the transparent resin coating film, an epoxy resin coating material (primer) may be applied.

[0023]

Example 1 Example 1 AC4C material (Al-Si) cast aluminum alloy with black skin removed by shot blasting
-Mg system, size: 5 x 10 cm, thickness: 1 cm),
Used as a substrate.

After chromic acid chromate conversion treatment of this substrate, acrylic powder coating was electrostatically applied (coating thickness: 12
0 μm) and dried at 140 ° C. for 1 hour.

Next, a resin coating film of polyester / melamine paint was formed with an air spray gun to a thickness of 30 μm and heated at 140 ° C.
And dried for 30 minutes.

Next, a metal thin film of Al-Ti alloy was formed to a thickness of 70 nm by a DC magnetron sputtering apparatus equipped with an Al-20 mass% Ti alloy target. Subsequently, the target was replaced with a titanium nitride target, and a compound thin film of titanium and nitrogen was formed to a thickness of 40 nm. The sputtering conditions were as follows for both the metal thin film and the compound thin film. That is, ultimate vacuum: 5 × 10 ⁻³ Pa, Ar gas pressure: 0.2 Pa, target-substrate distance: 100 mm, substrate rotation speed: 9 r
pm, cathode current: 3A.

Next, a coating film of a resin paint containing an epoxy resin as a main component was formed with an air spray gun to a film thickness of 5 μm.

On this, a transparent resin coating film of acrylic melamine resin was formed with an air spray gun to a film thickness of 25 μm and dried at 140 ° C. for 30 minutes.

The metal material thus prepared by surface treatment had no metallic deformation, cracks and wrinkles and had a golden metallic luster. Further, this metal material was subjected to various performance tests assuming automobile exterior parts. The results satisfied all performance tests as shown in Table 1.

[0030]

[Table 1]

Example 2 The same procedure as in Example 1 was repeated until a resin coating film of polyester / melamine paint was formed and dried.

Next, a metal thin film of Al-Ti alloy was formed to a thickness of 150 nm with a DC magnetron sputtering apparatus equipped with an Al-40 mass% Ti alloy target. Subsequently, the target was replaced with a titanium nitride target, and a compound thin film of titanium and nitrogen was formed to a film thickness of 100 nm. The sputtering conditions were the same as in Example 1 for both the metal thin film and the compound thin film.

Then, in the same manner as in Example 1, an epoxy resin-based resin coating film was formed, a transparent resin coating film was formed and dried.

The metal material produced by the surface treatment as described above was free from thermal deformation, cracks and wrinkles, and had a deep golden metallic luster. Further, this surface-treated material was subjected to the same various performance tests as in Example 1. As a result, all passed.

Example 3 The same procedure as in Example 1 was repeated until a resin coating film of polyester / melamine paint was formed and dried.

Then, a metal thin film of a nickel-based alloy was formed to a thickness of 30 nm with a DC magnetron sputtering device equipped with a nickel-based alloy (Hastelloy G) target. Subsequently, the target was replaced with a titanium nitride target, and a compound thin film of titanium and nitrogen was formed to a thickness of 80 nm. The sputtering conditions were the same as in Example 1 for both the metal thin film and the compound thin film.

Then, in the same manner as in Example 1, an epoxy resin type resin coating film was formed, a transparent resin coating film was formed and dried.

The metal material produced by the surface treatment as described above had no deep deformation, cracks, and wrinkles, and had a deep golden metallic luster. Further, this surface-treated material was subjected to the same various performance tests as in Example 1. As a result, all passed.

[Example 4] Aluminum alloy casting AC4
A C-made automobile wheel (nominal diameter 16 inches) was used as a substrate.

Chromic acid chromate conversion treatment, and then A
The same procedure as in Example 1 was performed until the metal thin film of 1-Ti alloy was formed to have a film thickness of 70 nm. Subsequently, the target was replaced with a titanium nitride target, and a compound thin film of titanium and nitrogen was formed under the same sputtering conditions as in Example 1 to a film thickness of 50 nm.

Next, in the same manner as in Example 1, an epoxy resin type resin coating film was formed, a transparent resin coating film was formed and dried.

The surface-treated wheel thus produced had no metallic deformation, cracks, and wrinkles, and had a golden metallic luster. Further, this wheel was subjected to various performance tests similar to those in Example 1. As a result, all passed.

Example 5 An ABS resin center cap (diameter: 150 mm) was used as a substrate.

A resin coating film of polyester urethane paint was formed on this substrate with an air spray gun to a film thickness of 25 μm and dried at 80 ° C. for 1 hour.

Next, in the same manner as in Example 1, Al--Ti
A metal thin film of an alloy and a compound thin film of titanium and nitrogen were formed (film thickness: 70 nm (metal thin film), 40 nm (compound thin film)).

On this, a transparent resin coating film of acrylic urethane paint was formed with an air spray gun to a film thickness of 20 μm.
It was dried at 70 ° C. for 1 hour.

The resin material thus prepared by surface treatment had no metallic deformation, cracks and wrinkles and had a golden metallic luster. Further, this resin material was subjected to various performance tests similar to those in Example 1. As a result, all passed.

[Example 6] A golden glitter material was formed in the same manner as in Example 1 except that a Ni-Cr 20% alloy target was used, but the performance test as shown in Table 1 was satisfied.

Comparative Example 1 A surface-treated metal material was produced in the same manner as in Example 1 except that the metal thin film was not formed. The appearance of this metallic material was light gray.

[Comparative Example 2] A surface-treated metal material was produced in the same manner as in Example 1 except that the metal thin film was formed to a thickness of 5 nm. The appearance of this metallic material was a light blue color.

[Comparative Example 3] A surface-treated metal material was produced in the same manner as in Example 1 except that the metal thin film was formed to a thickness of 200 nm. In the appearance of this metallic material, interference color was generated due to the wrinkles of the metallic thin film.

[Comparative Example 4] A surface-treated metal material was produced in the same manner as in Example 3 except that the metal thin film was formed to a thickness of 200 nm. In the appearance of this metallic material, interference color was generated due to the wrinkles of the metallic thin film.

Comparative Example 5 A surface-treated metal material was produced in the same manner as in Example 3 except that the metal thin film was formed to a thickness of 200 nm and the compound thin film was formed to a thickness of 150 nm. In the appearance of this metallic material, cracks occur,
The color was brown.

[0054]

As is clear from the above description, according to the golden luster material of the present invention, it is possible to provide a suitable automobile exterior component and the like. Further, according to the method for producing a golden luster material of the present invention, it is possible to apply to a wide range of materials without requiring strict control and waste liquid treatment, and to use it for automobile exterior parts etc. using a simple vacuum method. It is possible to produce a golden bright material.

Continued front page    F-term (reference) 4F100 AA12D AB00A AB00C AB10                       AB10C AB12C AB13C AB16C                       AB31C AK01A AK01B AK01E                       AK25 AK36 AK41 AT00A                       BA05 BA07 CB00B CB00E                       EH46 EH66C EH66D EJ62                       EJ69 GB32 JN01E JN24                       YY00C YY00D                 4K029 AA02 AA11 BA01 BA03 BA07                       BA12 BA17 BA21 BA23 BA25                       BA41 BA60 BB02 BC07 BD00                       BD06 CA05 EA01 FA07 GA03                 4K044 AA06 AA16 AB02 BA02 BA06                       BA10 BA18 BB05 BB16 BC02                       BC03 BC05 BC09 CA04 CA07                       CA13 CA16 CA53 CA62

Claims (10)

[Claims] 1. A base material made of a metal material or a resin material, a resin coating film formed on the surface of the base material, a metal thin film formed by sputtering on the resin coating film, and a metal thin film of the metal thin film. A compound thin film formed by sputtering on the above,
A golden glitter material having a transparent resin coating film formed as a protective layer on the compound thin film. 2. The gold color according to claim 1, wherein the metal thin film is one selected from the group consisting of Al, Ni, Ti, Cr and an alloy containing at least one of these metals as a main component. Bright material. 3. The golden luster material according to claim 1, wherein the metal thin film has a film thickness of 10 to 150 nm. 4. The golden glitter material according to claim 1, wherein the compound thin film is a compound containing Ti and N. 5. The golden bright material according to claim 1, wherein the compound thin film has a film thickness of 5 to 100 nm. 6. A step of forming a resin coating film on the surface of a base material made of a metal material or a resin material, a step of forming a metal thin film on the resin coating film by sputtering, and a sputtering process on the metal thin film. A step of forming a compound thin film with
And a step of forming a transparent resin coating film as a protective layer on the compound thin film. 7. The gold color according to claim 6, wherein the metal thin film is one selected from the group consisting of Al, Ni, Ti, Cr and an alloy containing at least one of these metals as a main component. Method for producing bright material. 8. The method for producing a golden bright material according to claim 6, wherein the metal thin film has a film thickness of 10 to 150 nm. 9. The method for producing a golden luster material according to claim 6, wherein the compound thin film is a compound containing Ti and N. 10. The compound thin film has a film thickness of 5 to 100 nm.
10. The method for producing the golden glitter material according to claim 6 or 9.