JPH01294032A - Heat ray shield plate having low visible light transmissivity - Google Patents

Abstract

PURPOSE:To obtain a heat ray shield plate having durability and low visible light transmissivity, by providing a nitride layer of a metal selected from zirconium, titanium and hafnium having a thickness of 50-600Angstrom to the single surface of a transparent substrate composed of glass or synthetic resin. CONSTITUTION:A nitride layer 12 of a metal selected from zirconium, titanium and hafnium having a thickness of 50-600Angstrom is formed to one surface of a transparent substrate 11 composed of glass or synthetic resin by a sputtering method. Whereupon, since the film 12 is composed of metal nitride, said film is not corroded in the atmosphere and has excellent abrasion resistance. By selecting the thickness of the film 12, a heat ray shield plate having solar radia tion transmissivity lower by 5% or more than visible light transmissivity within a visible light transmissivity range of 30-70% can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a heat ray shielding plate with low visible light transmittance suitable for use in window glass of buildings or automobiles.

[Conventional technology]

Conventionally, this type of heat ray shielding plate has been shown in FIGS. 5 and 6. The one shown in Figure 5 is the heat ray reflective film 1.
This is a laminated glass 105 in which a clear float glass panel 101 to which No. 03 is attached and a clear float glass plate 101 are bonded together with an intermediate resin film 104. Moreover, what is shown in FIG. 6 is a double-glazed glass 108 in which a clear float glass plate 101 having a heat ray reflecting film 103 attached thereto and a clear float glass plate 102 are combined by a separator 106 via a space 107. These laminated glass 105 and the clear float glass plate 101 to which the heat ray reflection jl 103 of the double-glazed glass 10B is attached are sequentially coated on the float glass plate 101 with a film thickness of 300 Å to 400 Å as shown in FIG.
00 people ZnO film 109, film thickness 70 Å ~ 150 people Ag
Film 110, ZnO film 111 with a film thickness of 300 to 400 people, 3
The layers are stacked.

In order to prevent the Ag film 10 from being oxidized when forming the ZnO film 111 farther from the substrate 101, the film 110 is
A Zn film of 10 Å to 20 Å is usually formed between the ZnO film 111 and the ZnO film 111, but this Zn film is later oxidized to become a ZnO film and is integrated with the ZnO of the ZnO film 111, so that the final film shown in FIG. 7 is formed. The structure is as follows.

These conventional products mainly utilize the excellent optical properties of the Ag film 10, that is, high visible light transmittance and low solar transmittance, and further utilize the ZnO films 1 provided above and below the Ag film 10.
09,111 acts as an antireflection layer between the Ag film 110 and the glass plate, air, or intermediate film, further improving the visible light transmittance, and at the same time, this ZnO film 109
, 111 force <Qg Corrosion of the film 110 was prevented to some extent. Furthermore, despite the ZnO films 109 and 111, the Ag film 10 corrodes in a few days to several months in humid outside air, so as shown in FIGS. And double-glazed glass 108 was used to prevent the Ag film 10 from being corroded even after several years by preventing exposure to humid outside air.

Those using these two conventional Ag films result in heat ray shielding plates having extremely high visible light transmittance and low solar transmittance.

[Problem that the invention seeks to solve]

However, if this heat ray reflective film 103 is directly exposed to humid outside air, Ag
When the formed film 10 corrodes and its optical properties change, the visible light transmittance decreases and the solar transmittance increases, and the corrosion points also appear mottled in appearance. Ta. For this reason, in applications where a single glass plate is used, such as the side window of a car, and the film formed on the surface is in direct contact with the outside air, conventional Ag1Ill is used.
It was not possible to use products containing 11O.

Moreover, it is difficult to obtain a film with a visible light transmittance in the range of about 30% to 70% and a solar light transmittance lower than the visible light transmittance by at least 5% or more with conventional heat ray reflective films.

[Means for solving problems]

The present invention has been made in order to eliminate the drawbacks of the conventional ones as described above, and has a relatively low visible light transmittance and a solar radiation transmittance of at least 5% higher than the visible light transmittance.
The object of the present invention is to provide a durable heat ray shielding plate that has a low coating thickness and can be used even in an environment where the coating is exposed to the outside air. That is, the present invention provides a transparent substrate made of glass or synthetic resin, and a thickness of zirconium (50 Å to 600 Å) formed on one surface of the transparent substrate.
This is a heat ray shielding plate with low visible light transmittance that is made of a nitride layer of either titanium or hafnium.

Further, in the present invention, the metal nitride layer has a refractive index of 1.
8 to 2.4, and a metal oxide dielectric layer having a thickness of 10 to 600 Å.

Furthermore, the present invention provides a transparent substrate made of glass or synthetic resin, and a substrate having a refractive index of 1.
a first metal oxide dielectric layer having a thickness of 8 to 2.4 and a thickness of 200 Å to 600 Å; zirconium, titanium, and a metal oxide dielectric layer having a thickness of 100 Å to 600 Å;
and hafnium, and the nitride layer of the metal has a refractive index of 1.9 to 2.1.
5 and a second metal oxide dielectric layer having a thickness of 200 Å to 600 Å, the heat ray shielding plate has a low visible light transmittance.

In the present invention, the nitride of the metal nitride layer is MNX
(M is zirconium, titanium, and hafnium, X=
0.1-1.2).

Further, in the present invention, any one of tin oxide 2M titanium oxide, tantalum oxide, aluminum oxide, tungsten oxide, zirconium oxide, zinc oxide, and tin-doped indium oxide is used as the metal oxide dielectric layer.

[Function] Since the film used in the present invention is composed of a metal nitride or a metal nitride and a metal oxide dielectric layer, it does not corrode in the atmosphere like the conventionally used Ag film. It has excellent wear resistance.

In addition, by selecting the thickness of the coating used in the present invention, it is possible to create a heat ray shielding plate that has a visible light transmittance in the range of 30% to 70% and a solar transmittance that is 5% or more lower than the visible light transmittance. Obtainable.

Embodiments of the present invention shown in the drawings will be described below.

[Example 1] Reference numeral 11 is a clear float glass plate having a refractive index of 1.51 and a thickness of 5 mm.
Zirconium nitride (ZrN,, x is 0.1~
1.2) The membrane 2 is formed by a sputtering method (FIG. 1).

The zirconium nitride film was prepared by applying -330 V to the zirconium target in argon gas containing 5.4% by volume nitrogen gas and reduced pressure to 5 x 10-'' Torr.
．． It is formed on the glass plate 11 by reactive direct current sputtering using a current of 9 A.

During this sputtering, argon gas and oxygen gas were
Sputtering atmosphere 5 x 10-'Tor while feeding at flow rates of 7.5 SCCM and 2.5 SCCM
I kept it at r. The optical properties of the obtained heat ray shielding glass were
It is shown in the table and Figure 4.

[Example 2] Reference numeral 21 is a clear float glass plate with a refractive index of 5.5 mm and a thickness of 51. Zirconium nitride (ZrN) 1% in thickness is sequentially coated on the surface of the glass plate 21. X
is a value from 0.1 to 1.2) The film 22 and the thickness are 1
A tin oxide (SnOz) film 23 of 0.00 mm is formed by sputtering (FIG. 2). Zirconium nitride film 2
2 is deposited in the same manner as in Example 1, and the tin oxide film 23 is 2.5
A metallic tin target was heated at 140°C in argon gas containing 80% by volume oxygen gas at a reduced pressure of 10-3 Torr.
It is formed by reactive direct current sputtering by applying 0V and flowing a current of 2.5A. During this sputtering, argon gas and oxygen gas were added for 10 minutes each. OSCCM
and 40. The sputtering atmosphere was maintained at 2.5 x 10''' Torr while supplying at the flow rate of OSCCM. The optical properties of the obtained heat ray blocking glass are shown in Table 1 and Figure 4. This heat ray blocking glass has two layers. The optical properties of the film are improved by optical interference, and the tin oxide film 23 improves durability such as wear resistance and chemical stability compared to that of Example 1.

[Example 3] Reference numeral 31 denotes a clear float glass plate having a refractive index of 1.51 and a thickness of 51mm, and a tin oxide film 32 with a thickness of 460mm and a tin oxide film 32 with a thickness of 45mm thick are sequentially formed on the surface of the glass plate 31. A 390 mm thick zirconium nitride (ZrNx, X has a value between 0.1 and 1.2) film 33 and a 390 mm thick tin oxide film 34 are each formed by sputtering (FIG. 3). The zirconium nitride film 33 and the tin oxide films 32 and 34 were formed in the same manner as in Example 2. The optical properties of the obtained heat ray blocking glass are shown in Table 1 and FIG. 4.

Table 1 Optical Properties This heat-shielding glass further improves its optical properties due to the optical interference of the three-layer film, and also improves its durability such as abrasion resistance and scientific stability.

〔Effect of the invention〕

As described above, according to the present invention, by selecting the thickness of the coating to a predetermined value, visible light and green transmittance can be kept in a relatively low range of 30% to 70%, and solar transmittance can be reduced to visible light js transmittance. It is possible to obtain a heat ray shielding plate that has a heat ray shielding rate lower than that by 5% or more, usually by 10% or more. Further, since the coating used in the present invention is made of a metal nitride or a metal nitride and a metal oxide dielectric layer, it is durable in the atmosphere and has excellent wear resistance.

[Brief explanation of the drawing]

1 to 3 are partial cross-sectional views of the heat ray blocking glass of the present invention, FIG. 4 is the spectral transmittance curve of the heat ray blocking glass of the present invention, and FIGS. 5 to 6 are the conventional heat ray blocking glass, 7th
The figure is a partially enlarged sectional view of a conventional heat-shielding glass. 11.21, 31 Glass plate 12.22, 33: Zirconium nitride film 23.32, 3
4: Tin oxide film Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7

Claims (3)

[Claims] (1) A transparent substrate made of glass or synthetic resin, and a metal nitride layer of zirconium, titanium, or hafnium with a thickness of 50 Å to 600 Å formed on one surface of the transparent substrate. Heat ray shielding plate with visible light transmittance. (2) A refractive index of 1.8 to 2.4 on the metal nitride layer
A heat ray shielding plate with low visible light transmittance according to claim 1, wherein a metal oxide dielectric layer having a thickness of 10 Å to 600 Å is formed. (3) A transparent substrate such as glass or synthetic resin, and a first metal oxide dielectric having a refractive index of 1.8 to 2.4 and a thickness of 200 Å to 600 Å, formed on one surface of the transparent substrate. The thickness formed on the body layer and the metal oxide dielectric layer is 10
A metal nitride layer of zirconium, titanium, or hafnium with a thickness of 0 Å to 600 Å, and a refractive index of 1.8 to 2.4 and a thickness of 20 nm formed on the metal nitride layer.
A heat ray shielding plate with low visible light transmittance comprising a second metal oxide dielectric layer with a thickness of 0 Å to 600 Å.