JPH0248432A - Heat ray-shielding plate and production thereof - Google Patents

Abstract

PURPOSE:To obtain a heat ray-shielding plate with high visible light transmission, heat ray-shielding property and such a durability that the subject plate can be used as single plate by forming a zirconium nitride film containing a suitable amount of silver on the surface of a glass base. CONSTITUTION:The subject heat ray-shielding plate is produced by forming a silver-containing zirconium nitride film 13 on the surface of one side of a transparent plate 11 such as a glass plate. The method for production of the subject plate is mentioned below. Glow discharge the target 43 in which is a noble metal (e.g., Ag) and arcing the target 47 in which is a metal (e.g., Zr) are simultaneously induced in a vacuum tank 41 capable of adjusting an ambient gas (preferably <=30vol.% N2 and >=70vol.% inert gas) composed of reduced inert and nitrogen gases and a noble metal-containing metal nitride film is formed on the surface of a transparent plate 52 such as glass placed opposite to the noble metal target 43 and the metal target 47. Transparent dielectric films 12 and 14 may be formed on the zirconium nitride film 13 and on one or more sides between the film 13 and the transparent plate 11.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention is a heat ray shielding plate used for windows of automobiles and buildings, which has particularly high visible light transmittance and can be used in the form of a single plate. The present invention relates to a durable heat ray shielding plate and a method for manufacturing the same.

[Conventional technology]

Conventionally, this type of heat ray shielding plate is shown in Figures 6 and 7.
There was something shown in the figure. What is shown in FIG. 6 is a laminated glass 9 in which a glass substrate 11 to which a heat ray shielding film 94 is attached and another glass substrate 11 are bonded together with an intermediate resin film 95.
It is 6. Also, what is shown in FIG. 7 is a heat ray shielding film 94.
The glass substrate 11 with
1 is combined with a separator 97 via a space 96 to form a double-glazed glass 98. Heat ray shielding film 94.9 used in these laminated glass 96 and double-glazed glass 98
5, a transparent dielectric film 98 with a thickness of 30 to 40 nm and a transparent dielectric film 98 with a thickness of 7 to 1
It is usually formed by laminating three layers: a 5 nm thick Ag film 99 and a 30 to 40 nm thick transparent dielectric film 100. Transparent dielectric films often used here include zinc oxide, tin oxide, and bismuth oxide. These conventional products utilize the excellent optical properties of the Ag film 99, namely high visible light transmittance and low solar transmittance. Ag film 9
9 and glass substrate 11 or air or intermediate resin film 95
By acting as an anti-reflection film between
The corrosion of the membrane was prevented to some extent. Further, an invention similar to the present invention is described in Japanese Patent Publication No. 62-369°79, in which Au is added to a titanium nitride film.

Furthermore, a sputtering method has been used as a method for manufacturing a zirconium nitride film containing Ag.

In this case, sputtering using a mixed gas of inert gas and nitrogen gas using zirconium nitride containing Ag as a target is usually carried out, but in such cases the target manufacturing method is extremely difficult and is generally not easy. It was not available, and if it was desired to change the Ag content in the zirconium nitride film, it was inconvenient that a target had to be prepared each time. In addition, in order to avoid such inefficiency, Ag and zirconium are sputtered simultaneously in an atmospheric gas containing nitrogen in the same vacuum chamber using two targets of 8g and zirconium.
There is a method of coating the substrate 6 with a zirconium nitride film containing Ag, but this method has the serious drawback that Ag is nitrided and silver nitride is mixed into the film. The aforementioned disadvantages are generally prevalent when metal nitride coatings containing noble metals are coated by prior art techniques.

[Problem to be solved by the invention]

However, if the heat ray constrictive membrane 94 having the above-mentioned structure is in a single-panel state that is directly exposed to the outside air, it will corrode within a short period of time.
I have no choice but to use it in conditions like 8. On the other hand, the above-mentioned titanium nitride film to which Au is added has a high absorption rate in the visible light wavelength range. It has the disadvantage that it is difficult to effectively block the transmittance.

L7 has a high visible light transmittance, and in order to suppress the heat inside a car under sunlight, the 1" light transmittance is 55%.
A heat ray shielding plate that has the following properties and can be used in the form of a medium plate is strongly desired.

The present invention has high visible light transmittance! ,,-1
Furthermore, the present invention provides a heat ray shielding board that has heat ray shielding performance and at the same time is durable enough to be used as a single board. Furthermore, in the manufacturing method of a metal nitride film containing a noble metal, it solves the problems of inconvenience and inefficiency that the conventional technology had, and it also solves the problem of inconvenience and inefficiency that existed in the conventional technology. The purpose of the present invention is to provide a method that can reliably contain C in a noble metal state in a film of a material.

[Means to solve the problem]

As a result of intensive research, the present inventors have found that by incorporating an appropriate amount of Ag into the zirconium nitride film, it can achieve high visible light transmittance and heat ray shielding without impairing the excellent durability of the zirconium nitride film. It has been found that properties with good effects can be obtained. In other words, the amount of Ag contained in the zirconium nitride film, when the film thickness is about 12 nm, is
When increasing the amount from 5% to 50% by weight, the visible light transmittance improves and the solar transmittance decreases without impairing the chemical and physical durability of the coating, so it has a high visible light transmittance. It was discovered that it has excellent properties as a heat ray shielding plate.

If the amount of Ag film that should be contained in the zirconium nitride film is less than 5% by weight, the effect of improving optical properties due to the inclusion of Ag will not be recognized, while if it exceeds 50% by weight, the chemical and physical durability of the film will be affected. Therefore, the amount of Ag that should be contained in the zirconium nitride film is 5% by weight or more and 50% by weight.
The following are preferred. Alternatively, a zirconium nitride film containing Ag may be formed directly on the substrate, or a transparent dielectric film of an appropriate thickness may be formed on the substrate first, and then a zirconium nitride film containing Ag may be formed. . Further, by coating the Ag-containing zirconium nitride film with a transparent dielectric film having an appropriate thickness as a third layer, the reflected color tone and transmitted color tone can be adjusted. Used for this purpose.

Films that are transparent in the visible light wavelength range include tantalum oxide,
Any one of oxide films such as titanium oxide, zinc oxide, zirconium oxide, tin oxide, indium oxide, or an indium oxide film doped with tin oxide, or a mixture thereof is preferably used. Further, a transparent dielectric film having a refractive index of 1.6 or more at a wavelength of 550 nm can also be used.

As a method for attaching the above-mentioned Ag-containing zirconium nitride film to a substrate, two film-forming evaporation sources are installed in the same vacuum chamber, one of which is used as a sputtering cathode and the other one as a vacuum arc evaporation cathode. , Ag is formed into a film from an Ag target by a method of generating a glow discharge using a mixed gas of an inert gas such as argon and nitrogen, and at the same time, zirconium nitride is coated from a zirconium target for vacuum arc evaporation of zirconium by an arc of the above atmospheric gas. We have found a method to implement this by forming a film using electrical discharge.

In other words, it was previously considered impossible to form a metal film by sputtering and a metal nitride film by vacuum arc evaporation at the same time in the same vacuum chamber. When the metal is a noble metal such as Ag, the noble metal can be contained in a metal state without being nitrided in the metal nitride film simultaneously formed by vacuum arc discharge.

In the vacuum arc evaporation method, compared to the sputtering method, the metal used as the target material has a higher probability of being ionized during the evaporation process, so it is extremely easy to form a compound film with the reactive gas, and therefore zirconium is more likely to form a zirconium nitride film. It has been found that the proportion of nitrogen gas in the atmospheric gas required to achieve this is extremely small compared to the spuckling method. That is, while the sputtering method requires approximately 100% by volume of nitrogen gas, the vacuum arc evaporation method can reduce the amount to 30% by volume or less. In such an atmospheric gas with a small mixing ratio of nitrogen gas, the coating of a noble metal such as Ag, which generally has low reaction activity, will not become a nitride even by sputtering, and the optical properties of the metal will remain in the state of the coating. can be held in

Further, according to the present invention, the content of Ag in the zirconium nitride film can be extremely easily changed by adjusting the power applied to either the sputtering target or the arc evaporation target, or both, and The optical properties of can be changed efficiently.

The zirconium nitride film containing Ag is prepared by fixing a substrate to be coated with the film as shown in Fig. 4, and facing it, a cathode for sputtering and a cathode for vacuum arc evaporation are set in the same vacuum chamber. Of course, as shown in Figure 5, a sputtering cathode and a vacuum arc evaporation cathode are installed side by side so that the surfaces of the targets attached to each are parallel, and each target is This can be carried out in an apparatus that coats a film when the substrate passes through a space facing the substrate. At this time, the substrate is transferred at a high speed to reduce the thickness of the coating coated by passing the sputtering cathode and the vacuum arc evaporation cathode once (by passing the substrate repeatedly over the cathode). Microscopically, the film has a layered structure, but from a macroscopic point of view, Ag has the same optical properties and durability as the film obtained using the apparatus shown in Figure 4. A coating is obtained which is a zirconium nitride film containing.

Examples of noble metals other than Ag that can form the metal nitride film containing noble metals according to the present invention include Pt,
Rh and Pd can be used, and as the metal nitride, nitrides of metals in Group 4A of the periodic table such as titanium nitride and haunium nitride can be used. Furthermore, as the metal nitride coating containing a noble metal, the above-described combination of a noble metal and a metal nitride can of course be applied.

[Function] According to the present invention, since the zirconium nitride film contains an appropriate amount of Ag, it acts to effectively reduce solar transmittance without impairing corrosion resistance. In addition, the transparent dielectric film coated before or after coating zirconium nitride containing Ag reduces the reflectance of visible light or increases the transmittance of visible light, and further changes the reflected color tone and transmitted color tone due to the interference effect of light. It has the effect of changing.

In addition, the arc discharge generated on the surface of the target for vacuum arc evaporation by the nitrogen-containing atmospheric gas in the vacuum apparatus has a nitriding effect on the metal due to its reactivity when the metal target is evaporated. The glow discharge generated on the surface of the target does not have a nitriding effect during the process in which the noble metal used in the sputtering target is sputtered to form a film, but has the effect of forming a film on the substrate in a metal state.

〔Example〕

Example 1 Examples of the present invention will be described below with reference to the accompanying drawings. Fourth
The figure shows an example of a device used to realize the present invention, in which a vacuum chamber 41 is connected to a vacuum evacuation pump (not shown), and a reduced pressure atmosphere is supplied to the inside of the chamber 41 through a gas inlet pipe 5.
It is adjusted by the valve 55 of No. 4. A glass substrate 52 with a thickness of five fins is set on a substrate support stand 53, and the vacuum chamber 41 is
After evacuating the inside to 10-3 Pa, a mixed gas of 30% by volume nitrogen gas and 70% by volume argon gas is introduced from the gas introduction pipe 54, and the pressure is adjusted to 0.5 Pa. Electrical insulator 5
6, an electric current A44 is applied to the Ag target 43 installed on the surface of the sputtering cathode 42, which is electrically isolated from the vacuum chamber 41 by closing the switch 45.
A direct current of A was applied. At the same time, the power source 48 connects the zirconium target 47 installed on the surface of the vacuum arc evaporation cathode 46, which is electrically isolated from the vacuum chamber 41 by an insulator 56, to close the switch 51 and close the switch 50. Trigger electrode 49 for discharge excitation
to generate an arc discharge, and the glass substrate 5 is simultaneously removed from the Ag target 43 and the zirconium target 47.
The coating was applied to No. 2 for 3 minutes. Switch 45, 50.5
1 was opened, the vacuum chamber 41 was returned to atmospheric pressure, and the coated glass was taken out.

The thickness of the coating on the glass substrate 52 was measured using a stylus needle.
nm was obtained. Furthermore, using a fluorescent X-ray analyzer, we measured the Ag content in the film.
When the amount was measured, it was 35% by weight.

Ag target 43 and zirconium target 47
By adjusting the power applied to the zirconium nitride films containing various amounts of Ag, films of zirconium nitride were obtained. The film thickness is 12 nm in both cases.
Then, the visible light transmittance and solar transmittance were measured, and FIG. 3 was obtained. It was observed that the visible light transmittance increased over the entire range of 5% to 50% by weight of Ag, and the solar transmittance decreased, which was the effect of improving the properties as a heat ray shielding plate with high visible light transmittance.

Next, an example of manufacturing a heat ray shielding plate having a three-layer structure of a zirconium nitride film containing Ag and a transparent dielectric film will be described.

Embodiment 2 FIG. 5 shows another example of the apparatus used to realize the present invention, and this apparatus has five chambers 62, 63°, 64.65°.
The basic structure is an integral grounded vacuum chamber 61 consisting of 66, and an electrical insulator 6 at the bottom of the second chamber 63 of the vacuum chamber.
A sputtering cathode 68.69 is installed via 7 and a DC power supply 70.71 is connected via a switch 72.73. Similarly, the valve 74 is inserted through the bottom.
A gas supply pipe 75 is installed. Further, at the bottom of the fourth chamber 65 of the vacuum chamber, a sputtering cathode 76 and an arc evaporation cathode 77 are installed via an electrical insulator 67, and a DC power source 78,79 is connected to a switch 80.
81, respectively. Similarly, a gas supply pipe 83 with a valve 82 is installed through the bottom. In addition, a trigger 84 for causing arc discharge is connected to the DC power source 79 via a switch 85 on the arc evaporation cathode 77 . A conveyor belt 85 is installed inside the vacuum chamber, and a film is formed while a glass substrate 86 having a thickness of 5 mm passes over each cathode on the conveyor belt.

The thickness of the coating to be formed is adjusted by adjusting the moving speed of the conveyor belt 85 and the electric power applied to the cathode. Movement between each chamber is via gate valves 87.88, 89.9
A mechanism is provided that enables this by opening and closing 0.

A method for manufacturing a heat ray shielding plate having high visible light transmittance according to the present invention will be described using a vacuum film forming apparatus configured as described below. Tin 91 was attached as a sputtering target to the top surface of the sputtering cathodes 68 and 69. Furthermore, the upper surface of the sputtering cathode 76 is made of Ag92.
was attached as a sputtering target, and zirconium 93 was attached as an arc evaporation layer target on the upper surface of the cathode for arc evaporation. A glass substrate 86 was set in the first chamber 62 of the vacuum chamber. After reducing the pressure in each chamber of the vacuum chamber to 10 Pa using a vacuum pump (not shown), gate valves 87 and 88 were opened and gate valve 89 was closed. Next, the valve 74 is opened and argon gas containing 80% by volume oxygen gas is supplied from the gas supply pipe 75, and a baffle valve (not shown) is opened so that the pressure in the second chamber 63 of the vacuum chamber becomes 0.5 Pa. adjusted.

Then, switches 72 and 73 were turned on, a voltage of 400 V was applied to the tin target, and a current of 2.5 A was applied to start sputtering. Transport belt 85 is 200mm
It traveled at a speed of 1/min and passed over the cathode 68° 69 to the third chamber 64. After the conveyance was completed, the switches 72 and 73 were turned off to complete the sputtering and the valve 74 was closed. In this way, a tin oxide film was formed on the glass substrate. Next, the gate valve 88 was closed and the gate valves 89 and 90 were opened. Then,
The valve 82 was opened and argon gas containing 30% by volume of nitrogen gas was supplied from the gas supply pipe 83, and the pressure was adjusted to 0.5 Pa by adjusting the baffle valve (not shown). Then, turn on the switch 80 and the cathode 76
A current of 0.8 A was applied to start sputtering.

Further, the switch 81 was turned on, and the switch 85 of the trigger 84 was turned on, and 100 A of electric slag was applied to the cathode 77 to generate an arc discharge. After that, transfer the transport heald 85 to 6
The glass substrate 86 is passed over the cathodes 76 and 77 five times, and the fifth
I sent him to room 66. Then, the conveyor belt stopped running, the switches 80 and 81 of the cathodes 76 and 77 were turned off to stop the discharge, and the valve 82 was closed. In this way, a zirconium nitride film containing Ag was formed on the tin oxide film. Next, the conveyor belt 85 was run to send the glass substrate 86 to the third chamber 64 of the vacuum chamber, the gate valve 89 was closed, and the gate valves 87 and 88 were opened. Then, a tin oxide film was again formed by sputtering on the Ag-containing zirconium nitride film under exactly the same conditions as described above.

Through these steps, a glass substrate 1 as shown in FIG.
1. 2. Tin oxide film with a thickness of 60 nm, 12° and 17 nm.
A zirconium nitride film 13 containing Ag and a 60 nm tin oxide film 14 were formed. The spectral transmittance of the thus obtained heat ray shielding plate is shown in FIG. 2 in comparison with that of the conventional heat ray shielding plate shown in FIG. The visible light transmittance was 78.5% and the solar transmittance was 50.3%, and compared to the case without Ag, the visible light transmittance increased by 4.5% and the solar transmittance decreased by 4.4%. , it showed excellent optical properties as a heat ray shielding plate with clearly high visible light transmittance.

Furthermore, the chemical and physical durability of the coating was investigated by acid resistance, alkali resistance, and reciprocating abrasion tests, and the results shown in Table 1 were obtained.

Table 8 Next, the amount of Ag in the fluorescent When the test shown in Table 1 was carried out on the heat ray shielding plate made from the technology as a single plate, the film almost completely disappeared.As a result, the heat ray shielding film according to the present invention has extremely strong acid resistance, It can be seen that it has alkali resistance and wear resistance.

〔Effect of the invention〕

According to the present invention, since the zirconium nitride film contains an appropriate amount of Ag, it has visible light & lil coverage ratio and heat ray shielding performance, and can be used in the state of a single plate where the film is directly exposed to the outside air. It is possible to obtain a heat ray shielding plate that has the ability to withstand. Furthermore, by coating with a transparent dielectric film before or after coating with the Ag-containing zirconium nitride film, a heat ray shielding plate with various reflected and transmitted colors can be obtained.

Furthermore, according to the manufacturing method of the present invention, Ag contained in the zirconium nitride film can be made into a metallic state, and the content of Ag can be easily adjusted. Coatings with different shielding properties can therefore be produced efficiently without changing the target material.

[BRIEF DESCRIPTION OF THE DRAWINGS] FIG. 1 is a cross-sectional view of one embodiment of a heat ray shielding plate obtained by the present invention, and FIG. 2 is a spectral transmittance curve of a heat ray shielding plate obtained by the present invention and the prior art. Figure 3 shows the effect of Ag in the film on the optical properties of a zirconium nitride film containing Ag.
Figures 4 and 5 are schematic sectional views of the apparatus used to carry out the present invention, and Figures 6 and 7 are diagrams showing the effect of the content, and Figures 6 and 7 are examples of the use of conventional heat shielding plates. A schematic cross-sectional view, FIG. 8, is a diagram showing the film structure of a heat ray shielding plate according to the prior art. 11: Glass substrate, 12: Tin oxide film, 13: Zirconium nitride film containing Ag, 14: Tin oxide film, 21: Spectral transmittance curve of heat ray shielding plate according to the present invention, 22: Spectral spectrum of heat ray shielding plate according to conventional technology Transmittance curve, 41: Vacuum chamber,
42 varnish buttering cathode, 46: vacuum arc evaporation cathode, 43: Ag target, 47: zirconium target, 44 varnish buttering power supply, 48: vacuum arc evaporation power supply, 49 Nidoriger, 52 Niglass substrate, 54: gas introduction tube, 61: Vacuum chamber, 68°69.7
6: Sputtering cathode, 7071.78 Varnish buttering power supply, 75.83: Gas supply pipe, 85: Conveyor belt, 86: Glass substrate, 87, 88, 89.90:
Gate valve, 91: Tin target, 92: Ag target, 93: Zirconium target, 94: Heat ray shielding film, 95: Intermediate resin film, 96: Space, 97: Separator, 98. ioo: transparent dielectric film, 99: Ag film. a11″″′-～- Ag content (wt%) Visible light transmittance solar transmittance chart

Claims (6)

[Claims] (1) A heat ray shielding plate in which a zirconium nitride film containing silver is formed on one surface of a transparent plate like glass. (2) The heat ray shielding plate according to claim 1, wherein the content of silver in the zirconium nitride coating is 5% to 50% by weight. (3) A transparent dielectric film is formed on the zirconium nitride film and on at least one side between the zirconium nitride film and the transparent plate, or The heat ray shielding plate according to item 2. (4) The heat ray shielding plate according to any one of claims 1 to 3, wherein the visible light transmittance is 70% or more. (5) Glow discharge targeting precious metals and arc discharge targeting metals are simultaneously generated in a vacuum chamber where the atmospheric gas consisting of reduced pressure inert gas and nitrogen gas can be adjusted. A method for manufacturing a heat ray shielding plate, comprising forming a coating of a metal nitride containing a noble metal on the surface of a noble metal target and a transparent plate such as glass facing the metal target. (6) The manufacturing method according to claim 5, wherein the composition of the atmospheric gas is 30% by volume or less of nitrogen gas and 70% or more of inert gas.