Composite film

Description: TECHNICAL FIELD [Detailed description of the invention]

(Industrial application field) The present invention relates to a composite mixed multilayer film. More specifically, the present invention relates to a multilayer film in which a composite mixed film of gold or an alloy thereof and an organic substance, which is excellent in decorativeness, functionality, etc., is arranged. (Conventional technology) It is possible to form a vapor-deposited thin film of metal, inorganic material, organic polymer, etc. on the surface of a substrate such as metal, glass, ceramic, plastic, etc. and use it as an insulating film, reflective film, optical thin film, display element, electronic device, etc. It is widely used. Various reaction processes for that purpose, such as vacuum deposition, sputtering, ion plating, CVD, MOCVD, and MBE, are also known. (Problems to be solved by the invention) However, in such a conventional thin film forming method and a thin film, there are still problems to be improved in order to produce a thin film having desired characteristics and functionality, and there are various uses of the thin film. The current situation is that consideration from the standpoint is needed. As one of such problems, a golden composite film that has excellent color tone, good functionality such as corrosion resistance, adhesion, and abrasion resistance, and can be used for exterior parts useful for watches and accessories has been used so far. It has not been realized, and in order to form this by a conventional method, it is necessary to prepare a layer made of expensive gold or an alloy thereof, and to form a composite film having excellent functionality and inexpensive. There was a problem that it was difficult. It is also known that a layer made of gold or an alloy thereof is layered with a TiN layer, but in this case, the color tone is inevitably inferior, and the wear resistance and interlayer adhesion are satisfactory. There wasn't. The present invention has been made to solve such a problem, and attempts to solve the above problem by forming a composite mixed multilayer film made of gold or an alloy thereof and an organic substance. (Means to solve the problem) The composite mixed multilayer film of the present invention is formed by disposing a TiN film vapor-deposited by plasma excitation, a composite mixed film in which gold or an alloy thereof and an organic substance are simultaneously vapor-deposited by plasma excitation on a substrate. It is characterized by. As the organic substance in this case, polycarbonate, polyacrylate, polysiloxane, polyester, polyolefin, polyethylene and the like are used. Usually, in thin film formation by vapor deposition, it is difficult to increase the density by metal particles and inorganic substances, and pinholes are likely to occur in the thin film. Further, improvement of wear resistance is also a difficult issue. In addition, since surface smoothness is difficult to obtain, problems tend to occur in adhesion between layers when multiple layers are used. However, as in the present invention, by forming a film by plasma excitation and forming a composite mixed film of an organic substance and gold or an alloy thereof, the generation of pinholes is suppressed, the wear resistance is improved, and the surface is smoothed. Since the property is ensured, the interlayer adhesion can be improved. And, more importantly, the golden color tone is kept good, and the amount of expensive gold used can be reduced by the multi-layered structure with TiN. In the present invention, a transparent plasma polymer film formed by plasma excitation can be integrally arranged under the composite mixed film depending on the material of the substrate forming the composite mixed multilayer film and the thickness of each layer. As a result, the adhesion between the layers is further improved, and the color tone is not impaired. Further, various transparent inorganic thin films and organic films may be arranged on the outermost surface of the multilayer film of the present invention by plasma excitation, and the abrasion resistance and color tone of the surface can be maintained and improved. As a method of vapor deposition by plasma excitation to form a composite mixed film of gold or its alloy and an organic substance, gold or its alloy and an organic substance are evaporated, and the evaporated particles are simultaneously plasma excited to form ionized particles and neutral particles. Alternatively, a method of forming by vaporizing in a radical state, or a method of introducing an organic substance as a monomer gas and similarly vaporizing gold or its alloy at the same time by plasma excitation is adopted. From the viewpoint of color tone and adhesion strength, it is indispensable to deposit at the same time in the excited state. In this case, the evaporated particles are excited by glow discharge in the vacuum reactor and plasma ionized. As the means for plasma ionization at this time, means such as ion plating such as a hollow cathode method and a high frequency excitation method, and plasma CVD can be adopted. In the case of the ion plating method, for example, the pressure in the vacuum reactor is 10^-2~10^-5An inert gas such as argon may be introduced in a vacuum state of about Torr. The temperature of the substrate can be in the range of room temperature to about 400 ° C. The TiN film can be vapor-deposited by reactive ion plating by introducing nitrogen gas and ammonia gas. The gas pressure in this case is 10^-4It is preferably Torr or higher. As described above, according to the present invention, it is possible to realize a composite mixed multilayer film having excellent color tone, abrasion resistance, corrosion resistance and the like and good adhesion strength. Next, examples of the present invention will be shown, and the configuration and effects of the present invention will be described in more detail. Of course, the present invention is not limited to the following examples. Example 1 A composite mixed multilayer film was formed using an ion plating apparatus based on a high-frequency excitation method. Figure 1 shows an example of this. That is, a stainless steel plate is used as the substrate (1), and 5 × 10^-5Introducing Torr's argon gas to bombard the stainless steel plate, then 8x10^-4A thin film (2) of TiN was deposited and formed by reactive ion plating of nitrogen gas and evaporated Ti particles under Torr conditions. A TiN thin film (2) with a thin film of 0.2 μm was formed by a reaction for 3 minutes under the conditions of a discharge power of 300 W and a substrate temperature of 100 ° C. Then 4x10^-3Under the conditions of Torr's argon pressure, the evaporated particles of gold and polycarbonate were plasma ionized by high-frequency excitation to form a composite mixed film (3) by vapor deposition on the substrate. As a result, a composite mixed film (3) that has the same color tone as gold is obtained, the wear resistance is about twice that when a thin film of gold is deposited on the substrate, and the adhesion strength is obtained by a 90 ° bending test. No peeling was observed, and the corrosion resistance was excellent. Example 2 Similar to Example 1, after forming the titanium nitride thin film (2) as shown in Fig. 2, 4 × 10^-3Under the conditions of Torr's argon pressure, the evaporated particles of polycarbonate were plasma ionized and a plasma polymer film was deposited on the substrate to form an undercoat (4). After that, the gold-chromium alloy (2% containing chromium) is evaporated at the same time as the polycarbonate evaporates, and a composite mixed film (3) of the polycarbonate and the gold-chromium alloy is formed on the polycarbonate polymer film with a thickness of about 0.2 μm. did. This product had the same color tone as the gold-chromium alloy, had excellent adhesion, did not peel off in the 90 ° bending test, and had excellent wear resistance and corrosion resistance. Example 3 Similar to Example 1, as shown in FIG. 4, after forming the titanium nitride thin film (2), 4 × 10^-3Under the conditions of Torr's argon pressure, the evaporated particles of polycarbonate were plasma ionized and a plasma polymer film was deposited on the substrate as an undercoat (4). After that, the gold-chromium alloy (2% containing chromium) is evaporated at the same time as the polycarbonate evaporates, and the composite mixed film (3) of the polycarbonate and the gold-chromium alloy is undercoated with a polycarbonate polymer film (3) with a thickness of about 0.2 μm. 4) Formed on top. Next, the evaporation of the gold-chromium alloy was stopped, and a polycarbonate-only polymer film was deposited on the composite mixed film as a top coat (5) to a thickness of about 0.2 μm. The obtained composite mixed multilayer film had the same color tone as the gold-chromium alloy, had excellent adhesion, did not peel off in the 90 ° bending test, and had excellent wear resistance and corrosion resistance. Example 4 On the surface of the composite mixed film (3) obtained in Example 1, as shown in FIG. 3, 4 × 10^-3A polycarbonate plasma polymerized film was deposited as a top coat (5) under the conditions of Torr's argon pressure. As a result, a hard transparent polymer film was obtained. This composite mixed multilayer film had the same color tone as gold, and became glossy and had a high dignity. In addition, this transparent polymerized film was excellent in protection of the composite mixed film, and was also excellent in adhesion, abrasion resistance, and corrosion resistance as in Example 1. Example 5 As shown in FIG. 5, on the surface of the composite mixed multilayer film obtained in Example 4, using ITO as an evaporation source, oxygen gas 3 × 10^-4A transparent conductive film (6) of ITO having a thickness of 0.3 μm was formed at Torr, a discharge power of 300 W, and a substrate temperature of 30 ° C. The composite mixed multilayer film in this case is also the same as the color tone of gold, and has a high glossy tone. The protective property of the composite mixed film is further increased, and the adhesion, abrasion resistance, and corrosion resistance are also the same as in Example 1. A composite mixed multilayer film of similarly excellent quality and surface conductivity (resistance, 200Ω / ) was obtained. (Effect of the invention) As described in detail above, gold or an alloy thereof and an organic substance are simultaneously vapor-deposited by plasma excitation to form a composite mixed multilayer film together with a TiN layer, and if necessary, a top coat, an undercoat, or a topcoat and an undercoat are used in combination. With the above configuration, the following excellent effects were obtained. 1. It is possible to use expensive gold without changing the color tone of gold. 2. Since the composite mixed film with the organic substance is arranged, the coefficient of friction can be reduced and the abrasion resistance can be improved. 3. The corrosion resistance of a thin film formed only of gold or its alloy, or a multilayer film of TiN, may change due to the occurrence of pinholes, etc., but the composite mixed multilayer film of the present invention significantly improves the corrosion resistance. Can be done. 4. By arranging the composite mixed multilayer film of the present invention on an item that comes into direct contact with the skin, it is less cold when it comes into contact with a metal, alloy or inorganic substance. 5. The surface of the composite mixed multilayer film can have functions such as conductivity. Such an advantage is particularly effective when applied to ornaments or practical products such as watches and eyeglasses, and has an extremely wide range of applications such as display elements in which various color tones are a part of the design.

[Simple explanation of drawings]

FIG. 1 shows an embodiment of the present invention, and is a partial cross-sectional view showing an example in which a metal composite mixed film is vapor-deposited on a substrate on which TiN is laminated in advance. FIG. 2 shows another embodiment of the present invention, in which an undercoat is applied on the TiN laminated on the substrate, and a golden composite mixed film is further formed on the undercoat. It is a cross-sectional view. FIG. 3 shows still another embodiment of the present invention, and shows an example in which a golden composite mixed film is formed on TiN laminated on a substrate and a top coat is vapor-deposited on the golden composite mixed film. It is a sectional view. FIG. 4 is a partial cross-sectional view showing an example in which an undercoat is applied on TiN laminated on a substrate, a golden composite mixed film is formed on the undercoat, and a topcoat is vapor-deposited on the undercoat. FIG. 5 is a partial cross-sectional view showing an example in which a transparent conductive film is formed on the surface of the composite mixed multilayer film shown in FIG. FIG. 6 is a partial cross-sectional view showing an example in which a composite mixed film is further formed on the composite mixed multilayer film shown in FIG. 1 ...... Board 2 ...... TiN thin film 3 ...... Composite mixed membrane 4 ...... Undercoat 5 ...... Top coat 6 ...... Transparent conductive film