JPH06330349A - Colored ti plated material - Google Patents

Abstract

PURPOSE:To color a Ti plated material with excellent designability by successively forming an insulating layer and a Ti plating layer on a metallic substrate and allowing the surface of the Ti plating layer to develop a color by anodic oxidation. CONSTITUTION:An insulating layer 2 and a Ti plating layer 3 are successively formed on a metallic substrate 1. The surface of the Ti plating layer 3 is anodically oxidized to form an oxidized film 4 and a color is developed. Any layer capable of inhibiting the transfer of electrons between the plating layer 3 and the substrate 1 may be used as the insulating layer 2. The pref. thickness of the Ti plating layer 3 is >=0.1mum. The metallic substrate 1 is not subjected to restriction at all. At the time of the anodic oxidation, corrosion can be inhibited.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a colored Ti excellent in designability.
The present invention relates to a plated material, and the colored Ti plated material according to the present invention can be used in a wide range of applications such as ornaments, building materials, and household electric appliances.

[0002]

2. Description of the Related Art Since Ti is light, strong and resistant to rust, it can be used not only in industrial products such as aviation equipment and electronic equipment, but also in ornaments, building materials,
It is also used for consumer products such as home appliances and sports equipment. Further, Ti can be given a higher design property by coloring the surface, and its color is extremely high in saturation and rich in color tone compared to other colored metal materials, so the range of use is further Is expanding. Examples of the Ti coloring method include an anodic oxidation method, an atmospheric oxidation method, and an immersion method in an oxidizing bath.

The anodic oxidation method is a method in which Ti is used as an anode and a constant voltage electrolysis is carried out in a nitric acid or phosphoric acid bath to form an oxide film, and the kind of color tone and colorfulness (high saturation) are obtained.
It is the most widely used method in terms of easiness of color tone control. Further, the anodic oxidation method has advantages that it is possible to electrolyze at room temperature, so that deterioration of materials and the like due to heat is small and there is no limitation on the type of substrate.

On the other hand, the atmospheric oxidation method and the immersion method in an oxidizing bath are methods of forming a Ti oxide film in an oxidizing atmosphere. However, this method is concerned about deterioration of the material due to heat and has a variety of color tones. It is inferior to the anodic oxidation method in terms of properties, color and opacity, and easy control of color tone. Further, as a method of imparting a design property by surface treatment, there is an ion plating method or the like in which a colored plating such as TiC or TiCN is deposited on a substrate, but the color is limited to gold or bronze, and it can be obtained by an anodizing method I can't get different kinds of colors.

Next, a general anodic oxidation method will be described. FIG. 2 is a diagram showing a Ti coloring flow by a typical anodic oxidation method. First, the Ti plate is degreased to remove rolling oil, and then pickled. This pickling is carried out in two steps. A hydrofluoric acid aqueous solution is used for the primary pickling, and a hydrofluoric acid / hydrogen peroxide mixed solution is used for the secondary pickling.

Then, Ti is colored by anodic oxidation.
In anodic oxidation, a 1 wt% phosphoric acid aqueous solution is used as the electrolyte,
Constant voltage electrolysis was performed using the Al plate as the cathode and the Ti plate as the anode.
Thereby, an oxide film is grown on the Ti surface. At this time, the film thickness of the oxide film increases as the electrolytic voltage increases.
That is, the film thickness can be controlled by the voltage.

The coloration of Ti occurs due to the interference effect on the surface of the oxide film, which corresponds to the thickness of the oxide film, such as golden, brown, blue, yellow, purple, green, yellow-green, and pink.
It produces a wide variety of colors. As described above, the color tone of Ti is determined by the thickness of the oxide film, that is, the anodic oxidation voltage, so that the color tone can be easily controlled.

By the way, since Ti is an expensive material,
In recent years, by using an inexpensive material as a base material and subjecting its surface to Ti plating and coloring treatment, it is possible to make use of the corrosion resistance, abrasion resistance, designability, etc. of colored Ti while reducing the product price of Ti plated materials. Manufacturing is desired.

As a general method of Ti plating, a vacuum deposition method, an ion plating method, a sputtering method,
A so-called vapor deposition method such as a CVD method, in other words, a dry coating method is used. Alternatively, it can be obtained by electrolysis in a Ti molten bath at room temperature or high temperature. However, in this Ti molten bath, if it is not treated in an inert gas, it will be oxidized. Need to be replaced. Therefore, there is a problem that processing of a large area cannot be performed, or a problem that productivity is poor due to a slow processing speed, and it is not often adopted. Incidentally, Ti cannot be deposited on the object to be treated by electroplating from a normal aqueous solution.

[0010]

By the way, in the plating layer obtained by the vapor deposition method, there is inevitably a pinhole which extends to the substrate. When the anodizing method is applied to the plated layer, the substrate is corroded in the pinhole portion during constant voltage electrolysis, and a good appearance cannot be obtained. Incidentally, it is impossible to completely eliminate the pinholes in this plating layer by the vapor deposition method.

The present invention has been made in view of the above circumstances, and is inexpensive Ti having corrosion resistance and wear resistance.
The purpose is to obtain a colored Ti plated material having various color tones by subjecting the plated material to anodization without corrosion.

[0012]

The colored Ti plating material according to the present invention is one in which an insulator is arranged between a metal base and a Ti plating layer, and this is colored by an anodic oxidation method.

[0013]

The operation of the present invention will be described in detail below. For example, if Ti is vapor-deposited on a cold-rolled steel sheet and anodized, Ti
Since there are pinholes in the plating layer, the substrate undergoes anodic corrosion from here, which promotes the corrosion of the base steel sheet. Therefore, the inventors of the present application found that a film (insulator) that suppresses the movement of electrons was provided between the Ti plating layer and the metal substrate, and that it had a remarkable effect on the suppression of anodic corrosion, leading to the present invention. It was

FIG. 1 is an example of a sectional view showing a colored Ti plating material according to the present invention, in which an insulating layer 2 is arranged on a metal substrate 1,
A Ti plating layer 3 is formed thereon, and anodic oxidation is performed to form an oxide film 4 for color development. The insulating layer 2 may be anything as long as it can suppress the movement of electrons between the plating layer 3 and the metal substrate 1, and may be an organic insulating layer or an inorganic insulating layer. Further, an organic coating film, which is one of the organic insulating layers, may contain various pigments.

As a method of disposing the organic insulating layer, there are a method of forming a coating film by coating on a substrate, a method of laminating a resin film, and the like. As the inorganic insulating layer, a ceramic layer or the like is preferable, and as a method of disposing the inorganic insulating layer, for example, there is a method of forming water glass to form a SiO ₂ layer. The thickness of the insulating layer 2 is T
The thickness is preferably 0.2 μm or more in order to prevent the base material from being exposed through the pinholes in the i-plated layer 3.

The thickness of the Ti plating layer 3 is preferably 0.1 μm or more, more preferably 0.1 μm or more so that the surface of the substrate is sufficiently covered and the coating is not damaged by pickling and anodic oxidation. Is 0.5 μm or more. The upper limit is
In order to prevent the deterioration of the plating adhesion caused by the increase in stress, the thickness is preferably 10 μm or less, and is unnecessarily thick
Providing layer 3 only worsens economics.

As a method for forming the Ti plating layer 3, a dry coating method using a high energy electron beam is desirable from the viewpoint of productivity. In this method, a Ti raw material is placed in a crucible, the surface is heated by an electron beam to be evaporated and vapor-deposited on a substrate. By controlling the output of this electron beam, the vapor deposition rate and vapor deposition thickness of Ti Can be changed.

The material of the metal substrate 1 is not particularly limited, and examples thereof include mild steel, stainless steel, Al, Al alloys, Cu, Cu alloys, and the like, and Zn, Z on the surface thereof.
It may be plated with n-Ni or the like. Further, the shape of the metal substrate 1 is not limited to a plate, a rod, a mold material, or the like.

When Ti is colored by the anodic oxidation method, the Ti plating layer 3 and the metal substrate 1 are electrically insulated from each other, so that the Ti plating layer 3 is preferably energized. Further, the surface of the colored layer of the colored Ti-plated product of the present invention may be subjected to clear coating for the purpose of preventing scratches.

[0020]

EXAMPLES Examples of the present invention will be shown below, but the following examples are not intended to limit the present invention, and all modifications within the scope of the spirit of the invention are included in the technical scope of the present invention. .

A commercially available steel plate was used as the metal substrate 1. The steel sheet is an Al-killed steel sheet having a thickness of 0.5 mm and electro-Zn plated at a basis weight of 20 g / m ² . A coating for high processing was double-coated on this surface as an insulating layer 2 under the following conditions.

Undercoat-Polyester paint ("4130NU Primer" manufactured by NOF Corporation) -Dry film thickness ... 5μm-Baking conditions ... 488K x 40s Topcoat-Polyester paint ("4130 White" manufactured by NOF Corporation)・ Dry film thickness… 17μm ・ Baking conditions… 503K × 60s

Next, the steel sheet having the above-mentioned coating is applied to a width of 150.
mm was cut into a size of 150 mm in length, and this was used as a plating substrate, and Ti was plated by a vacuum deposition method. In this vacuum vapor deposition method, a batch type vacuum vapor deposition apparatus is used, and the temperature is set to 37 in advance by infrared heating in a vacuum having a pressure of about 5 × 10 ⁻³ Pa.
The temperature of the plated substrate was raised to 3K, and the Ti raw material placed in the crucible was irradiated with an electron beam to be vaporized and vapor-deposited on the plated substrate. Plating film thickness is 0.5μ
m: With a constant value, a film thickness sensor using a crystal oscillator was provided in the adjacent portion of the plating substrate for monitoring, and the plating time was controlled.

On the other hand, as a comparative example, an Al killed steel sheet and a SUS304 plated steel sheet in which Ti was directly vapor deposited were tested. When producing a plated steel sheet, the plate temperature before plating was set to a high temperature of 573K in order to secure the plating adhesion, and the plating was performed in the same manner as above.

Next, each of the test materials of the above Examples and Comparative Examples was colored. As the coloring method, first, the end face and the back face of each of the above-mentioned test materials are insulated by sealing with Teflon tape, and then 0.6 vol% HF + 10 vo at room temperature.
It was pickled in 1% H ₂ O ₂ for 3 minutes. Then, it was washed with ion-exchanged water and dried. After that, 1 wt% H at 20 ° C ± 2 ° C
_{In a 3} PO ₄ bath, constant voltage electrolysis was performed at 0.5 A / dm ² or less using an aluminum plate as a cathode and a test material as an anode. The voltages were adjusted to the voltages shown in Table 1 below so as to obtain a predetermined color.

The number of spot rust was visually determined on the obtained test material, and the appearance color was visually observed. The evaluation results are shown in Table 1. In the table, ◯: The number of visually spotted rusts is less than 1 / dm ² Δ: The number of visually spotted rusts is 1 / dm ² or more and less than 50 / dm ² ×: Of visually spotted rust The number is 50 / dm ² or more.

[0027]

[Table 1]

As is clear from Table 1, in the examples (Nos. 1, 2, 3) satisfying the specified conditions of the present invention, all the test materials had excellent appearance and design. On the other hand, an Al killed steel sheet (No. 4, 5, 6, 6) which is a comparative example.
In 7), the number of point rusts was large, and the rust covered the entire surface. S
US304 (No. 8, 9, 10, 11) also had many point rusts. Normally, the same color should be obtained at the same voltage, but due to the generation of spot-like rust, the color was different even at the same voltage, resulting in a brownish color. Further, in order to obtain a rainbow color, it is necessary to make the oxide film thicker than brown or yellow, but it is necessary to increase the electrolysis voltage. Became to cover the entire sample, and the designability was greatly deteriorated.

[0029]

As described above, according to the present invention, since an insulating layer such as a coating or a resin film is provided between the Ti plating layer and the metal substrate, corrosion at the time of anodic oxidation can be suppressed, and inexpensive Ti can be obtained. There is an effect that the plated material can be colored with excellent design.

[Brief description of drawings]

FIG. 1 is a sectional view showing an example of a colored Ti plated material according to the present invention.

FIG. 2 is a diagram showing a Ti coloring flow by a typical anodizing method.

[Explanation of symbols]

 1 Metal Substrate 2 Insulating Layer 3 Ti Plating Layer 4 Oxide Film

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Atsushi Kihara 2222 Ikeda, Ikeda, Igami, Onoue-cho, Kakogawa-shi, Hyogo Pref., Kakogawa Research Area, Kobe Steel Co., Ltd. (72) Kuniyasu Araga Oue-cho, Kakogawa-shi, Hyogo Ikeda character Ikeda development 2222 Address 1 Kakogawa Research Area, Kobe Steel, Ltd.

Claims (1)

[Claims] 1. A colored Ti plating characterized in that an insulating layer is arranged on a metal substrate, and a Ti plating layer is further formed on the insulating layer, and the outermost surface of the Ti plating layer is colored by an anodic oxidation method. Material.