JPH0310063A - Multicolored ornament and its production - Google Patents

Abstract

PURPOSE:To easily produce a multicolored ornament having high durability at a low cost by forming a film of metal and/or a film of metallic compound on a base material in the same batch into multiple layered state and dissimilar colors and then applying masking and selective etching to the above film. CONSTITUTION:At least one kind among the films composed of metals and/or metallic compounds is formed on a base material of stainless steel, titanium, etc., into multilayered state and dissimilar colors in the same batch by a PVD method or a CVD method. As the above film, TiN, TiC, and TiCN are used, and further, as the intermediate layer of the above, ZrN, HfN, metallic Ti, Zr, Hf, etc., are used. Subsequently, masking of dissimilar pattern is applied onto the above film, followed by selective etching. By carrying out the above stages at least once, a dissimilar-color phase is allowed to appear. By this method, the ornament having high durability and also having colorful patterns of >=2 kinds can be easily obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a multicolored ornament and a method for manufacturing the same.

[Conventional technology] Traditionally, decorative items such as watch cases, eyeglass frames, pendants, and pressed threads were often plated with gold, silver, platinum, etc. on the base metal, but these were monochrome. Therefore, in recent years, there has been a demand for products with even more multicolors.For multicolors, for example, a primary plating film of metal is formed by vapor deposition on the base material, and masking is applied at a predetermined position on this plating film. After applying and cleaning, a secondary plating film of a different type of metal is layered on the plating film in another batch, and then the mask is removed.

[Problem M to be solved by the invention] However, in this method, the plating process and the accompanying cleaning process have to be divided into the primary and secondary stages and repeated in separate batches, so the process is complicated and takes a lot of man-hours. There was also a problem that the yield was not good. In addition, when forming a film using the ion blating method, a heat-resistant mask is required for masking, and a mask (
If the drying of the organic mask was insufficient, gas would be generated from the mask, causing discoloration of the plating film.

[Means for Solving the Problems] The present invention aims to solve these problems, and its gist is to provide at least a film made of a metal and/or a metal compound on a base material. A multicolored decorative article is obtained by forming two layers of different colors in the same batch and performing selective etching at least once to reveal a different color. or at least one of the films made of a metal compound.
A method for producing a multicolored decorative article, characterized in that two layers are formed in different colors in the same batch, and a process of masking different patterns and selective etching is performed on the film at least once to reveal different colors. It is in.

Examples of decorative items to which the present invention is applied include watch cases and eyeglass frames made of metals such as stainless steel, titanium, and titanium alloys.

Examples include pendants and press threads. In the present invention, first, on these substrates, at least one layer of a metal or a metal compound having a different color from the substrate is deposited in the same batch by PVD or CVD, and then layered together with the substrate or the deposited film. and a unique laminate.

According to the present invention, by stacking two or more of these deposited layers, it is possible to further increase the number of colors. By selectively using agents, decorative articles with a variety of patterns can be produced.

Any metal or metal compound that forms such a different color film may be used in the present invention as long as the film is formed by PVD (ion blasting, sputtering, metal vapor deposition, or CVD) in the same batch. Examples of combinations of such materials include titanium carbide and titanium nitride, titanium carbide and zirconium nitride, and titanium carbide and hafnium nitride.

Here, between the base material and a brown or black (other than gold) film of titanium nitride, titanium carbide, titanium nitride carbide, etc.,
When zirconium nitride or hafnium nitride is provided as an intermediate layer, the upper layer has a rough surface and is susceptible to abrasion, but the intermediate layer has high hardness and excellent corrosion resistance, which ensures the strength of the decorative layer as a whole. Although the upper film is etched with a nitric acid-based remover, the middle film is not etched, which has the advantage that two-tone color processing becomes easier and a multi-colored decorative film can be easily obtained.

Note that if a metal zirconium, hafnium or titanium film is formed on the surface of the substrate before forming these zirconium nitride or hafnium nitride films on the substrate, the bond between the substrate and the metal or metal compound will be reduced. This has the effect of further improving the adhesion with the film and increasing the durability of the decorative film as a whole.

The manufacturing process of the multicolored decorative article according to the present invention will be explained in more detail with reference to the attached drawings. As shown in FIG. A thin film 2 of metal or metal compound is deposited (
b), the composition of the reaction gas is subsequently changed to produce a thin film 3 of a different color from the thin film 2, for example a black metal film or a metal compound;
(c) ion plating step in which the two layers are deposited in a layered manner; (d) masking step in which a mask 4 is provided at an appropriate position on the thin film 3; and (e) an etching agent is applied on the thin film 3.
It consists of an etching process, and finally the mask is peeled off (
f) and 1. For example, a multicolored ornament 5 of gold and black is obtained.

FIG. 2 shows another embodiment, in which (a) first a thin film 12 of metallic zirconium or hafnium is deposited on a raw metal 11 (b), and then a golden zirconium nitride or hafnium nitride film 12 is deposited thereon. A thin film 13 is deposited from each reaction gas (c). Furthermore, by changing the composition of the reaction gas, ion blating is applied onto this thin film 13 to create a film of the general formula T
A black thin film 14 of a titanium nitride compound represented by iN is deposited in layers (d), a mask 15 is provided at a predetermined location on this thin film 14 (e), and then a nitric acid-based etching agent is applied. When a part of the thin film 14 is removed (f) and finally the mask is peeled off (g), a multicolored ornament 20 of, for example, gold and black is obtained.

Hereinafter, specific aspects of the present invention will be explained with reference to Examples.
The present invention is not limited to these descriptions.

[Example Example 1] Attach a titanium eyeglass frame to a basic holder, set it in the vacuum chamber of an ion blating device,
After evacuation, argon gas was introduced to bring the internal pressure to 1X10-'Pa, and an accelerating voltage with a negative potential of 50 V was applied to the eyeglass frame to ionize the argon gas with an anode current of 40 A to perform bombardment cleaning on the surface of the eyeglass frame.

Next, ethylene gas is introduced into the vacuum chamber, and the internal pressure is set to 7XIO-1Pa using a mixed gas with argon gas as a reaction gas.
was held at Next, the titanium metal evaporation source is irradiated with an electron beam generated at an appropriate acceleration voltage, and the generated titanium vapor and ethylene gas are ionized in the plasma, forming a gray titanium carbide film with a thickness of 2p on the eyeglass frame. formed.

Next, nitrogen gas is introduced instead of ethylene gas, titanium and nitrogen gas are ionized, and a thickness of 1.5 mm is formed on the titanium carbide film. A gold-colored titanium nitride film of n was formed to obtain a frame with a two-layer structure film.

After taking out the frame from the vacuum chamber and printing a solvent-soluble organic mask layer on a part of it, the titanium nitride film was etched with a hydrofluoric acid stripper at room temperature for 30 to 60 minutes, and then in trichloroethane for 30 minutes. When the organic mask layer was peeled off by dipping, a two-tone eyeglass frame with a beautiful gray and gold contrast design was obtained.

Example 2 Using the same method as in Example 1, a stainless steel watch band was placed in a vacuum chamber, and after exhaust and necessary bombardment cleaning, a mixed gas of argon and nitrogen was ionized, and similarly ionized titanium was ionized. to a film thickness of 1.5
- A black titanium nitride film was formed. Next, the nitrogen gas was stopped, and gold was formed to a thickness of 1 Oprs to form a two-layer film structure. Thereafter, a patterned mask was formed in the same manner as in Example 1, and the gold was etched with a cyan-based release agent and the mask was removed, resulting in a beautiful gold-black two-tone watch band.

Note that the gold in the upper layer may be replaced with an alloy such as Au-Ni, Au-Pd, Au-Ni-Cu, etc., which can be etched with a cyanide stripping agent.

Example 3 Examples 1 and 2 were further developed to obtain a three-color design. That is, the titanium wristwatch side was placed in a vacuum device in the same manner as in Example 1.2, and first a gray titanium carbide film was applied to a thickness of 2p, and then a brown titanium nitride film was applied to a thickness of 1.5p.
In 5 μs, a gold film was further continuously formed to a thickness of 1.01 to form a three-layer laminated film.

Thereafter, masking and etching were repeated at predetermined positions, and finally the mask was peeled off to obtain a laminated film with a beautiful three-color pattern of gold, brown, and gray. The properties of this product were tested and the results are shown in the table below.

(Each test was repeated 30 times) Example 4 After cleaning a stainless steel watch band, it was set in an ion brating device, and after exhausting, argon gas was introduced to maintain the internal pressure of the device at 4 × 10° 1 Pa, and a negative Argon gas was ionized using an acceleration voltage of 50 V and an anode current of 30 A, and bombardment cleaning was performed on the surface of the watch band.

Next, the metallic zirconium evaporation source was irradiated with an electron beam generated at an appropriate acceleration voltage to evaporate the zirconium and form a zirconium layer on the surface of the watch band. Nitrogen gas was introduced into the vacuum chamber, and zirconium vapor and nitrogen gas were ionized in plasma under a pressure of 2.5 x 1O-1Pa to form a golden zirconium nitride layer on the above-mentioned zirconium layer. Furthermore, an electron beam is irradiated onto the metal titanium as the evaporation source, ethylene gas and nitrogen gas are introduced into the tank at the same time, and the titanium vapor and ethylene gas are ionized in the plasma to form a black titanium nitride carbide film. Formed on top of a zirconium layer.

A solvent-soluble organic mask layer was printed on the watch band thus produced. Add this to nitric acid at room temperature at 60~9
The black film was etched by immersion for 0 minutes. The organic mask layer was then removed by immersion in a chlorinated solvent such as trichloroethane for 30 minutes, resulting in a two-tone watch band consisting of a gold zirconium nitride layer and a black titanium nitride layer.

About this watch band, CASS test (CASS: J
As a result of conducting the test (ISH-8617), I passed with 0,730 pieces. In addition, in the case of a black watch band without a zirconium nitride layer, rust occurred with 2 saws and 0 pieces.

Example 5 After cleaning, a titanium alloy eyeglass frame is set in an ion blating device. In the same manner as in Example 4, metal hafnium was used instead of metal zirconium as an evaporation source, and a film was formed in the order of hafnium and hafnium nitride. Furthermore, a brownish titanium nitride film was formed on this using nitrogen gas and titanium vapor.

A solvent-soluble organic mask layer was printed on the spectacle frames thus produced. Add this to nitric acid at room temperature for 60~
The brown film was etched by immersion for 90 minutes.

After that, the organic mask layer was removed by immersion in a chlorinated solvent such as trichloroethane for 30 minutes, resulting in a two-tone LIT! consisting of a golden hafnium nitride layer and a brown titanium nitride layer. There was a mirror frame.

In this embodiment, a titanium nitride layer is etched with nitric acid, but a zirconium nitride layer or a hafnium nitride layer is not etched. Further, the zirconium nitride layer and the hafnium nitride layer are etched using the property that they cannot be etched unless they are aqua regia or a mixed acid of hydrofluoric acid and nitric acid.

Incidentally, in each of the above Examples, examples of manufacturing multicolored ornaments by the reactive ion blating method were shown.

It goes without saying that various other methods such as arc vapor deposition, sputtering, PVD, and CVD can be used instead.

[Effects of the Invention] According to the present invention, a highly durable decorative article having two or more various patterns can be obtained very easily.

In particular, during its production, the time required for reaction, cooling, exhaust, cleaning, etc. conventionally required when forming a metal film on a base material is significantly shortened, and the number of man-hours is significantly reduced. In addition, there is no need for a heat-resistant mask during masking, and the mask can be easily peeled off, resulting in significant cost benefits.

[Brief explanation of drawings]

FIGS. 1 and 2 are explanatory diagrams sequentially showing different steps for obtaining a multicolored decorative article according to the present invention.

Claims (5)

[Claims] 1. A multicolored decorative article formed by providing at least one film made of a metal and/or a metal compound in different colors on a base material in a multilayered manner, and then performing selective etching at least once to expose different colored layers. 2. 2. The multicolored decorative article according to claim 1, wherein the at least one film made of metal and/or metal compound is made of titanium nitride, titanium carbide, or titanium nitride carbide. 3. 3. The multicolored decorative article according to claim 2, wherein a film of zirconium nitride or hafnium nitride is provided as an intermediate layer between the base material and the film of titanium nitride, titanium carbide, or titanium nitride carbide. 4. 4. The multicolored decorative article according to claim 3, wherein a film made of a metal selected from titanium, zirconium, and hafnium is provided between the base material and the film made of zirconium nitride or hafnium nitride. 5. At least one film made of a metal and/or a metal compound is formed in the same batch on a base material by a PVD method or a CVD method in a layered manner and in a different color, and a process of masking different patterns and selective etching is performed on the film. A method for producing a multicolored decorative article, which is characterized in that it is applied at least once to reveal different hues.