Heat processable metallic appearing coatings

Suitable for thermal processing including tempering for coated objects with a metallic appearance

The present invention generally relates to the technique of vacuum coating, and more particularly to the technique of manufacturing vacuum coating, which maintains the appearance of metal and other metallic properties during high-temperature treatments such as bending, lamination, and tempering.

Most of the glass vacuum coating films that have the desired metallic appearance and other metallic properties during deposition lose their characteristic metallic appearance and properties when subjected to high-temperature processing. The vacuum coating film with metallic appearance and other metallic properties, such as conductivity and infrared reflectivity, is usually metal, metal nitride, metal carbide or metal boride, which oxidizes when heated in the air to form insulation, which is relatively transparent and transparent. Less absorbing metal oxide. Although many metals can be heated in the air to the glass formation temperature (600 to 700°C) that protects the oxide surface layer, the thinness of the transparent metal coating film and its inevitable non-macro or even porous nature prevents the formation of a suitable protective layer. Therefore, the thin transparent metal surface film usually cannot be heated to a temperature at which the glass can be bent without degrading the metal properties.

US Patent No. 4,992,087 of Holscher discloses a method of manufacturing a tempered or bent glass plate to reduce the penetration of the coating film, wherein one side of the glass plate is applied with at least one opaque metal coating film of a metal or alloy mainly composed of elements 22 to 28, and aluminum A metal-containing protective coating film with at least 10 atomic% titanium and/or zirconium alloy with a thickness such that the metal coating film does not significantly diffuse oxygen during tempering or bending.

The titanium nitride coating has metallic properties that make it suitable as a long-lasting solar control coating. The transmittance and sunlight properties can be changed by changing the thickness of the coating film, and the reflectance and color can be changed by adding an appropriate combination of dielectric layers to maintain chemical and mechanical durability.

This coated article has a specific application in monolithic automotive glass windows. When the coating is deposited on Solargray^®When the glass is dark, it can be used as a hidden glass window with enhanced sunlight properties and desired reflectance and color. In transparent glass, the titanium nitride layer can be adjusted to obtain a standard light source A (LTA) transmittance with low internal reflection, neutral appearance and enhanced sunlight properties of greater than 70%. However, most vehicle glass is curved and tempered.

A vacuum coating film with a metallic appearance during deposition can be manufactured to maintain its metallic appearance when bent with a dissimilar metal coating that forms a thick oxide. Further improvement of the oxidation resistance of the metal film can be achieved by introducing another layer of dissimilar substances, especially an additional interface of amorphous metal oxide.

The vacuum coating of metallic compounds with metallic properties, such as titanium nitride, maintains its metallic properties when it is coated with a dielectric substance, and is stable when an extended metal, alloy or semiconductor layer is added below the titanium nitride to be tempered. The bottom layer with the thermal expansion coefficient equal to or less than the substrate has good adhesion to the glass substrate and the titanium nitride layer, eliminates fog, mottle, image and surface pollution, and greatly increases the operating temperature range of tempering. Preferred underlying materials include silicon, titanium, zirconium, tantalum, chromium, niobium, silicon alloys, and nickel-chromium alloys.

Figure 1 contains the reflectance of the heated but unoxidized metal layer (A) and the reflectance of the oxidized metal layer (B) and the reflectance of the unheated metal layer (C) according to the present invention.

Figure 2 contains the transmittance of the heated but unoxidized metal layer (A) and the transmittance of the heated oxidized metal layer (B) and the transmittance of the unheated metal layer (C) according to the present invention.

3 depicts the coated object of the present invention. The substrate 10 is coated with a first expanded metal layer 20, which stabilizes the second metal compound layer 30 with metallic properties, and protects the silicon-based dielectric layer 40 from oxidation.

Figure 4 depicts the transmittance of the coating film of the present invention heated at 1300°F (704°C) for 3.5 minutes as a function of wavelength.

Description of preferred concrete examples

According to the present invention, some of the more oxidation-resistant coatings are preferably chromium nitride and titanium nitride, which generally rapidly oxidize at 700°C, which can be protected by another oxidation-resistant metal. The protective layer must be thick enough to prevent oxidation of the underlying metal layer. Since the metal oxide is usually not thick enough during vacuum deposition, the protective layer is deposited with metal to form a thick oxide surface layer that prevents oxidation of the underlying material. The metal of the protective layer must be different from the metal of the metal layer to prevent oxidation during interface treatment. Therefore, for example, the titanium protective layer can prevent the oxidation of the chromium nitride layer, but the chromium layer does not. Similarly, the titanium protective layer cannot prevent the oxidation of the titanium nitride layer, while the silicon protective layer does.

When the unprotected coating film is heated and oxidized, it produces a higher transmittance and lower reflectance than the metal coating film according to the present invention, as shown in Figs. 1 and 2, and a hazy and translucent appearance. On the contrary, a metal appearance vacuum coating such as chromium nitride or titanium nitride is protected by a different anti-oxidation layer such as titanium or silicon according to the present invention, and will retain its characteristic metal reflectance when heated to the bending temperature of the glass. The transmittance and absorption properties are shown in Figure 1 and Figure 2. The slightly lower reflectance and higher transmittance of the heated coating are the result of the oxidation of the protective layer surface.

Further improvement of oxidation resistance can be achieved by introducing an additional interface formed by another different type of substance. This substance is preferably glass substrate, such as amorphous metal oxide, such as zinc-tin oxide, preferably Zn₂SnO₄The similar composition.

In order to use titanium nitride in a substantially tempered flat glass substrate, it has been found that it must not only be protected by the oxidation of the protective topcoat layer, but also have to interact with the glass substrate titanium nitride layer or in the tempering process. The stress caused by the required high temperature causes the "crack" to stabilize. For example, a titanium nitride/silicon nitride coating made by a magnetron spraying method with a silicon nitride topcoat to prevent oxidation of titanium nitride was found to be unable to temper through a silicon nitride layer up to 800Å thick. This coating film becomes foggy, mottled, cracked and image effect occurs after tempering (the coating film breaks along the edge of the glass plate). In addition, the coating film is likely to be contaminated on the glass surface after heating, such as stripe-shaped filling tape marks, gasket contamination, or coating film spots.

According to the present invention, the anti-oxidation metal oxide coating film, especially titanium nitride, is generally rapidly oxidized at 700°C, and can be protected by the oxidation of dielectric oxide or nitride. If the stabilizer layer is also deposited on the nitride Under the titanium layer. These stabilizer layers should have good adhesion to adjacent layers, be slightly ductile, and have a coefficient of thermal expansion less than or equal to that of glass. The preferred stabilizer layer is silicon and silicon alloys, titanium, zirconium, tantalum, chromium, niobium, nickel-chromium, and nickel-chromium-containing alloys. Aluminum nitride can also be used as a stabilizer layer, especially to maintain high transmittance. The light source transmittance value of the same standard light source A (LTA) with silicon-aluminum as the stabilizer layer generates a higher total solar energy transmittance (TSET) value than silicon-nickel and aluminum nitride.

The stabilizer layer isolates the glass substrate and the metallized metal compound layer and provides a uniform control surface. The heat treatment here prevents, for example, the titanium nitride layer from reacting with the glass surface and provides a mechanical transition layer between the glass substrate and the titanium nitride layer. The stabilizer layer reacts with the glass substrate to form an oxide, which increases the penetration rate and still maintains the adhesion to the metallized metal compound. The stabilizer layer should be thick enough to separate the metallized metal compound layer from the glass, but thin enough to oxidize and provide maximum transmittance, because this layer does not significantly enhance the sunlight properties. The thickness of the stabilizer layer is preferably in the range of 5 to 100 Å. Preferably, the stabilizer layer is silicon, and the thickness is preferably in the range of 20 to 50 Å. Titanium is another preferred stabilizing layer, especially the thickness is in the range of 15-40 Å.

According to the present invention, the dielectric properties of the silicon alloy are better for the topcoat. The dielectric properties of the silicon alloy used in the topcoat are strict to prevent the coating film from cracking when heated. Silicon can be alloyed or mixed with many dissimilar elements. Each element adds unique properties to silicon in the form of spray-deposited target substance or spray-coated film. In addition, the target structure by casting mold or plasma injection is convenient by alloy. According to the present invention, elements that are alloyed or mixed with silicon include aluminum, nickel, chromium, iron, nickel-chromium alloy, boron, titanium, and zirconium. The amount of other metals in the silicon alloy varies with the metal and is only limited by the target and the desired properties of the coating. Generally, 50% by weight of additional metal up to silicon can be used, preferably 5 to 25% alloy metal and/or up to 2% of admixture.

The oxygen-argon mixture is sprayed with a spraying ratio 40% higher than the spraying silicon-aluminum flat target. For example, the silicon-nickel flat target is more stable, and the absorption of 20% by weight of nickel in the oxide film and the refractive index effect are effective The application described here is not important. However, when absorbing with nitride spraying, the degree of silicon-nickel depends on the amount of nickel, while silicon-aluminum nitride does not. When a refractive index change or absorption is required, such as a concealed coating film, the alloy content can be changed. In this way, the increased flexibility of the additional layer changes the optical properties and in particular reduces the transmittance. Chromium and chromium-nickel alloys act like nickel, with increased chemical durability, especially for nitride coatings. On the other hand, silicon-aluminum nitride is not chemically persistent.

Generally speaking, silicon alloy oxide, nitride and oxynitride coatings provide a long-lasting topcoat, which helps prevent the oxidation of the underlying metallized metal compound layer during the tempering process. Silicon-iron with an extra layer on the metallized metal compound is most effective. In addition, the heat treatment during tempering further strengthens the chemical and mechanical durability of these layers. For example, silicon-aluminum or silicon-nickel nitrides, nitrides or oxynitrides are particularly effective. Silicon-iron nitride with an intermediate silicon-aluminum nitride, aluminum nitride, silicon or silicon alloy layer between the titanium nitride and the silicon-iron nitride layer is most effective. Silicon alloy oxide protective topcoat is particularly effective in the range of 400 to 1100 Å, preferably 500 to 1000 Å, and silicon alloy nitride protective topcoat is particularly effective in the range of 125 to 1000 Å, preferably 200 to 800 Å.

Generally speaking, in daylight control glass windows of automobiles, the coating film stack is generally composed of titanium nitride sandwiched between dielectric layers to form an interference coating film stack and provide a protective topcoat. According to the present invention, the stabilizer metal layer is inserted between the glass substrate and the metal compound with metallic properties. The preferred metal compound is titanium nitride, which generally has a thickness of 20 to 1000 Å, and preferably has a thickness of 30 to 500 Å. The metal compound layer is protected by a topcoat of a dielectric material and is not oxidized, preferably a silicon-based dielectric material. The coating film is then stabilized by bending or tempering. The combination of these layers and heat treatment enhances the properties of the coating film. The daylight properties of this tempered or bend coated glass with a stable metal layer, titanium nitride and silicon alloy dielectric materials are always better than the equivalent unheated coating film without a stable layer. Preferred silicon-based dielectric materials are oxides, nitrides and oxynitrides containing silicon and silicon alloys, such as aluminum, nickel and/or chromium.

The silicon alloy oxide topcoat has specific applications in the vehicle vision field where the light source transmittance (LTA) is required to be greater than 70%, and long-lasting, neutral appearance, anti-reflection, and daylight strengthened glass are required. Higher light source transmittance (LTA) requirements, such as the European requirement of 75%, can be met by reducing the thickness of the titanium nitride layer, which can also be achieved by compensating for the lower transmittance when the colored glass substrate is coated in accordance with the present invention .

However, where there is no requirement for LTA greater than 70%, a combination of oxide, nitride and oxynitride layers can also be used as a top coat. The combination of silicon nitride or oxide, nitride and oxynitride as the top coat layer provides a long-lasting coating film with increased flexibility in the choice of color and reflectance. These topcoats have specific applications for concealed glass with enhanced sunlight properties.

The preferred coated object of the present invention has general configuration glass/M1/M3/silicon (M2) dielectric properties, where M1 is a semiconductor or a metal alloy or a combination thereof, M2 is an element combined with silicon in a silicon alloy target, and M3 To protect the metallized metal compound that is not oxidized and stable during high temperature treatment such as tempering. The selective intermediate layer can be deposited between the metal compound and the silicon-based dielectric substance.

Referring to Fig. 3, the glass substrate (10) is first coated with a stabilizer layer (20) by spraying, which is used to prevent the coating film from cracking during high temperature treatment. Then there is a metallized metal compound layer (30) with metallic properties, which is mainly used to reduce the solar heat load, and secondly to meet aesthetic requirements. This layer can then be a selective intermediate layer (not shown), if necessary, its function is to strengthen the performance of the protective topcoat, and to selectively increase the elasticity of the coating film and penetration. This layer is followed by a dielectric protective topcoat layer (40), which is used to prevent the metal compound layer from being oxidized during high-temperature processing and provide a durable topcoat.

The stabilizer layer is preferably selected from silicon, titanium, zirconium, tantalum, chromium, niobium, silicon alloys, nickel-chromium alloys, and aluminum nitride. The metal compound layer (30) with metallic properties is mainly used to reduce the solar heat load, and secondly to provide aesthetic requirements, and is selected from metal borides, metal nitrides, metal carbides and oxynitrides. The selective intermediate layer is preferably selected from silicon, titanium, silicon metal alloys and oxides, nitrides and oxynitrides thereof. Finally, the dielectric protective topcoat layer (40) is used to prevent the coating film from cracking during high temperature processing and provide a durable topcoat, which is selected from silicon nitrides, oxides and oxynitrides and silicon metal alloys.

In addition, in order to provide flexibility to control the color, reflectance, and transmittance that meet the requirements of daylight properties, a selective layer can be sprayed. For example, a silicon nitride layer can be inserted between the stabilizer layer (20) and the metallized metal compound layer (30). The other selective layer sequence and the group selected from the stabilizer layer are alternately stacked with metalized metal compound layers, and a metal layer is added on the protective topcoat layer (40). The layers can also be repeated, for example, an additional layer of metallized metal compound under the protective topcoat layer can also be sprayed on the protective topcoat layer (40).

In a preferred embodiment of the present invention, the coating film is manufactured in a large-scale magnetron spraying device capable of coating glass up to 100x144 inches (2.54x3.66 meters). In the following example, the coating is deposited using a planar magnetron anode with a 5x17 inch (12.7x43.2 cm) metal target such as chromium or titanium, or a 3 inch (7.6 cm) diameter silicon or silicon alloy rotating anode. scale. In each example, the 6mm thick glass substrate passed the target on the conveyor roller at a speed of 120 inches (3.05 meters) per minute. Base pressure is 16^-6The scope of Torr.

The coating film can be manufactured by first setting the spraying gas to a pressure of 4 millitorr and then setting the anode to a fixed power. In each example, unless otherwise indicated, the 6mm thick glass substrate passed the target at a speed of 120 inches (3.05 meters) per minute on the transfer roller, unless otherwise indicated. This step is repeated at each level of the configuration.

The coating film is suspended by hanging 2x12 inches (5.1x30.5 cm) and coated with 6.0mm clear glass on the belt of pliers and lifted to 48x30x12 inches (1.2x0.76x0.3 meters) and heated to a vertical "box-type" furnace at 705°C And test thermal stability. Bring to heat for 3.5 minutes, unless otherwise instructed, assuming tempering. The quenching of the air during the tempering process did not cause any degradation of the coating film. In order to determine the compatibility with the manufacturing method, the coated glass plate 12 inches (0.3 m) square was edged, cleaned, the black circle glass material was filtered and tempered in a vertical and horizontal furnace. Check the film properties of transmittance, reflectance, color, total solar energy transmittance and total solar infrared transmittance (TSET and TSIR). Carry out stiffness abrasion test and record the haze ratio.

The present invention is further understood by the description of the following specific examples.

<u style="single">Example 1</u>

The chromium metal target was sprayed with 7.5 thousand watts, 587 volts and 4 millitorr of pure nitrogen gas (2 times) until the light source transmittance was 9% to produce a 380 Å thick chromium nitride coating. The coated glass is then heated at 570°C for 10 minutes. The coating film is oxidized by heat, and its transmittance curve is similar to Figure 2 B.

<u style="single">Example 2</u>

For comparison of Example 1, a chromium metal target was sprayed (2 times) with 7.5 thousand watts, 586 volts and 4 millitorr of pure nitrogen until the light source transmittance was 10% to produce a 380 Å thick chromium nitride coating. Then the target layer of titanium was sprayed at 0.5 thousand watts and 346 volts (1 time) until the light source transmittance dropped to 8.9% and a titanium metal layer of about 40 Å thick was deposited. The sample was heated at 570°C for 10 minutes and although the transmittance of the coating film was slightly reduced, it still had a metallic appearance and showed a spectroscopic curve similar to (A) in Figures 1 and 2. The coating film oxidized when heated at 625°C for 10 minutes.

<u style="single">Example 3</u>

The chromium nitride film with a thickness of about 380Å as used in the above example has a penetration rate of 906%. The Zn-2Sn composition is sprayed at a thickness of about 60Å with a thickness of 1.8 thousand watts and 3466 volts in a mixture of 50% by volume oxygen and 50% by volume argon. Zn-tin alloy target and similar composition Zn₂SnO₄Of zinc/tin oxide. The penetration rate was 10.2%. Finally, a 40Å thick titanium metal layer as in Example 2 was applied until the penetration rate was reduced to 8.7%. The coating film maintained its metallic appearance after heating at 570°C for 10 minutes and at 625°C for 10 minutes.

<u style="single">Example 4</u>

In order to compare Example 3, the same chromium nitride layer and titanium nitride layer as in Example 3 were produced by spraying the chromium target (2 times) with 8 thousand watts, 532 volts and 4 millitorr of 50% argon-oxygen mixture pressure, but in There is a titanium layer about 40Å thick between the two layers. The penetration rate increased from 9.5% to 10.4%. The coating film was oxidized after heating at 625°C for 10 minutes.

<u style="single">Example 5</u>

The chromium target was sprayed (1 time) with a pure nitrogen atmosphere of 8 thousand watts, 532 volts at a pressure of 4 millitorr, and the coating film with the same chromium nitride layer and titanium nitride layer as in Example 3 was heated at 625°C for 10 minutes After complete oxidation.

<u style="single">Example 6</u>

A chromium metal target was sprayed in a pure nitrogen atmosphere at a pressure of 4 millitorr to deposit a titanium nitride layer of about 450Å thick. The voltage is 764 volts and the power is 8 thousand watts. The coating film was completely oxidized after heating in air at 570°C for 10 minutes.

<u style="single">Example 7</u>

For comparison with Example 6, a titanium nitride layer of about 500 Å thick was deposited as in Example 6. The penetration rate is 20.2%. The silicon layer of about 200Å thickness was deposited by spraying the Airco coating technology C-Mag rotating anode with silicon target substance at 1 thousand watts, 583 volts (2 times). The penetration rate is 10.8%. After heating at 625°C for 10 minutes, the coating film still has a blue and metallic appearance.

<u style="single">Example 8</u>

A titanium nitride layer of about 470 Å thick as in Example 6 was used. The penetration rate is 22.8%. A silicon nitride layer of about 100Å thick was used on the C-Mag anode as in Example 7 by spraying the silicon target with 3 kilowatts, 416 volts and 4 millitorr of pure nitrogen. After a single pass, the penetration rate is increased to 25%. The appearance of the sample remained unchanged after heating at 625°C for 10 minutes.

<u style="single">Example 9</u>

The titanium layer was sprayed with a flat titanium anode of 0.6 thousand watts and 332 volts in argon to achieve a penetration rate of 62% (1 time), and then 9 times with a flat titanium anode in pure nitrogen at 4.0 thousand watts, 536 volts to 18.5%. Transmittance, then 5 times using a rotating anode with silicon-5% aluminum sprayed in pure nitrogen with a penetration rate of 2.8 thousand watts, 473 volts to 23%. The coating thickness of each individual layer is 25Å for titanium, 400Å for titanium nitride, and 270Å for silicon-5% aluminum nitride. The properties of transparent glass before and after heating are as follows:<tables><img file="TW219953B_D0001.tif" /></tables>

Penetrating total daylight infrared radiation (TSIR) shows that titanium nitride is not degraded after heating, but is slightly strengthened. It is also confirmed that the TSIR is 1% lower than the unheated sample in the wavelength region greater than 900nm. The abrasion resistance after heating is lower than 2% required by the glass mist limit. The scratch resistance before heating far exceeds that by completing the manufacturing tempering treatment (cutting, edging, cleaning, filtering and tempering) without scratches or deterioration of the coating film.

Solargray for 4.0mm car side light and backlit hidden glass windows^®This coating film of glass reduces the light source transmittance to about 20% and the total sunlight transmittance is 13%.

<u style="single">Example 10</u>

The first layer was sprayed with a flat silicon-7.5% nickel anode in argon at 0.4 kilowatts and 500 volts to a penetration rate of 81.4% (1 time), and then a flat titanium anode was used in pure nitrogen at 6.0 kilowatts, 596 volts. With a penetration rate of 90 inches (2.3 meters) per minute to 53.7%, and then 12 times using a flat anode with silicon-7.5% nickel, 50% argon-50% oxygen, 3.0 thousand watts, 348 volts to 63.2% Penetration rate while spraying. The coating thickness of each individual layer is silicon-7.5% nickel 23Å, titanium nitride 100Å and silicon-5% aluminum oxide 790Å.

As described in Figure 4, the properties of 6.0 mm transparent float glass before heating (unheated) and after heating at 1300°F (740°C) for 3.5 minutes (heating) are as follows:<tables><img file="TW219953B_D0002.tif" /></tables>

Figure 4 shows the% transmittance in the sunlight region of the spectrum before and after heating as a function of wavelength (nm). These data show that the transmittance increases in visible light, but decreases in the infrared region after heating, thus enhancing the overall solar performance of the coating film.

When the coating film is deposited on such as Solex^®In the case of glass heat absorption glass, the titanium nitride layer of 4.0mm Solex glass is reduced to 45Å to meet the 70% (light source A) transmittance requirement. This coating film is heated on 4.0mm Solex glass at 1300°F for 1.75 minutes to the daylight properties of standard light source A with a transmittance of 71.03% TSET=47.78% TSIR=27.67%.

The resulting coating film resists reflection on the film side and has a neutral appearance in transmittance and reflectance. The thickness range of 790Å (12 times) to 925Å (14 times) and the transmittance of silicon-7.5% nickel oxide of titanium nitride with a thickness of less than or equal to 100Å (light source A) is the largest and the TEST is the smallest.

The silicon-7.5% nickel (0.4 thousand watts) mentioned in this example is the minimum thickness of the stable coating film after tempering. As mentioned above, the coating film breakage occurs quickly in the thinner layer. The beginning of coating film rupture can be seen when the penetration rate of the bottom layer decreases. On the other hand, if the bottom layer is sprayed at more than 0.7 kilowatts (40Å), the coating film does not meet the required light transmittance of 70% or greater (light source A). Generally speaking, if this layer is sprayed at 0.6 thousand watts and 525 volts, it will generate 73% transmittance after one pass (34Å) of 6.0 mm clear glass, and the coating has a transmittance greater than 70% (light source A). stable.

<u style="single">Example 11</u>

The coated object prepared as in Example 10, but with the following configuration: glass/Si-5%Al/Ti nitride/Si-5%Al nitride with Si-5%Al nitride layer thickness greater than or equal to 125Å, Si- The thickness of 5% Al is greater than or equal to 25Å, which is stable after tempering.

<u style="single">Example 12</u>

The coated article prepared as in Example 11, but with the following configuration: Glass/Si-8%Fe-0.25%B/Ti nitride/Al nitride/Si-8%Fe-0.25B nitride has a Si- with a thickness of 25Å 8%Fe-0.25%B, Al nitride with a thickness of 80Å and Si-8%Fe-0.25%B nitride with a thickness of 200Å are stable after tempering. Although the aluminum nitride of the coating film with the above configuration is dissolved in water, the unheated coating film is stable by tempering in water for 30 minutes. The coating film was heated and boiled for 30 minutes. Use Si-8%Fe-0.25%B in the coating when absorption is desired, such as in concealed glass.

<u style="single">Example 13</u>

The coated article prepared in the above example has the following configuration glass/Si-8%Fe-0.25%B/Ti nitride/Si-8%Fe-0.25%B/Si-8%Fe-0.25B nitride. This coating has Si-8%Fe-0.25%B with a thickness of 25Å and Si-8%Fe-0.25B with a thickness of 350Å, which is stable in tempering. In addition to thermal stability, the additional layer has increased flexibility in changing color, transmittance and reflectance.

<u style="single">Example 14</u>

The coated article prepared as in the above example has the following configuration glass/Ti/Ti nitride/Si-13% Al nitride or oxynitride. These coatings describe the difference between Si-M2 nitride and oxynitride topcoats. These coating films are stable to tempering. The first three layers of the coating film were prepared by spraying the layers described in Example 1 on 6mm transparent glass, except that the 9 titanium nitride layers were sprayed at 4.4 thousand watts and 543 volts to a penetration rate of 16.5%. The thickness of the titanium nitride layer is 440Å. The two-sided paint layer is then sprayed to the same physical thickness of 220Å. The Si-13%Al nitride topcoat was prepared by spraying 5 times on the plane anode with pure nitrogen at 3.0 kilowatts and 456 volts to a final penetration rate of 19.7%. The Si-13% Al oxynitride was prepared by anodic spraying 5 times to 18.9% in a 6% oxygen-nitrogen mixture at 2.6 kilowatts and 450 volts on the same plane. After heating the film and the glass side, compare the CIE color coordinates of the coating film.

<tables><img file="TW219953B_D0003.tif" /></tables>From the above results, it can be seen that when the topcoat with a fixed physical thickness changes from a nitride to an oxynitride, there is a color shift and change in the reflectance due to the change in the refractive index of the coating film.

<u style="single">Example 15</u>

The coated article prepared in the above example has the following configuration: glass/Si-7.5%Ni/Ti nitride/Si-10%Cr nitride, for example, Si-10%Cr nitride with a thickness ranging from 290Å to 1050Å, with a thickness of 100Å The titanium nitride and Si-7.5% Ni layer with a thickness of 34Å are stable after tempering.

The first two layers of the coating film were prepared by spraying on 6mm transparent glass as described in Example 4. The third layer was prepared by spraying 4 times with pure nitrogen at 3.0 thousand watts and 510 volts on the plane Si-10%Cr anode spraying to a final penetration rate of 53.1%. The thickness of this layer is 290Å.

The above examples are only provided to describe the present invention. Other metals, metal nitrides and metal carbide metallized appearance films can be protected from oxidation by forming a metal layer on the thick oxide surface as described above. Other metal nitrides, metal carbides, and metal borides The range of metal films and compositions can be used as protective topcoats with other oxide, oxynitride and nitride layers, and other stable metal layers as metallized metals Compound layer. The deposition conditions vary according to the deposition device and material. The thickness of the coating film can be changed to produce the desired reflectance and transmittance properties. The scope of the present invention is defined by the scope of the following patent applications.