JPS6114942B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to decorative multilayer coatings, and in particular to decorative multilayer coatings that combine various necessary properties. Proposals have already been made for decorative articles such as watch cases in which a gold-colored coating of TiN or the like is applied on a substrate of cemented carbide, ceramic, cermet, or the like by a vapor phase chemical vapor method or the like. However, various difficulties were encountered in implementing this. In other words, the main characteristics required of a decorative coating layer are: (1) It must have a color with high decorative value. (2) It must be thick enough to smooth out minute scratches (unevenness) on the surface of the substrate. (3) It has a certain degree of hardness. (4) High bonding strength with the substrate. (5) The outermost layer of the coating must be dense and its constituent particles must be fine. etc., and it is necessary to have both of these. However, in practice, it has often been difficult to impart these properties to a single layer. The present invention has been made with attention to this point.The base is made of ceramic or cermet, and the lower layer is one or more layers of metal and ceramic that have a high bonding strength with the base, and has a color with high decorative value. , a decorative multilayer coating characterized by having two or more laminated coating layers, the outermost layer of which is ceramic having high hardness, density, and fine constituent particles. The decorative multilayer coating of the present invention satisfies the requirements for a decorative coating by laminating two or more coating layers each having different characteristics, that is, two layers with different purposes. It has the above laminated coating layers. As a preferred embodiment of the present invention, a silver-colored material having a high bonding strength with the substrate is added to the Al ₂ O ₃ ceramic substrate.
There is a coating with a TiC coating as the bottom layer and a golden TiN coating as the outermost layer. In another preferred embodiment of the present invention, a TiC-based cermet substrate is laminated with a titanium nitride coating having a lower layer and a titanium nitride coating having a good color tone, which has a high bonding strength with the substrate, and a titanium nitride coating having a good color tone as an outermost layer. There is a covering. Such differences in the properties of titanium nitride are caused by the atomic ratio of nitrogen and titanium in titanium nitride, the amount of impurities, and the like. It is even more effective if there is an intermediate layer between the lower layer and the outermost layer in which such components change continuously through diffusion. Example 1 The surface of a watch case material made of cermet consisting of 10% Mo ₂ C, 15% Ni, 0.5% Co, and the balance TiC by weight was mirror-finished. This was coated with Ti metal (silver white) to a thickness of 0.2 μm using the ion plating method (500℃).
Next, Ti ₂ N (silver white) was coated to a thickness of 0.1 μm, and the outermost layer was coated with TiN having a deep golden color to a thickness of 1 μm.
Thickly coated. Let this be A. Next, Ti ₂ N was applied directly to the mirror-finished surface of the same watch case material as above without coating it with Ti metal.
0.3μ by ion plating method (500℃)
m thickness, then 1μm of TiN as the outermost layer.
Thickly coated. Let this be B. For comparison, TiN was coated on the mirror-finished surface of the same watch case material using the ion plating method (500°C) to a thickness of 1.3 μm, the same as the total coating thickness in A and B. . Let this be C. Regarding the above, the results of hardness (Vickers hardness under a load of 50 g), scratch test (indicated by critical load value) to evaluate the peeling resistance of the coating, and color tone are shown in Table 1. .

[Table] The results of the scratch test showed that A and B were superior to C, demonstrating the effects of the present invention. Example 2 The surface of a tie bottle material made of alumina-based ceramics consisting of 30% TiC, 1% Ni, and the balance Al ₂ O ₃ by weight was made so that the mirror-wrapped portion and the satin-finished portion formed a stripe shape. The surface was finished. By using ion plating method, _{TiC 0.8}
(silver white) to a thickness of 0.2 μm _, and then Ti( _{N 0.9} O _0.1 ) (pale golden yellow) was coated to a thickness of 1.5 μm as the outermost layer. Let this be D. For comparison, the same tie pin material was made with the _same surface finish, and Ti (N _0.9 O _0.1 ) was coated with the same total coating thickness as D using the ion plating method _.
It was coated to a thickness of 1.7 μm. Let this be E. The above tests were conducted in the same manner as in Example 1, and the results are shown in Table 2.

[Table] The results of the scratch test showed that D was superior to E, demonstrating the effects of the present invention. Example 3 On the mirror-finished surface of a bracelet component material made of zirconia ceramics consisting of 20% TiC, 5% NbC, and the balance ZrO ₂ by weight,
ZrO ₂ (semi-transparent) was coated to a thickness of 0.2 μm using the ion plating method, and then Zr(N,O)
(Pale white yellow) was coated to a thickness of 0.2 μm, and as the outermost layer, a deep golden yellow ZrN was coated to a thickness of 1.1 μm. Let this be F. Next, Zr(N,O) was applied to the mirror-finished surface of the same material as above using the ion plating method.
ZrN was coated to a thickness of 1.4 μm, and then ZrN was coated as the outermost layer.
was coated to a thickness of 1.1 μm. Let this be G. In addition, 0.4μ of ZrO ₂ was applied to the mirror-finished surface of the same material as above using the ion plating method.
ZrN is coated to a thickness of m, and then 1.1μ of ZrN is coated as the outermost layer.
It was coated to a thickness of m. Let this be H. For comparison, ZrN was coated on the mirror-finished surface of the same material by ion plating to a thickness of 1.5 μm, the same as the total coating thickness for F, G, and H. Let this be I. The above tests were conducted in the same manner as in Example 1, and the results are shown in Table 3.

[Table] The results of the scratch test showed that F, G and H were superior to I, demonstrating the effects of the present invention. The present invention is not limited to the embodiments and examples described above. In addition, in the method for manufacturing the decorative multilayer coating of the present invention, if all layers are coated by vapor phase chemical vapor deposition and ion plating, coating can be carried out continuously while the substrate is heated. Although preferred, it is not limited thereto. The decorative multilayer coating of the present invention can be widely applied to watch cases, basket heads, hands, and other watch exterior parts, accessories, lighters, and the like.

Claims (1)

[Claims] 1. The substrate is ceramic or cermet,
The lower layer is one or more layers of metal and ceramic that have high bonding strength with the base, and the outermost layer is ceramic that has a color with high decorative value, is highly hard, dense, and has fine constituent particles. 1. A decorative multilayer coating, characterized by having more than one laminated coating layer. 2. The decorative multilayer coating according to claim 1, wherein the substrate is Al ₂ O ₃ ceramic and has a two-layer coating layer of TiC as the lower layer and TiN as the outermost layer. 3. The decorative multilayer coating according to claim 1, in which the base is a TiC-based cermet and has a two-layer coating layer, with a lower layer made of titanium nitride, which has a high bonding strength with the substrate, and an outermost layer made of titanium nitride, which has a good color tone. .