JPH09241041A - Glass plate having enhanced amenity - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a glass plate which has a simple film structure, etc., and yet, concurrently and effectively meets the requirements with respect to transparency, mirrory properties and heat insulation a well balanced manner and also, us human- or environment-friendly and excellent in amenity and shows light blue tone by glass surface reflection and further, has radio wave transmissivity. SOLUTION: This glass plate is obtained by forming on one surface of a transparent glass plate, a laminated film consisting of a thin film of a metal such as Ti, Cr, a stainless steel, Ta or a Ni-Cr alloy, or a thin film of nitride- oxide of such a metal, that is formed on the glass plate as the first layer from the glass surface and has a 1 to 30nm thickness and a thin film of oxide of Ta, Ti or Sn, that is formed on the first layer as the second layer from the glass plate and has a 3 to 50nm thickness. The glass plate has 48 to 75% visible light transmissivity and yet, the visible light reflectivity of the glass surface is <=33% and also, the average visible light reflectivity of the glass surface and the laminated film surface is <=33% and the difference in visible light reflectivity between the glass surface and the laminated film surface is <=15% and further, the glass plate also has <=71% solar radiation transmissivity and shows a <=13% excitation purity by transmitted visible light though it.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention provides a simple two-layer laminated film to have a good balance of transparency, mirror effect and heat insulating property of a glass plate, and at the same time, satisfying the requirements. A glass plate that is environmentally friendly, has a glass-like appearance, and has a neutral perspective color and a pale blue glass reflection color tone. Of course, the present invention provides a glass plate which is excellent in habitability and environment and can utilize its function in various applications such as buildings.

[0002]

2. Description of the Related Art In general, high-performance heat ray reflective glass having a high reflectance has been proposed and commercialized. Among them, there is an infrared reflective glass having a high transmittance, and furthermore, a non-reflective glass and the like are known. ing.

For example, Japanese Patent Application Laid-Open No. 2-164744 describes an optical body having excellent durability and a heat ray reflective glass, and an optical body having an optical thin film having at least two layers formed on a substrate, It is disclosed that the outermost layer on the air side is made of a tantalum oxide film, and that a heat ray absorbing film such as a nitride film and a tantalum oxide film having a thickness of 5 to 20 nm are sequentially formed on the substrate. To be done.

Further, for example, in Japanese Patent Laid-Open No. 2-44046,
A transparent plate exhibiting a blue to green reflection color and a method for manufacturing the same are described. A titanium nitride film is formed on one surface of a transparent substrate, and a film made of a transparent metal oxide is formed on the titanium nitride film. Disclosed is a formed transparent body in which the light reflected on the other surface of the transparent substrate is blue to green, and it is described that the metal oxide is titanium oxide, tin oxide, tantalum oxide, or the like. .

Further, for example, Japanese Patent Publication No. 4-59258 discloses that
A method for producing a plate having a transmittance of 5 to 40% in the visible spectrum band and a reflectivity for heat rays is described, wherein a transparent substrate is coated by cathode sputtering, and a transmittance of 5 to 40% and heat rays in the visible spectrum band. In a method of manufacturing a plate having reflectivity to, a first layer is directly sputtered with an oxide layer having an optical thickness of 20 to 280 nm in an oxygen-containing atmosphere, and a second layer is formed from a rare gas and titanium. It has been described to sputter a chromium titanate layer having a geometrical thickness of 10-40 nm in different atmospheres.

[0006]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention In the above-mentioned conventional publications, for example, in the optical body and the heat ray reflective glass having excellent durability described in JP-A-2-164744, the undercoat film is simply resisted. Abrasion resistance and chemical resistance are added to improve the durability by smoothing the surface and lowering the friction resistance so that it can be used as a single plate, the appearance is neutral, high transmittance, low reflectance, automobile It is a simple heat-reflecting glass that is most suitable for use, such as glass substrate / TiNx (about 4 nm) film / TaOx (about 10
nm) film, etc., the visible light transmittance is 71.1%, the sunlight transmittance is 61.6%, the coated surface visible light reflectance is 11.4%, and the glass surface visible light reflectance is 9.1%. However, there is no consideration about the underlying film, especially about various characteristics and color tones depending on the film thickness, and the conditions necessary for making the glass plate with high comfort that the present invention aims to be achieved. What you do is hard to say.

Further, for example, in a transparent plate exhibiting a blue to green reflection color and a method for manufacturing the same as disclosed in Japanese Patent Laid-Open No. 2-44046, for example, a glass substrate / TiNx (about 15 nm) film / TiOx
(Approximately 15 nm) It is disclosed that the reflection color of the glass surface different from the coating surface is blue and the visible light transmittance is 45.5% in the structure composed of a film, etc. Titanium nitride is required to secure the heat ray shielding property. The film thickness of 5 nm or more is necessary, and it is only described that the film thickness of the metal oxide is 5 nm or more in order to obtain the vividness of the reflected color. It is extremely difficult to say that the glass plate has the necessary conditions for forming a glass plate having improved properties.

Further, for example, in the method for producing a plate having a transmittance of 5 to 40% in the visible spectrum band and a reflectivity for heat rays described in Japanese Patent Publication No. 4-59258, the visible light transmittance becomes too low, resulting in a dark color tone. Therefore, it is not possible to improve the transparency, and by making the glass plate have a good balance of transparency, mirror effect and heat insulation, and at the same time satisfying it, it is friendly to people and the environment and has a glass-like appearance and presence. It is hard to say that the glass surface reflection color tone of a light blue color which is neutral and has a transparent color and which has radio wave transparency.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and has a combination of a specified simple film structure and its film thickness, and has a specified visible light transmittance. Visible light reflectance, solar radiation transmittance, and stimulus purity of visible light transmission are used to fully demonstrate the glassiness and appeal, and the transparency and presence, the design, the transparency, the mirror property, and the heat insulating property. Among them, it has well-balanced optical characteristics, has durability such as chemical resistance, weather resistance or abrasion resistance, yet exhibits a soft pale blue glass surface reflection color tone and further has radio wave transmission. It is possible to inexpensively provide a glass plate with improved habitability.

That is, according to the present invention, one surface of a transparent glass plate has a thickness of 1 nm as a first layer from the glass surface side.
Oxide of Ti, Cr, SUS, Ta, NiCr metal thin film or nitrogen oxide thin film having a thickness of 30 nm or less, and Ta, Ti, Sn having a thickness of 3 nm or more and 50 nm or less as a second layer on the first layer Consists of a laminated film of thin films with visible light transmittance of 48 to 75%, and the visible light reflectance of the glass surface is 33% or less and the average visible light reflectance of the glass surface and the film surface is 33% or less. And the difference in visible light reflectance between the glass surface and the film surface is 15% or less, the solar radiation transmittance is 71% or less, and the stimulus purity of visible light transmission is 13% or less. A glass plate with enhanced habitability.

Further, the above-mentioned glass having enhanced comfortability, characterized in that the first thin film is a nitrogen oxide thin film of Ti, Cr, SUS, or NiCr having a film thickness of 3 nm or more and 25 nm or less. Board.

Further, the above-mentioned glass having enhanced comfortability is characterized in that the first thin film is a metal thin film of Ti, Cr, SUS, Ta or NiCr having a film thickness of 1 nm or more and 10 nm or less. Board.

Further, the glass plate with enhanced comfortability has a visible light transmittance of 50 to 73%, a visible light reflectance of the glass surface of 30% or less, and an average visible light between the glass surface and the film surface. Light reflectance of 30% or less, visible light reflectance difference between glass surface and film surface of 10% or less, solar radiation transmittance of 71% or less, and stimulus purity of visible light transmission of 13% or less The glass plate with improved comfort as described above.

Furthermore, the surface resistance value of the laminated film is 0.5 k.
Ω / mouth or more, the above-mentioned glass plate with enhanced comfortability. Furthermore, the above-mentioned glass plate with enhanced habitability, wherein the surface resistance value of the laminated film is 1 kΩ / mouth or more.

Furthermore, the above-mentioned glass plate with improved habitability is provided with the above-mentioned glass plate with improved habitability, characterized in that it has radio wave permeability.

[0016]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Here, the glass plate is, for example, an inorganic glass plate which is a commercially available soda lime glass used for various glass plates such as buildings as well as window materials for buildings. Float glass is optimal, or may be a so-called glass plate made of an organic material such as polycarbonate or acrylic,
It may be a flat or bent glass, and may be variously processed glass such as tempered glass, laminated glass, double-glazed glass and surface-treated glass, or glass for various uses. The shape of the glass plate is not particularly limited, but may be a substantially quadrilateral having a long side and a short side.

Further, the thickness of the transparent glass plate is preferably about 5 to 19 mm, and for example, a thickness of 4 mm or less cannot be used as an outer wall material for buildings in view of wind load in most cases. Further, for example, if it exceeds 19 mm, the absorptivity in the glass becomes high, so that it is not possible to satisfy both sides of the transmittance and the reflectance at the same time. A more preferable plate thickness is about 6 to 15 mm.

The film thickness is 1 nm or more and 30 nm or less.
First of all, a metal thin film of Ti, Cr, SUS, Ta, or NiCr or a nitrogen oxide thin film was coated as the first layer from the glass surface side.
Regarding the metal thin film of Ti, Cr, SUS, Ta, and NiCr (using Ar gas during sputtering), the film thickness is preferably about 1 nm or more and 10 nm or less, more preferably about 1 nm or more and 5 nm or less, and visible. In the blue color tone with the above-mentioned specific value being secured as the light transmittance, it is assumed to have radio wave transmittance, and even when the thin film of the second layer is covered, the visible light reflectance of the glass surface is 33% or less, preferably 30% or less, and the average visible light reflectance between the glass surface and the film surface is, for example, 33%.
Below, preferably 30% or less and the visible light reflectance difference between the glass surface and the film surface is 15% or less, preferably 10% or less, further solar radiation transmittance is 71% or less and the stimulus purity of visible light transmission. Since it can be 13% or less, it is selected as the first layer.

Next, the film thickness is 1 nm or more and 30 nm or less
The first layer of Ti, Cr, SUS, and NiCr nitrogen oxide thin films was coated from the glass side. First, TiNxOy [x and y was determined by the flow rate ratio of Ar gas and N ₂ gas during sputtering. . The flow rate ratio may be such that the value of O ₂ / (O ₂ + N ₂ ) is in the range of 0.001 to 0.05. Also, if the surface resistance of the TiNxOy thin film obtained as needed is 1 kΩ / hole or more, the film formation rate is increased or the optical constants (n = refractive index, k = extinction coefficient) of the TiNxOy thin film are controlled. Ar gas may be introduced for the purpose of doing so. The thin film is the same as the above-mentioned metal thin film, and among them, in order to secure visible light transmittance, a solar radiation transmittance of 71% or less, preferably 67% or less, which is a thermal performance of a heat ray absorbing glass is secured. However, in addition to blue color tone and other optical characteristics, for example, the visible light reflectance of the heat ray reflective glass can be made to be unmatched, and it is suitable for mass production as a functional film having heat insulation performance and the like. Good adhesion to glass, so choose as the first layer.

Further, CrNxOy [x and y are determined by the flow rate ratio of O ₂ gas and N ₂ gas at the time of sputtering. The flow ratio is O ₂
The value of / (O ₂ + N ₂ ) may be in the range of 0.001 to 0.05. Also, if necessary, increase the deposition rate or use CrNx
Ar gas may be introduced for the purpose of controlling the optical constants (n = refractive index, k = extinction coefficient) of the Oy thin film. The thin film is similar to the above-mentioned metal thin film, and in particular, it has a visible light transmittance of 48% or more and has a blue color tone, and has a thermal performance that is about the same as or close to that of heat-absorbing glass. While maintaining a transmittance of 71% or less, preferably 70% or less, it is possible to mass-produce it as a functional film having heat insulating performance, etc., even with respect to other optical characteristics, for example, the visible light reflectance of heat ray reflective glass. It is suitable for the first layer because it is suitable for glass and has good adhesion to glass.

Furthermore, SUSNxOy or NiCrNxOy [x
And y are determined by the flow ratio of O ₂ gas and N ₂ gas at the time of sputtering, and the flow ratio is a value of O ₂ / (O ₂ + N ₂ ), and the SUSNxOy obtained as needed. Or NiCrNxOy
In order to increase the deposition rate if the surface resistance of the thin film is 1 kΩ / port or more, or to control the optical constants (n = refractive index, k = extinction coefficient) of the SUSNxOy or NiCrNxOy thin film Ar gas may be introduced. ] The thin film is the same as the above-mentioned metal thin film, and in particular, in securing visible light transmittance, the solar radiation transmittance of 71% or less, which is the thermal performance of heat ray absorbing glass, is preferably 70% or less. While ensuring the color tone of the blue color system and other optical characteristics, for example, the visible light reflectance of the heat ray reflective glass can be made to be less than that, and it is suitable for mass production as a functional film having heat insulation performance. Therefore, select it for the first layer.

Next, T having a film thickness of 3 nm or more and 50 nm or less
First, the SnOx (1 <x ≤ 2) thin film was formed as a protective film for the first thin film by coating the laminated film of oxide thin films of a, Ti, and Sn as the second layer. And is useful as an interference film, and has a higher film formation speed than the TiOx thin film and TaOx thin film in the structure of the heat insulating thin film / oxide thin film,
Especially for the second layer because it has excellent productivity and color unevenness is less likely to appear. The cost can be reduced by adopting a simple film configuration as the two-layered film and eliminating the need for complicated steps.

Further, the TiOx (1 <x≤2) thin film serves as a protective film for the first thin film to enhance durability and is useful as an interference film, and is suitable for light blue color tones. Of course is necessary, of course, because it is particularly excellent in productivity, so select it as the second layer.

Further, the TaOx (1 <x≤5 / 2) thin film serves as a protective film for the first thin film to enhance durability and is useful as an interference film, and has a pale blue color tone. On the other hand, it is necessary, so choose the second layer.

The TiNxOy or CrNxO used as the base
y, or the thickness of SUSNxOy or NiCrNxOy thin film layer is 3n
The thickness of the TaOx, TiOx, or SnOx thin film layer to be coated is 3 nm or more and 50 nm or less.
If the NxOy or CrNxOy or SUSNxOy or NiCrNxOy thin film layer is less than 3 nm thick and the TaOx, TiOx or SnOx thin film layer is less than 3 nm thick, for example, the visible light transmittance is 75
%, The transparency becomes stronger, the solar radiation transmittance, which is the thermal performance, exceeds 71%, and the heat insulation becomes unsatisfactory, and TiNxOy or CrNxOy or SUSNxOy or
NiCrNxOy thin film layer thickness exceeds 25nm and TaOx or TiOx
Or if the thickness of the SnOx thin film layer exceeds 50 nm,
For example, the visible light transmittance is low, the visible light reflectance is too high, and the light blue-tone reflection color tone is not developed, so that it cannot be said that it is a glass plate with extremely high habitability. is there. Preferably, the thickness of the TiNxOy or CrNxOy, or the SUSNxOy or NiCrNxOy thin film layer is about 4 nm or more and 25 nm or less, and the thickness of the TaOx, TiOx or SnOx thin film layer is about 4 nm or more and 40 nm or less.

Furthermore, the above-mentioned Ti, Cr, SUS used as a base
The thickness of the metal thin film layer of Ta, NiCr is 1 nm or more and 10 nm or less, and the film thickness of the TaOx, TiOx, or SnOx thin film layer to be coated is 3 nm or more and 50 nm or less is Ti, Cr, SUS,
Ta or NiCr metal thin film thickness is less than 1 nm and TaOx
Alternatively, if the thickness of the TiOx or SnOx thin film layer is less than 3 nm, for example, the visible light transmittance exceeds 75% and the transparency becomes strong, and the solar radiation transmittance, which is the thermal performance, exceeds 71% and the heat insulation property is increased. Is not satisfied, and Ti, Cr, SUS, Ta
Or, if the film thickness of the NiCr metal thin film layer exceeds 10 nm and the film thickness of the TaOx or TiOx or SnOx thin film layer exceeds 50 nm, for example, the visible light transmittance becomes low, and the visible light reflectance also becomes high. This is because the glass plate is too high and it cannot be said that it is a glass plate with enhanced comfortability. Preferably Ti, Cr,
The thickness of the metal thin film layer of SUS, Ta or NiCr is 1 nm or more and 8 nm
The thickness of the TaOx or TiOx or SnOx thin film layer is 4 or less.
It is to be about 40 nm or less between nm

Further, the visible light transmittance is 48 to 75%, the visible light reflectance of the glass surface is 33% or less, and the average visible light reflectance between the glass surface and the film surface is 33% or less and the glass surface is The difference in visible light reflectance of the film surface is 15% or less, and further the solar radiation transmittance is 71% or less is that the visible light transmittance is
In the range of less than 48% or the visible light reflectance of more than 33%, the visible light reflection performance, especially the reflection performance of the glass surface becomes too high, and the transparency deteriorates, and the visible light transmittance exceeds 75% or the solar radiation transmission. In the range of 71% or more, the reflection performance becomes too low and the specified mirror effect cannot be obtained.For example, the solar radiation transmittance exceeds 71%, and the thermal performance cannot be ensured, and the desired heat insulation is exhibited. Because you cannot do it. Preferably the visible light transmittance is 50 ~
75%, the visible light reflectance of the glass surface is 30% or less, and the average visible light reflectance of the glass surface and the film surface is 30% or less.

The visible light reflectance difference between the glass surface and the film surface is 15
% Or less is because there is a problem that the transparency is not utilized when the visible light reflectance difference exceeds 15%, for example, absorption in glass or multiple reflection. The visible light reflectance difference is preferably about 12% or less, more preferably about 10% or less, and the transparency and the mirror property are remarkably balanced.

Generally, the optical characteristic is a combination of transmittance (t), reflectance (r) and absorptance (a) as shown in the characteristic diagram of FIG. Within the above range (for example, the hatched portion in FIG. 1 as an example), the transmissivity and the reflective property, that is, the mirror property and the heat insulating property are well balanced at the same time, which is friendly to humans and the environment and more comfortable to live in. be able to.

Further, the stimulation purity of visible light transmission is 13%.
The reason why it is the following is that when the stimulus purity exceeds 13% in the film structure and optical characteristics, the transparency is impaired, a sense of discomfort is likely to occur, and it is difficult to say that it is friendly to people and the environment. Is.

Further, the laminated film of the thin films is made of Ti, Cr, SU.
S, Ta, NiCr or TiNxOy, CrNxOy, SUSNxOy or
The combination of each thin film of NiCrNxOy and the thin film of TaOx, TiOx, or SnOx shows a light blueish tint in the glass surface reflection tone, but rather, it is a neutral tone or a tone close to it in transmitted light. It is also possible to obtain the desired visible light transmission by the two-layer design and to have the required transparency, and also to have the desired visible light reflection and to appropriately provide the mirror effect. Moreover, it is possible to impart heat insulation.

Furthermore, the reason why the glass plate having the radio wave transmission property is used is that the radio wave reflection type glass plate causes a so-called radio wave interference such as a ghost phenomenon on the TV in the surrounding residents.
As described above, according to the glass plate of the present invention with enhanced comfortability, a glass plate having a thin film layer formed on the surface of a transparent substrate has a film thickness of 1 nm or more as the first layer from the glass surface side.
Ti, Cr, SUS, Ta or NiCr metal thin film having a thickness of 3 nm or less, or nitrogen oxide thin film, and a TaOx, TiOx or SnOx thin film having a thickness of 3 nm or more and 50 nm or less as a second layer on the first layer The film has a visible light transmittance of 48 to 75%, and the glass surface has a visible light reflectance of 33% or less, and the average visible light reflectance between the glass surface and the film surface is 33% or less and the glass surface. The visible light reflectance difference between the film and the film surface is 15% or less, the solar radiation transmittance is 71% or less, and the stimulus purity of visible light transmission is 13%.
By setting the content to be less than or equal to%, it is possible to obtain, for example, a characteristic diagram of FIG. 1 [a triangular diagram (transmittance (t), reflectance (r), absorptance (a) in visible light) (see In the unit:%)], as shown by hatching, an example of a glass plate area with enhanced comfortability, while utilizing the excellent characteristics of clear glass and the characteristics of heat-ray-reflecting glass, a characteristic comparable to heat-ray-absorbing glass is developed. It has a good balance of optical characteristics, including heat insulation, while at the same time being able to exhibit a glass-like appearance to appeal its design and to provide transparency and a sense of existence, as well as transparency and mirrorability. A glass plate that is durable and has chemical resistance, weather resistance, abrasion resistance, etc., and has a light blue glass surface reflection color tone and radio wave transmission that enhances habitability. It can be provided at a low cost with a simple film structure, etc., for example, in the courtyard, at the same time, it is possible to achieve a mirror property that makes the courtyard inside the building look large, and a see-through property that makes it visible from the inside. While enjoying the night view from the room in hotels, etc., it has the advantage of being comfortable and optimal for people and the environment.

[0033]

The present invention will be described below in detail with reference to examples. However, the present invention is not limited to such an embodiment.

Example 1 A float clear glass (6) having a size of about 300 mm × 300 mm and a thickness of about 6 mm was sequentially washed with a neutral detergent, water rinse, isopropyl alcohol, and dried, and then the vacuum chamber of a DC magnetron sputtering apparatus. The target is set so that it can reciprocate upward, facing the target of Ti and Sn, and then the inside of the chamber is degassed to about 5 × 10 ⁻⁶ Torr with a vacuum pump, Ar gas is introduced into the chamber to adjust the vacuum to about 2 × 10 ^-3
The power of about 0.12 kW was applied to the Ti target while maintaining it at Torr, and the speed of the DC magnetron reactive sputtering with the mixed gas was increased above the Ti target.
By transporting the plate glass at 270 mm / min, a metal thin film of Ti having a thickness of about 3 nm was formed as the first layer. After the film formation was completed, the application to the Ti target was stopped.

Then, the plate glass is placed in the vacuum chamber.
Approximately 5 × 10 inside the tank with a vacuum pump^-6Up to Torr
After degassing to_TwoGas and Ar gas (however, Ar
Gas and O_TwoGas flow rate ratio of gas is O_Two/ (Ar + O_Two) Has a value of 0.5 to
1.0 (Note that the Ar gas flow rate is zero when the value is 1.0)
It should be in the range of. ] To introduce a vacuum of about 2 × 10 ^-3
Hold it at Torr and supply about 1.0kW of power to the Sn target.
Apply the DC magnetron reaction spatter with the mixed gas.
Speed above the target of Sn.
By transporting the plate glass at 107mm / min
Approximately 40 nm thick SnOx (1
<X ≦ 2) A thin film was laminated as a second layer. Film formation is complete
After that, the application to the Sn target was stopped.

With respect to the obtained flat glass with a laminated thin film composed of two layers, visible light transmittance (Tv: 380 to 780 nm), visible light reflectance (Rv: 380 to 780 nm), visible light reflectance difference, stimulus purity (Pv : 380-780nm) and solar radiation transmittance (Ts: 340
Up to 1800 nm) and solar reflectance (Rs: 340 to 1800 nm) are measured with a 340 type self-recording spectrophotometer (manufactured by Hitachi Ltd.), and each data of transmittance and reflectance for each predetermined wavelength and JIS Z
The optical characteristics (light source: D ₆₅ 2 ° field of view) were determined according to 8722 and JIS R 3106, and some of them are shown in Tables 1 and 2 for visible light transmittance, average visible light reflectance, visible light reflectance difference, and solar radiation. The transmittance and the stimulation purity are shown.

Regarding the surface resistivity, the one having a resistance of 10 ⁵ Ω / port or less is a four-point probe resistance measuring device RT-8 (manufactured by NAPSON),
10 ⁵ Ω / mouth to 10 ⁵ MΩ / mouth is a surface high resistance meter HIREST
A Measured by HT-210 (Mitsubishi Yuka), 0.5 kΩ /
A sample having a mouth or more, preferably 1 kΩ / mouth or more, was marked with a mark 透過 as having radio wave transmission, and a mark less than 0.5 kΩ / mouth was marked with a triangle.

[0038] Furthermore, the one with good cost in consideration of productivity, etc., and the one with a glass plate having desired habitability improved from the above-mentioned characteristics and appearance etc. as a comprehensive evaluation, Those that are not expected are shown in Table 2 by crosses.

As a result, G (glass) / Ti (3 nm) / SnOx
As shown in Table 1 and Table 2, the laminated glass with laminated thin film composed of (40 nm) and a two-layer film has a visible light transmittance (Tv)
Is 67.0%, the visible light reflectance (Rv) on the glass surface is 17.8%, the average visible light reflectance between the glass surface and the film surface is 15.3%, and the visible light reflectance difference (△ Rv) between the glass surface and the film surface is Is 4.9%, the stimulus purity of visible light transmission is 2.3%, and the stimulus purity of glass surface reflection is 16.5%. It has a well-balanced transparency and mirror effect, is friendly to humans and the environment, and has a high degree of solar radiation. It has adiabatic properties such as a transmittance (Ts) of 61.9%, and exerts a large cooling load reduction effect, for example.

Further, it is a glass plate which has a light blue reflection tone on the glass surface, has a surface resistance value of 1.0 kΩ / mouth and is also radio wave transmissive, and is intended to enhance the comfort level of the present invention. It was

Example 2 A float clear glass (6) having a thickness of 6 mm as in Example 1
As shown in Tables 1 and 2, the laminated glass with laminated thin film was obtained in the same manner as in Example 1 except that only the first layer was changed to a Cr thin metal film. The Cr metal thin film is a Cr target.
Using a get, introduced gas is Ar gas, applied power is 0.12kW,
A metal thin film of Cr having a film thickness of about 1 nm was obtained under the condition that the transport speed was about 1628 mm / min.

With respect to the obtained laminated glass with laminated thin film, each device was used to measure and evaluate in the same manner as in Example 1.
As a result, the obtained laminated glass with laminated thin film was as shown in Tables 1 and 2, and each optical property such as visible light transmittance, visible light reflectance, visible light reflectance difference and stimulus purity was the same as in Example 1. Not only the characteristics but also the thermal performance due to the solar radiation transmittance, the color tone and the radio wave transparency were all within the desired range, and it was a glass plate with the desired comfortability.

Example 3 Float clear glass (6) with a thickness of 6 mm as in Example 1
As shown in Tables 1 and 2, the first layer was changed to a metal thin film of Ta and the second layer was changed to
A glass sheet with a laminated thin film, which was changed to a thin film of TiO ₂ , was obtained.

That is, as in the first embodiment, first, Ta
For the metal thin film, a Ta target was used, the introduced gas was Ar gas, the applied power was 0.12 kW, and the plate glass conveyance speed was about 340 mm.
A metal thin film of Ta having a film thickness of about 4 nm was obtained under the condition of / min. Then, for the TiO ₂ thin film, a Ti target was used, and the introduced gas was
O ₂ gas and Ar gas (However, the gas flow ratio of Ar gas and O ₂ gas is
The value of O ₂ / (Ar + O ₂ ) may be in the range of 0.5 to 1.0 (the Ar gas flow rate is zero when the value is 1.0). ], The applied power is about 3.0kW, the sheet glass transport speed is about 70mm / min
Under the conditions described above, a TiOx (1 <x ≦ 2) thin film having a film thickness of about 20 nm was obtained as a second layer on the first metal thin film of Ta.

The obtained laminated glass with laminated thin film was measured and evaluated in the same manner as in Example 1 by using each device.
As a result, the obtained laminated glass with laminated thin film was as shown in Tables 1 and 2, and each optical property such as visible light transmittance, visible light reflectance, visible light reflectance difference and stimulus purity was the same as in Example 1. Not only the characteristics but also the thermal performance due to the solar radiation transmittance is excellent, it has a light blue color tone, and it is within the target range including 0.5 kΩ / mouth and a little marginal radio wave transmission, and the desired habitability is achieved. It was a raised glass plate.

Example 4 Float clear glass (6) with a thickness of 6 mm as in Example 1
As shown in Tables 1 and 2, only the first layer in Example 3 was changed to a NiCr metal thin film, and the other layers were formed in the same manner as in Example 3 except that TiOx (1 <x ≦ 2) A thin film was coated to obtain a laminated glass with a thin film. The NiCr metal thin film uses a NiCr target, the introduced gas is Ar gas, the applied power is 0.2 kW, and the plate glass transport speed is about 1325 mm.
A metal thin film of NiCr having a film thickness of about 2 nm was obtained under the condition of / min.

The obtained laminated glass with laminated thin film was evaluated by performing each measurement using each device in the same manner as in Example 1.
As a result, the obtained laminated glass with laminated thin film was as shown in Tables 1 and 2, and each optical property such as visible light transmittance, visible light reflectance, visible light reflectance difference and stimulus purity was the same as in Example 1. Not only the characteristics but also the thermal performance due to the solar radiation transmittance, the color tone and the radio wave transparency were all within the desired range, and it was a glass plate with the desired comfortability.

Example 5 As in Example 1, float clear glass having a thickness of about 6 mm
Using (6), as shown in Table 1 and Table 2, first, the Cr and Sn targets set in the vacuum chamber of the DC magnetron sputtering apparatus are set so as to be able to reciprocate upwards, and then set as described above. Approximately 5 × 10 ^-6 Torr with a vacuum pump in the tank
And then degassed it in the vacuum chamber with N ₂ gas and O ₂ gas [O ₂ /
(O ₂ + N ₂₎ = 0.02, however, the gas flow ratio of O ₂ gas and N ₂ gas O ₂
The value of / (O ₂ + N ₂ ) may be in the range of 0.001 to 0.05. Also, the surface resistance of the CrNxOy thin film obtained as required is 1 kΩ.
/ Mouth or more to increase the deposition rate or Cr
Ar gas may be introduced for the purpose of controlling the optical constants (n = refractive index, k = extinction coefficient) of the NxOy thin film. ], The degree of vacuum is maintained at about 2 × 10 ^-3 Torr, about 0.5 kW of electric power is applied to the Cr target, and DC by the mixed gas is applied.
A CrNxOy thin film having a thickness of about 4 nm was formed as a first layer by transporting the plate glass in the magnetron reactive sputtering above the Cr target at a speed of about 450 mm 3 / min. After the film formation was completed, the application to the Cr target was stopped.

Then, in the same manner as in Examples 1 and 2, Sn glass having a thickness of about 10 nm was formed on the surface of the CrNxOy thin film of the glass sheet by changing only the conveying speed of the glass sheet to about 426 mm / min.
An Ox (1 <x ≦ 2) thin film was deposited as a second layer.

Each of the obtained two-layered sheet glass with laminated thin films was measured and evaluated in the same manner as in Example 1 by using each device. As a result, the obtained laminated glass with laminated thin film was as shown in Tables 1 and 2, and each optical property such as visible light transmittance, visible light reflectance, visible light reflectance difference and stimulus purity was the same as in Example 1. Not only the characteristics but also the thermal performance due to the solar radiation transmittance, the color tone and the surface resistance value are 590 kΩ / mouth and excellent radio wave transmission are all within the target range, and it is a glass plate that aims to enhance the desired habitability. It was

Examples 6 to 7 Float clear glass (6) with a thickness of 6 mm as in Example 1
Was used, and only the film thickness of the second layer was changed to the values shown in Table 1 and Table 2 with the same film configuration as in Example 5, to obtain a laminated thin film-attached plate glass.

With respect to the obtained laminated glass with laminated thin film, each measurement was performed using each device and evaluated in the same manner as in Example 1.
As a result, the obtained laminated glass with laminated thin film was as shown in Tables 1 and 2, and each optical property such as visible light transmittance, visible light reflectance, visible light reflectance difference and stimulus purity was the same as in Example 1. Not only the characteristics but also the thermal performance due to the solar radiation transmittance, the color tone, and the excellent radio wave transmission were all within the desired range, and it was a glass plate with the desired comfortability.

Examples 8 to 9 As in Example 1, float clear glass having a thickness of 6 mm (6)
As shown in Table 1 and Table 2, the second layer of CrNxOy
A thin film was obtained in the same manner as in Example 5, and only the second layer was changed to a TaOx thin film to obtain a plate glass with a laminated thin film.

That is, the inside of the tank is about 5 × with a vacuum pump.
After degassing to 10 ^-6 Torr, O ₂ gas and Ar gas were added to the vacuum chamber (however, the gas flow rate ratio of Ar gas and O ₂ gas was O ₂ / (Ar + O ₂ )
Value of 0.5 to 1.0 (the Ar gas flow rate is zero at the value of 1.0). ] And the vacuum degree is maintained at about 2 × 10 ⁻³ Torr, and the target of Ta is about 2.
Applying a power of 0 kW, and in the DC magnetron reactive sputtering with the mixed gas, the transport speed of the plate glass is about 65 mm / min in Example 8 and about 43 mm / min in Example 9 above the target of Ta. By the plate glass
On the surface of the CrNxOy thin film, a thickness of about 20 nm in Example 8 and Example 9 was used.
To obtain a TaOx (1 <x≤5 / 2) thin film having a thickness of about 30 nm as the second layer.

With respect to the obtained laminated glass with laminated thin film, each measurement was performed using each device and evaluated in the same manner as in Example 1.
As a result, the obtained laminated glass with laminated thin film was as shown in Tables 1 and 2, and each optical property such as visible light transmittance, visible light reflectance, visible light reflectance difference and stimulus purity was the same as in Example 1. Not only the characteristics but also the thermal performance due to the solar radiation transmittance, the color tone, and the excellent radio wave transmission were all within the desired range, and it was a glass plate with the desired comfortability.

[0056]

[Table 1]

[0057]

[Table 2]

Example 10 As in Example 1, a float clear glass (6) having a thickness of 6 mm
As shown in Tables 3 and 4, Ti is used as the first layer.
A plate glass with a laminated thin film was obtained in which the SnOx thin film similar to that in Example 5 was used as the second layer in place of the NxOy thin film.

That is, as with the CrNxOy thin film, the TiNxOy thin film uses a Ti target, and the introduction gas is N ₂ gas and O ₂ gas [O ₂ / (O ₂ + N ₂ ) = 0.02, where O ₂ The gas flow rate ratio between the gas and the N ₂ gas may be such that the value of O ₂ / (O ₂ + N ₂ ) is in the range of 0.001 to 0.05. Also, if the surface resistance of the TiNxOy thin film obtained as needed is 1 kΩ / hole or more, the film formation rate is increased or the optical constants (n = refractive index, k = extinction coefficient) of the TiNxOy thin film are controlled. Ar gas may be introduced for the purpose of doing so. ], The applied power is about 1.0 kW,
A TiNxOy thin film with a thickness of about 12 nm was obtained by setting the thickness to 263 mm / min.

With respect to the obtained plate glass with a laminated thin film, each measurement was carried out using each apparatus in the same manner as in Example 1 and evaluated.
As a result, the obtained laminated glass with laminated thin film was as shown in Tables 3 and 4, and each optical property such as visible light transmittance, visible light reflectance, visible light reflectance difference and stimulus purity was the same as in Example 1. Not only the characteristics but also the thermal performance due to the solar radiation transmittance, the color tone, and the excellent radio wave transmission were all within the desired range, and it was a glass plate with the desired comfortability.

Examples 11 to 12 As in Example 1, float clear glass (6) having a thickness of 6 mm
Was used to form a film having the same structure as in Example 10, and only the film thickness of the second layer was changed in the same manner as in Examples 6 and 7, as shown in Table 3, to obtain a laminated thin film-attached plate glass.

The obtained plate glass with a laminated thin film was subjected to various measurements and evaluations in the same manner as in Example 1 using each apparatus.
As a result, the obtained laminated glass with laminated thin film was as shown in Tables 3 and 4, and each optical property such as visible light transmittance, visible light reflectance, visible light reflectance difference and stimulus purity was the same as in Example 1. Not only the characteristics but also the thermal performance due to the solar radiation transmittance, the color tone and the radio wave transparency were all within the desired range, and it was a glass plate with the desired comfortability.

Examples 13 to 14 As in Example 1, float clear glass having a thickness of 6 mm (6)
As shown in Tables 3 and 4, the same TiNxOy thin films as in Examples 10 to 12 were changed only in thickness to about 7 nm in Example 13 and to about 16 nm in Example 14, and the second layer was implemented. The same TiOx thin films as in Examples 3 and 4 were used, except that the thickness was changed to about 3.7 nm in Example 13 and about 20 nm in Example 14 to obtain a laminated glass with a thin film.

The obtained laminated glass with laminated thin film was measured and evaluated in the same manner as in Example 1 by using each device.
As a result, the obtained laminated glass with laminated thin film was as shown in Tables 3 and 4, and each optical property such as visible light transmittance, visible light reflectance, visible light reflectance difference and stimulus purity was the same as in Example 1. Not only the characteristics but also the thermal performance due to the solar radiation transmittance, the color tone and the radio wave transparency were all within the desired range, and it was a glass plate with the desired comfortability.

Examples 15 to 16 Float clear glass (6) with a thickness of 6 mm as in Example 1
As shown in Tables 3 and 4, Example 15 uses the same TiNxOy thin film and film thickness as the first layer film of Example 14, and Example 16 uses the first layer of Example 14 as the first layer. The same TiNxOy as the film
A thin glass having a laminated thin film was obtained by changing the thickness of the thin film to about 24 nm and using the same SnOx thin film and thickness as the second layer of Examples 7 and 12 as the second layer.

The obtained laminated glass with laminated thin film was measured and evaluated in the same manner as in Example 1 by using each device.
As a result, the obtained laminated glass with laminated thin film was as shown in Tables 3 and 4, and each optical property such as visible light transmittance, visible light reflectance, visible light reflectance difference and stimulus purity was the same as in Example 1. Not only the characteristics but also the thermal performance due to the solar radiation transmittance, the color tone and the radio wave transmittance are all within the target range, and even if the visible light reflectance is slightly high and the radio wave transmittance is slightly lowered, the aim is It was a glass plate that improved the habitability of the period.

Examples 17 to 18 Float clear glass having a thickness of 6 mm as in Example 1 (6)
As shown in Tables 3 and 4, using the same TiNxOy thin film and film thickness as the first layer film of Examples 10 to 12, the same TaOx thin film as the second layer of Examples 8 and 9 was used as the second layer. By using only the film thickness of about 5 nm in Example 17 and about 20 nm in Example 18, a plate glass with a laminated thin film was obtained.

With respect to the obtained laminated glass with laminated thin film, each measurement was performed using each device in the same manner as in Example 1 and evaluated.
As a result, the obtained laminated glass with laminated thin film was as shown in Tables 3 and 4, and each optical property such as visible light transmittance, visible light reflectance, visible light reflectance difference and stimulus purity was the same as in Example 1. Not only the characteristics but also the thermal performance due to the solar radiation transmittance, the color tone and the radio wave transparency are all within the target range, and even if the visible light reflectance is slightly high and the radio wave transparency is excellent, it is the desired residence. It was a glass plate with improved properties.

[0069]

[Table 3]

[0070]

[Table 4]

[0071]

As described above, according to the present invention,
The film constitution of a glass plate having a laminated thin film layer consisting of two layers and its film thickness are specified, and visible light transmittance, average visible light reflectance and visible light reflectance difference, and further solar radiation transmittance and stimulus purity By specifying such as,
The glass-likeness is fully exhibited to enhance the design, and the transparency and the presence, as well as the transparency and the mirror property, are expressed, and the heat insulation and the balance can be satisfied at the same time, which is durable and has a pale blue color. It is possible to provide a glass plate that is friendly to people and the environment and has enhanced habitability at a low cost with a simple film structure, etc. As well as a window material for windows, it provides a glass plate excellent in habitability and environment, which exhibits its function in various applications such as buildings.

[Brief description of drawings]

FIG. 1 shows an example of a glass plate area having improved livability according to the present invention.
Characteristic diagram represented by transmittance (t), reflectance (r) and absorptance (a) in visible light (triangle diagram, unit:%)
FIG. 4 is an explanatory diagram shown by hatching.

Front Page Continuation (72) Inventor Shinichi Araya 3-7-1, Kandanishikicho, Chiyoda-ku, Tokyo Central Glass Co., Ltd.

Claims (7)

[Claims] 1. A transparent glass plate having a film thickness of 1 nm or more and 30 nm or less as a first layer from the glass surface side on one surface thereof.
Ti, Cr, SUS, Ta, NiCr metal thin film or nitrogen oxide thin film, and a laminated film of Ta, Ti, Sn oxide thin films having a thickness of 3 nm or more and 50 nm or less as the second layer on the first layer. It has a visible light transmittance of 48 to 75%, a visible light reflectance of the glass surface of 33% or less, and an average visible light reflectance of the glass surface and the film surface of 33% or less and the glass surface. The difference in visible light reflectance of the film surface is 15% or less, the solar radiation transmittance is 71% or less, and the stimulus purity of visible light transmission is 13% or less. Glass plate. 2. The thin film of the first layer has a thickness of 3 nm or more.
The glass sheet with enhanced habitability according to claim 1, which is a nitrogen oxide thin film of Ti, Cr, SUS, or NiCr having a thickness of 25 nm or less. 3. The first thin film has a film thickness of 1 nm or more.
The glass sheet with enhanced habitability according to claim 1, which is a metal thin film of Ti, Cr, SUS, Ta, or NiCr having a thickness of 10 nm or less. 4. The glass plate having enhanced comfortability has a visible light transmittance of 50 to 73%, a visible light reflectance of the glass surface of 30% or less, and an average visible light between the glass surface and the film surface. The light reflectance is 30% or less and the visible light reflectance difference between the glass surface and the film surface is
The glass plate with enhanced habitability according to claim 1, wherein the glass transmittance is 10% or less, the solar radiation transmittance is 71% or less, and the stimulus purity of visible light transmission is 13% or less. . 5. The glass plate with enhanced comfortability according to claim 1, wherein the surface resistance value of the laminated film is 0.5 kΩ / mouth or more. 6. The glass plate with enhanced habitability according to claim 1, wherein the surface resistance value of the laminated film is 1 kΩ / mouth or more. 7. The glass plate with enhanced habitability according to claim 1, wherein the glass plate with enhanced habitability has radio wave transparency.