JPH0570928A - Colored silver product, colored silver film and method for coloring silver surface - Google Patents

Abstract

PURPOSE:To provide a colored silver product easily changeable in color and capable of changing color in a longitudinal direction. CONSTITUTION:A surface of silver or a silver alloy 5 is coated with indium oxide 6 in a plasma incorporating oxygen. The activated indium oxide 6 is diffused into the inside of the silver to form a diffusing layer 5A and an interference color is produced. The interference color is easily changed by changing the thickness of the diffusion layer 5A. By changing a sticking amount of indium oxide in the longitudinal direction, color is changed in the longitudinal direction.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored silver product which can be suitably used as a packaging material, a wallpaper, a decorative yarn for textiles and decorative products, and is capable of producing various colors, and a method for producing the same.

[0002]

2. Description of the Related Art For example, a colored silver vapor deposition film has been conventionally used as a material for a decorative film, a decorative gold thread, or a silver thread.

The production of colored silver films of this type is
First, after vacuum-depositing silver on a substrate such as a plastic film (first step), a transparent resin coat layer for preventing silver corrosion is formed on it (second step), and further on this film. This is performed by applying a colored resin layer to (3rd step). The transparent resin coat layer may be formed after forming the colored resin layer on the silver vapor deposition film.

[0004]

However, in the above-described manufacturing method, there is a problem that the color cannot be easily changed because the color development is uniquely determined by the colored resin layer.

Further, in the above manufacturing method, it is difficult to change the color in the longitudinal direction of the film.

On the other hand, there has been a technique in which a metal oxide film is formed on a silver vapor-deposited film and colored by an interference color. In this case, however, the thickness of the metal oxide film is set to a wavelength of n. Since it needs to be set to / 2 times, it is necessary to form a thick film, resulting in an increase in cost and also a problem that color development is limited.

The present invention has been made in view of the above-mentioned circumstances, and a colored silver product, a colored silver film, and a colored silver film capable of arbitrary coloring by forming a thin single type coloring layer without incurring manufacturing cost. It is intended to provide a manufacturing method.

[0008]

In the colored silver product according to claim 1, an indium oxide layer is formed on the surface of silver or a silver alloy, and a part of the indium oxide layer is diffused into the silver or silver alloy. It was taken as a solution.

The colored silver film according to claim 2 has a plastic film and a layer of silver or a silver alloy provided on the film, and an indium oxide layer is provided on the surface of the silver or silver alloy layer. Was formed and a part thereof was diffused into the silver or silver alloy as a means for solving the problem.

In the method for coloring a silver surface according to a third aspect of the present invention, the means for solving the problem is to coat the surface of silver or a silver alloy with indium oxide in a plasma containing oxygen.

[0011]

When the surface of silver or its alloy is coated with indium oxide in a plasma containing oxygen, the activated indium oxide diffuses inside silver to form a diffusion layer, which causes an interference color. This interference color is easily changed by changing the thickness of the diffusion layer.

[0012]

The colored silver product, the colored silver film and the method for coloring the silver surface of the present invention will be described below with reference to the drawings.

(Example 1) FIG. 1 shows an example of the colored silver product of the present invention. In this figure, reference numeral 1
Is a silver substrate. An indium oxide layer 2 is provided on the base 1, and an indium oxide diffusion layer 1A is formed on the indium oxide layer 2 side of the base 1.

Other than the above, the base body 1 may be engraved bodies of various shapes, silver cards, coins, films and the like.

The substrate 1 is not limited to one formed entirely of silver or a silver alloy, but only the surface thereof.
It may be formed of silver or a silver alloy.

The thickness T ₁ of the indium oxide layer 2 is not particularly limited, but is preferably 10 to 500 Å. If it is less than 10Å, it is difficult to form a diffusion layer, and if it exceeds 500Å, manufacturing becomes difficult.

Thickness T of the indium oxide diffusion layer 1A
₂ is preferably 30 to 1000Å. If it is less than 30Å, it is difficult to develop color, and if it exceeds 1000Å, it becomes difficult to control the thickness of the diffusion layer.

In order to manufacture this colored silver product, the surface of the substrate 1 is coated with indium oxide in a plasma containing oxygen. For coating indium oxide, a method of sputtering an indium target in a plasma containing oxygen is suitable. When the indium oxide is coated by the above method, a part of the activated indium oxide of the coated indium oxide layer 2 diffuses inside the silver of the substrate 1 to form the diffusion layer 1A. At this time, the thicknesses of the indium oxide layer 2 and the indium oxide diffusion layer 1A can be controlled by changing the sputtering time and the input power.

The colored silver product thus formed is
Since the indium oxide diffusion layer 1A is formed on the side of the indium oxide layer 2 of the substrate 1, an interference color is easily generated even if the amount of indium oxide vapor deposited is small, and coloring is performed as compared with the conventional coloring method. The cost for can be reduced. Further, the interference color can be changed to various color tones simply by changing the conditions at the time of coating to change the thicknesses of the indium oxide layer 2 and the indium oxide diffusion layer 1A.

During the vapor deposition, the vapor deposition surface of the substrate 1 may be partially masked to partially change the vapor deposition amount of indium oxide. In that case, it is possible to draw arbitrary patterns in different tones, and the decorative effect is great.

Example 2 FIG. 2 shows an example of the colored silver film of the present invention. In this figure, reference numeral 4 is a plastic film. As the plastic film 4, polyester, polyimide,
A film such as polypropylene can be used.

A silver layer 5 made of silver or a silver alloy is formed on the film 4. The thickness of the silver layer 5 is not limited, but generally 200 to 1000Å is preferable. If it is less than 200Å, it is difficult to obtain a coloring effect and 1000
If it exceeds Å, the economy is poor. An indium oxide layer 6 is provided on the silver layer 5, and an indium oxide diffusion layer 5A is formed on the indium oxide layer 6 side of the silver layer 5.

The thickness of the indium oxide layer 6 and the thickness of the indium oxide diffusion layer 5A may be the same as those in the above embodiment.

On the indium oxide layer 6, an acrylic type,
A transparent resin layer 7 made of polyester or epoxy is provided. The resin layer 7 is for preventing damage to the indium oxide layer 6, and the thickness is preferably 1 to 10 μm. If it is less than 1 μm, it does not play the role of a protective layer and it is 10 μm.
If it exceeds, manufacturing becomes difficult.

This colored silver film can be manufactured as follows. First, the film 4 is run in a vacuum chamber partitioned by a slit into a vapor deposition chamber and a sputtering chamber, and the film 4 is moved in a vacuum atmosphere in the vapor deposition chamber.
Vacuum-deposit silver while winding. Here, the degree of vacuum in the vapor deposition chamber is set to about 5 × 10 ⁻⁵ torr, and the vapor deposition distance between the silver evaporation source and the film 4 in the vapor deposition chamber is set to, for example, about 40 cm.

After depositing a silver layer 5 having a predetermined thickness on the film 4, the film 4 is introduced into a sputtering chamber, and an indium target is sputtered by a magnetron sputtering method in an atmosphere in which argon gas and oxygen are introduced to run the film. The film 4 is coated with an indium oxide layer 6. At this time, it is desirable that the flow rate ratio of the argon gas and oxygen introduced into the sputtering chamber be about 1: 1. The sputter distance between the target and the film 4 is, for example, about 9 cm. When the indium oxide is coated by the above method, a part of the activated indium oxide of the coated indium oxide layer 6 diffuses inside the silver layer 5 to form the diffusion layer 5A. Further, the thickness of the indium oxide layer 6 and the diffusion layer 5A in the longitudinal direction of the film 4 can be continuously changed by changing the input power at the time of sputtering.

After forming the indium oxide layer 6, a transparent resin layer 7 of acrylic type, polyester type, epoxy type or the like is further formed on this surface in the same manner as in the conventional method, whereby a colored silver film can be obtained.

In the colored silver film thus produced, the film color can be easily changed by changing the amount of indium oxide attached. Further, in this colored silver film, since the indium oxide layer 6 is coated in the plasma containing oxygen, indium oxide easily diffuses in the surface layer of silver to form the diffusion layer 5A, thereby forming the colored film. Even if the thickness is thin, a sufficient coloring effect can be obtained. Further, since the surface of this colored silver film is coated with a transparent resin layer 7 such as an acrylic resin, a polyester resin or an epoxy resin, it has excellent corrosion resistance and is less likely to be scratched.

Further, in the above method for producing a colored silver film, the vapor deposition of silver and the coating of indium oxide in the plasma containing oxygen are performed in the same vapor deposition machine.
The coloring process after vapor deposition can be simplified.

Next, the effects of the present invention will be demonstrated with reference to experimental examples.

[Experimental Example 1] A # 12 (about 12 μm thick) polyester film 4 was run in a vacuum chamber partitioned by a slit into a vapor deposition chamber and a sputtering chamber, and the film 4 was first placed in a vacuum atmosphere in the vapor deposition chamber. While winding, silver was vapor-deposited under the following conditions to form a silver layer 5. Silver thickness 690Å Degree of vacuum 5 × 10 ^-5 torr Deposition distance 40 cm

Next, the film 4 is introduced into a sputtering chamber, and an indium target is sputtered under the following conditions by a magnetron sputtering method in an atmosphere in which argon gas and oxygen are introduced to coat the running film 4 with an indium oxide layer 6. did. At this time, the amount of indium oxide deposited in the longitudinal direction of the film 4 was continuously changed by changing the applied power. Introduced gas Ar: O ₂ = 1: 1 (flow rate ratio) Pressure 3 × 10 ⁻³ torr Sputtering distance 9 cm Input power 0.4 to 3.3 W / cm ²

Further, a colored silver film was obtained by coating the surface of the film 4 with an epoxy resin layer 7.

[0033]

[Experimental Example 2] Polyethylene terephthalate film #
Six sheets of 125 (thickness: about 125 μm) were prepared, and silver was vapor-deposited on one surface of these films under the following conditions. Silver thickness 690Å Degree of vacuum 5 × 10 ^-5 torr Deposition distance 40 cm

Next, sputtering was performed on these silver vapor-deposited films by using the magnetron sputtering method under the following conditions. At this time, 3 films are sequentially converted to 6 films.
0, 50, 100, 150, 200, 250 Å indium oxide was deposited respectively. Introduced gas Ar: O ₂ = 1: 1 (flow rate ratio) Pressure 3 × 10 ⁻³ torr Sputtering distance 9 cm Input power 0.4 W / cm ²

In the film thus obtained, the relationship between the wavelength and the reflectance according to the amount of indium oxide deposited is shown in FIGS. 3 to 8. Table 1 shows the relationship between the amount of deposited indium oxide and the color of the deposited film.

[Table 1]

From the above results, it was found that a colored silver film having a different film color can be easily manufactured by changing the amount of indium oxide deposited.

[0037]

As described above, in the colored silver product according to claim 1 and the colored silver film according to claim 2, an indium oxide layer is formed on the surface of silver or a silver alloy, and a part of the indium oxide layer is formed into the silver. Alternatively, since it is diffused in the silver alloy, an interference color is easily generated even if the formed indium oxide layer is thin, and the interference color has various color tones depending on the thicknesses of the indium oxide layer and the diffusion layer. Can be adjusted. Therefore, the manufacturing cost is lower than that of the conventional product, and the degree of freedom in color development is greatly increased.

In the method for coloring a silver surface according to a third aspect of the present invention, since the surface of silver or its alloy is coated with indium oxide in plasma containing oxygen, the deposition amount and diffusion amount of indium oxide are controlled. By doing so, a wide range of color tones can be easily obtained.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing an embodiment of a silver colored product of the present invention.

FIG. 2 is a cross-sectional view showing an example of the silver colored film of the present invention.

FIG. 3 is a graph showing the relationship between the wavelength and the reflectance when 30Å indium oxide is attached in terms of film thickness.

FIG. 4 is a graph showing a relationship between a wavelength and a reflectance when 50Å indium oxide is attached in terms of film thickness.

FIG. 5 is a graph showing a relationship between a wavelength and a reflectance when 100Å indium oxide is attached in terms of film thickness.

FIG. 6 is a graph showing the relationship between the wavelength and the reflectance when 150Å indium oxide is attached in terms of film thickness.

FIG. 7 is a graph showing the relationship between the wavelength and the reflectance when 200Å indium oxide is attached in terms of film thickness.

FIG. 8 is a graph showing the relationship between the wavelength and the reflectance when 250Å indium oxide is attached in terms of film thickness.

[Explanation of symbols]

 1 Substrate 1A Diffusion layer 2 Indium oxide layer 4 Plastic film 5 Silver layer 5A Diffusion layer 6 Indium oxide layer 7 Acrylic resin layer

Claims (3)

[Claims] 1. A colored silver product, wherein an indium oxide layer is formed on a surface of silver or a silver alloy, and a part of the indium oxide layer is diffused in the silver or the silver alloy. 2. A plastic film and a silver or silver alloy layer provided on the film, wherein an indium oxide layer is formed on the surface of the silver or silver alloy layer, and a part of the indium oxide layer is formed. A colored silver film which is diffused in the silver or silver alloy. 3. A method for coloring a silver surface, which comprises coating the surface of silver or a silver alloy with indium oxide in a plasma containing oxygen.