JPH0369531A - Single-sheet heat insulating glass - Google Patents

Abstract

PURPOSE:To obtain the single-sheet heat insulating glass having wear resistance, durability and weatherability, capable of transmitting an electric wave through a vehicle and effectively used for air conditioning by forming a specified transparent dielectric film on the surface of a specified transparent colored glass base sheet in prescribed optical thickness. CONSTITUTION:The transparent dielectric film having 1.9-2.4 refractive index is formed on the surface of a transparent colored glass base sheet having >=65% transmissivity and <=75% solar radiation transmissivity in 2200-3100Angstrom optical thickness by sputtering or CVD to produce the single-sheet heat insulating glass. The glass has the following characteristics. Namely, the visible light transmissivity is controlled to >=65% and the visible light reflectivity to <=15%. The solar radiation transmissivity is >=5% lower than that of the transparent colored glass base sheet. Furthermore, the variations in the transmissivity and haze in the taper test by CS-10F after 1000 rotations are controlled within 10% of those before test, and the surface volume resistivity is controlled to >=100OMEGA.cm.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention improves heating and cooling effects and has a relatively high visible light transmittance, and is also relatively resistant to radio wave transmission. The present invention relates to a single-pane insulating glass with excellent abrasion resistance, which is particularly useful as an insulating glass for vehicles, and which can be used as a single-pane in particular as a side or door window glass or a rear window glass.

[Prior art] Conventionally, for example, vehicle window glasses have achieved high visible light transmittance with a configuration of transparent dielectric or transparent conductive film/silver/transparent dielectric or transparent conductive film, and utilized the high reflective performance of silver. This laminated glass is used as insulating glass with low solar transmittance. However, silver film has poor abrasion resistance and moisture resistance, and if it is left untreated on laminated glass, abnormalities will appear in the film within a few days, causing discoloration and deterioration of the film, and even if it is touched by hand. It was a very weak phenomenon that caused it to peel off.

For this reason, various types of glass have recently been proposed that are weather resistant and durable even when used as a single sheet instead of laminated glass. For example, in Japanese Patent Application Laid-open No. 63206333,
Single-panel heat-reflective glass is described, and the glass plate has a first layer and a third layer counted from the glass plate side as a heat-reflective film on the glass plate surface.
The layer is a transparent dielectric film or a transparent conductive oxide film, the second layer is a nitride film, and the top layer on the third layer is a thick oxide film, and the top layer is an exposed surface. For example, SiO□ film/T
A structure consisting of i02M/TiN film/T i O,L film/glass plate has been disclosed, and JP-A-64-1999
Publication No. 5930 describes a high transmittance solar control glass, in which a tin oxide film is formed as a first layer, a low light absorption film is a second layer, and a nitride film is a third layer on the glass plate surface in order from the glass plate side. A titanium film, a low light absorption film as the fourth layer, a tin oxide film as the fifth layer, and in some cases an overcoat protective film mainly composed of silicon oxide film or aluminum oxide film as the sixth layer. may be coated, for example, SiO film/Sn□ film/TjO1 film/Ti
A structure of N film/TI% film/Sn% film/glass plate has been disclosed, and furthermore, Japanese Patent Application Laid-Open No. 63-247
Publication No. 352 describes a transparent coating by reactive sputtering, and describes a coated article comprising a base material, a coating film on the base material, and a protective film on the coating, where the protective film is made of aluminum. and a silicon-containing alloy target in a reactive gas, especially 0% N2. 10-30% in ten gas
JP-A No. 60-81048 discloses a film containing an amorphous layer of a reaction product formed by sputtering in the presence of a TiO film on glass. A glass with a titanium nitride thin film and a method for producing the same are described, in which a titanium nitride thin film is formed, and then a conformal layer of TiO and TiN is provided, and a TiN film is laminated thereon.

The highly durable infrared reflecting mirror described in JP-A-61-55603 or JP-A-63-242948 uses a metal film of Zr, Ta, Ni or stainless steel.
A heat ray reflective glass described in Japanese Patent Publication No. 2003-110000 is known.

Furthermore, glasses having an antireflection film or an electromagnetic shielding film in which a high refractive index film and a low refractive index film are sequentially laminated have been proposed. At least one of the refractive index films is a high refractive index first film formed using reactive sputtering.
A multilayer anti-reflection film is disclosed in which a film-like body with a second film-like body having a refractive index higher than that of the first film-like body is laminated. The publication describes that on the outside of a glass substrate, a transparent conductive thin film for electromagnetic shielding such as an ITO film and a heat ray reflective film made by alternately laminating TiO□ and SiO□ are laminated, and on the inside, a transparent conductive thin film for electromagnetic shielding and visible light are laminated. A radio wave shielding window glass is described in which by laminating an anti-reflection film, noise caused by external radio waves can be prevented, solar radiation can be suppressed from entering, and good visibility can be ensured. The publication describes an automobile that has a radio wave shielding effect that can prevent noise caused by electromagnetic waves from outside of in-vehicle electronic devices by providing a transparent conductive film on the glass, particularly one with a sheet resistance value of 100 Ω/mouth or less. It is known that glass is described.

In either case, in order to ensure its performance as an insulating glass, the structure contains a conductive component, and this conductive film provides heat insulation properties, and in combination with the remaining dielectric material, transmittance and reflectance. It was intended to adjust the

[Problems to be solved by the invention] As mentioned above, for example, the single-pane heat ray reflective glass described in JP-A-63-206333 and JP-A-64-59
In order to obtain the same conductivity as metal for the high transmittance solar control glass described in Publication No. 30, it is necessary to use a considerably thicker and more durable conductive film to replace it. It also caused a shielding effect regarding radio waves. Also, JP-A-63
Although the transparent coating by reactive sputtering described in Publication No. 247352 improves the abrasion resistance and corrosion resistance on the surface, it cannot necessarily provide sufficient adhesion and chemical resistance in each layer. In some cases, the transparency may not be sufficient. Furthermore, the material described in JP-A No. 60-81048 is not necessarily sufficient in terms of wear resistance;
The materials described in Publication No. 3 or JP-A No. 63-242948 tend to have a large visible light reflectance when viewed from the glass side, and are not necessarily sufficient in terms of adhesion or abrasion resistance. In particular, it cannot be said that it can be sufficiently adopted for door or side glass used as a single sheet of window glass for automobiles, for example.

Furthermore, the above-mentioned Japanese Patent Application Laid-Open No. 63-131101, as well as those described in Japanese Patent Application Laid-open No. 60-81047 and Japanese Utility Model Application No. 60-183497, are all suitable for automobile telephones, TVs, and shutter opening/closing. When transmitting and receiving radio waves, such as when operating a remote control, it causes an electromagnetic shielding effect, making it difficult to obtain sufficient functionality.Also, even if the glass antenna itself has excellent performance, it reflects and absorbs, resulting in This results in very poor antenna performance and has negative effects. In addition, many proposals have been made for combinations of only transparent oxides for non-reflective glass, but these require a large number of films and the thickness of each layer is λ.
/4, λ/2, etc., are thick and very bad for production.
Furthermore, they are mainly made by dipping, sol-gel, etc., but these films have extremely poor abrasion resistance and cannot be used as veneers.

[Means for Solving the Problems] The present invention has been made in view of the above-mentioned drawbacks of the conventional art. It provides sufficient visibility for drivers, etc., and has sufficient wear resistance and durability even when used as a single plate.
It is weather resistant and can transmit radio waves inside and outside the car.
It provides single-pane insulating glass that is effective for heating and cooling.

That is, the present invention sputters a transparent dielectric film having a refractive index of 1.9 to 2.4 on the surface of a transparent colored glass substrate having a visible light transmittance of 65% or more and a solar radiation transmittance of 75% or less. The bottom film is coated with an optical thickness of 2,200 to 3,100 by the method or CVD method, and the visible light transmittance is 6.
5% or more, the visible light reflectance is 15% or less, and the solar transmittance is reduced by 5% or more compared to the transparent colored glass substrate, and the transmittance after 1000 rotations in the Taber test using CS-10F. The change in haze is within 10% compared to before the test, and the surface volume resistance is 100Ω.
・Single-pane insulating glass characterized by being CM or higher.

Furthermore, in the bottom film, the refractive index is 1.9 to 2.4.
SnOx, ZrOx, TiO as a transparent dielectric film
The present invention provides a single-pane insulating glass characterized by using x, TaOx.

Here, the reason why we decided to use a transparent dielectric film as the heat insulating single layer film is that the transmission of radio waves is related to the electrical resistance value of the film, and moreover, it is 100Ω・CM or more, preferably 1000Ω.
・Things with extremely high electrical resistance value higher than CM, such as TiO
5nOx, etc., and conventional conductive metals such as Ag, TiN, rT
O etc. have a low electric resistance value and radio wave shielding performance, and for example, the negative value is several dB or more than 10 dB compared to a transparent colored glass substrate, and for example, the negative value is 1.2 dB, which is almost the same as a transparent colored glass substrate. Moreover, these transparent dielectric films have excellent chemical resistance, moisture resistance, adhesion, etc. In addition, the dielectric film has a refractive index of 1.9-2.4, for example, 5nOx (0< x≦2
), Ta0x (0<x≦2.5), ZrOx (0<
x ≦ 2) and TiOx (0 < Alternatively, only the interference effect of the film can be used in order to approach the film, and in order to increase the interference effect, it is necessary to have a large difference in refractive index between the transparent colored glass substrate and the film, and between the film and the air. This is because the solar transmittance can be lowered by 5% or more, preferably by 7% or more, than the zero solar transmittance of the colored glass substrate alone, and the solar transmittance is preferably 65% or less. More preferably, it is around 60% or less.

Furthermore, the reason for setting the optical thickness of the single layer to 2,200 to 3,100 layers is that if the thickness is less than 2,200 layers, it may be difficult to maintain the film strength, and the visible light reflectance, solar transmittance, etc. should also be satisfactory values. This is because difficult items may appear depending on the case, and if there are more than 3,100 people,
This is because it may lead to various problems such as deterioration of productivity, distortion caused by the thickness, and in some cases, the formation of cracks or racks. Furthermore, as a manufacturing method for the bottom film, it is necessary to use the spack method or the CVD method in order to achieve wear resistance. For example, dipping methods, etc. have very weak abrasion resistance and are not suitable for use on veneers. It is to become something.

Note that, for example, either the bottom film after bending process or the bending process after film formation may be used, and this is because the film is not altered by heating because it is only a dielectric film.

Furthermore, among the optical properties, the reason why the visible light transmittance is set to 65% or more is to ensure a sufficient field of view for a driver in a car, for example, and it is preferably 70% or more, and the visible light reflectance is set to 15% or more. % or less, because if it exceeds 15%, when used as a car window glass, a mirror effect will cause the image inside the vehicle to enter the driver's field of vision, impeding the driver's safety, and conversely causing damage to the driver of an oncoming vehicle. This is to provide glare, and is preferably 13% or less, more preferably 10% or less, and in particular, the visible light transmittance or reflectance is more effective at night and in the rain. Furthermore, the reason why the solar transmittance is reduced by 5% or more compared to when only a transparent colored glass substrate is used is that if the difference is at least within 5%, the cooling and heating effects will be improved, and for example, the livability of the inside of a car will be improved. This is because it is difficult to say that it is necessarily useful, and the effect is small.

Furthermore, in the Taber test using CS-10F, the amount of change in transmittance and haze (ΔT and Δ
①) should be within 10% compared to before the test because if it exceeds 10%, the field of view and transparency of the film will deteriorate after long-term use, resulting in noticeable discomfort to the driver, and in some cases. This is because it may occur even if it impairs safety, and is preferably within 8%, more preferably within 5%.

Furthermore, the surface volume resistance of a single layer is considered to be 100Ω・CM or more at frequencies of 100 to 1000100O (7).
It is necessary to prevent radio waves from being blocked, especially at around 100 to 700 MH2, by several dB compared to a glass substrate.In particular, it is necessary to make use of the insulation performance as automobile glass while transmitting radio waves, such as TV waves and telephone waves. This is because, in order to transmit radio waves for remote control operations such as opening and closing a shutter, it is necessary to reduce the drop by approximately the same level as that of a transparent colored glass substrate, or by 1 to 2 dB.

Next, as a transparent colored glass substrate, for example, gray,
Bronze, blue, etc., and visible light transmittance (Y
g) is 65% or more and the solar transmittance (Tg) is 75% or less because it is important to match the optical properties of the transparent colored glass substrate and the monolayer film.
If it is less than 6, the visible light transmittance is 6 as a single plate of insulating glass.
It becomes quite difficult to secure more than 5%, and 75%
If it exceeds , the solar transmittance will be considerably high, for example 65%.
This is because it is a single sheet of glass that extends beyond the front and back, and it is difficult to say that it has thermal insulation performance.

More preferably, Yg is 68% or more and Tg is 73% or less.

It goes without saying that it can be used not only as a single glass but also as a multilayer or laminated glass.

[Function] As described above, the single-pane insulating glass of the present invention includes a transparent colored glass substrate 34 having specific optical properties, and a dielectric film having a specific refractive index formed on the surface of the plate to a specific optical thickness by sputtering or CVD. We formed a single-layer film using the method, determined the optical properties such as visible light transmittance, visible light reflectance, and solar transmittance, and then determined the amount of change in transmittance and haze using the Taber test. Furthermore, by specifying the surface volume resistance, the adhesion is improved, and the wear resistance and corrosion resistance of the laminated single-layer film are improved, and it has excellent durability and can be used as a veneer. It has an interference effect, has a heat insulating function, and has a sufficiently low reflectance of visible light to ensure a sufficient field of view.For example, it has almost no effect when viewed from inside or outside the car, and does not obstruct the field of vision. It has high safety and livability, and is transparent to TV radio waves, etc., and is widely used not only as architectural window glass, but also as vehicle window glass, such as front, side, and door glass, and even rear glass. It is possible to provide single-pane insulating glass.

[Example] Hereinafter, the present invention will be specifically explained with reference to Examples. However, the present invention is not limited to these embodiments.

Example 1 A gray glass (NGFL5) with a size of 600 x 60011O12 and a thickness of 5 mm was sequentially washed with a neutral detergent, a water rinse, and isopropyl alcohol, dried, and then set in a vacuum chamber of a magnetron reaction sputtering device. It was set so that it could reciprocate above a certain Sn target, and then the inside of the tank was degassed to about 5 x 10 Torr using a vacuum pump, and then 02 gas was introduced into the vacuum tank to create a vacuum. The temperature was maintained at approximately 2X 10 Torr, and a power of approximately 0.5KIt1 was applied to the Sn target, and 02 gas (however,
The flow rate ratio of Ar and 02 gases may be in the range of 1:1 to 0:1. ) at a speed of about 15 m above the Sn target in DC magnetron reaction sputtering.
By conveying the plate glass at a speed of about 15
A SnO□ thin film with a thickness of 5 6 was deposited.

First, the film thickness and refractive index of the single-panel insulating glass having the single-layer film obtained were measured using an ellipsometer (D
B-10A, laser light wavelength 6328.2A), and then visible light transmittance (380-780 nm), visible light reflectance (380-780 nm), and solar transmittance (340-1800 nm) were measured using 340 type self-recording. Spectrophotometer (newly manufactured by Hitachi) and JISZ8722. J15
The optical properties of each were determined using R3106.

Furthermore, regarding the difference in transmittance due to the Taber test, use the Taber tester (MODEL 503. manufactured by TYBER).
A test piece of lQcm square with the membrane surface facing up was set on the surface of the wear ring (CS-10F) with a load of 500 g applied to the membrane surface.
After rotating 1000 times, the visible light transmittance is first measured and compared with the measured value before the test, and the value is expressed as the amount of change, that is, the difference (ΔT). Next, for the haze (cloudiness) value, use a haze meter (manufactured by Nippon Heavy Industries, NDH-20D).
It is a numerical value measured by ΔT and expressed by the amount of change (Δ11).

Next, the acid resistance test of chemical resistance was determined by immersing the test piece in a 1N IIcL melt at room temperature for about 6 hours, and then observing the state of deterioration of the film, and the alkali resistance test. The test pieces were immersed in a 1N NaOH solution at room temperature for about 6 hours, and then the deterioration state of the film was observed. The ○ mark indicates that almost no deterioration was observed, and the × mark indicates that there was almost no deterioration. The deterioration was clearly noticeable.

In addition, the humidity resistance is approximately 50°C1 relative humidity approximately 95%.
After being left in a room for 30 days, the state of deterioration of the film was observed and the same judgment as chemical resistance was made and it was marked with a ○x mark.

Furthermore, for surface resistance, use the four-probe resistance measuring device RT-
8 (manufactured by NAPSON), 100Ω・C
A value of M or more is marked with a circle, and a value of 100Ω·CM or less is marked with a cross or a measured value. These aforementioned measurement values are as shown in Table 1.

Furthermore, regarding the radio wave transmittance, in order to understand the shielding effect, that is, the extent to which radio waves are more difficult to pass through compared to a transparent colored glass substrate, TR17302 and TR4172 (
Both were determined using ■Atopan Test).
It is shown in Figure 1.

As is clear from Table 1 and Figure 1, the solar transmittance is more than 5% lower than that of gray glass (solar transmittance 71.4%), and it has excellent heat insulation properties and exhibits better livability and safety. , has sufficient wear resistance, corrosion resistance, weather resistance,
The product has improved durability, transmits radio waves sufficiently, and is useful as a single-pane insulating glass, achieving the desired goal.

Note that the transparent colored glass substrates in the table are gray for NGFL, bronze for NFL, and blue for HFL. Furthermore, the measured value of the refractive index of the 5n02 film is 2
．． It was 0.

Examples 2 to 14 Monolayer films shown in Table 1 were obtained in the same manner as in Example 1, and measured by the measuring method shown in Example 1, etc., and performed using the same evaluation means, and the results are shown in Table 1. Shown below.

In each Example, the same product as Example 1 was obtained.

In addition, in each example, the measured value of the refractive index of each layer is T
i% was 2.25, Zr%, Ta, and Og were 2.0.

Comparative Example 1 Blue glass (HFL 5) with a size of 600 x 600 ml and a thickness of 3.5 mm was sequentially washed with a neutral detergent, rinsed with water, and isopropyl alcohol, dried, and then set in a vacuum chamber of a magnetron reaction sputtering device. I n ZO13I-5n Ol (5%) was set so that it could reciprocate above the target, and then the inside of the tank was degassed to about 5 x 10 Torr using a vacuum pump, and then heated to 200°C. and then put 0 in the vacuum chamber.
2/(0,+Ar)=2/100 gas was introduced to maintain the degree of vacuum at about 2 X 10 Torr, and about 2. OK
A thin film of ITO having a thickness of about 4,000 mm was formed by applying a power of W and transporting the plate glass above the target at a speed of about 2090 mm/min. Thereafter, heat treatment was performed at 400°C for 30 minutes in a vacuum atmosphere.

The single-panel insulating glass having the single-layer film thus obtained was evaluated by the measuring method shown in Example 1 and by the same evaluation means, and the results are shown in Table 2 and in FIG.

As is clear from Table 2 and FIG. 1, the surface volume resistance is lower than that of the example, indicating that the substrate has a conductive film layer, and as is clear from FIG. 1, only a transparent colored glass substrate is used. It has a better shielding effect, but has no abrasion resistance or chemical resistance, and can hardly be called a single-pane insulating glass with excellent properties.

The measured refractive index of the ITO film was 1.9.

Comparative Examples 2 and 3 Comparative Examples 2 and 3 were carried out in the same manner as in Comparative Example 1, except that the heat treatment in a vacuum atmosphere after film formation was not performed, and the results are shown in Table 2 and FIG.

The obtained Comparative Examples 2 and 3 lost their film after one test and had no wear resistance and could not be used as a veneer. It also had poor radio wave shielding properties. In any case, it cannot be called a single-pane insulating glass with excellent properties and cannot be used.

Comparative Examples 4 to 10 Comparative Examples 4 to 10 were carried out by the same method as in Example 1, by the measuring method shown in Example 1, and by the same evaluation means, and the results are shown in Table 2.

In each case, it would be difficult to say that the single-pane insulating glass had superior optical properties compared to the examples. In particular, the films of Examples 4 and 10 are not necessarily strong.

Note that the measured refractive index of the ZnO film was 2.0.

(The following is a blank space) 1 2 [Effects of the Invention] As described above, the present invention is capable of forming a dielectric film as a single layer film with a specific refractive index or optical thickness on a specific transparent colored glass substrate by a sputtering method or a CVD method. It can be formed into a film, and the optical and safety characteristic values can be specified, making it a unique insulating glass with excellent abrasion resistance, corrosion resistance, weather resistance, and good radio wave transparency.
It is possible to efficiently provide an effective and useful single-pane insulating glass that is equipped with a glass antenna, etc., and can be used as a single-pane as well as a double-layer or laminated glass.

[Brief explanation of drawings]

FIG. 1 is a diagram showing an example of the difference between a transparent colored glass substrate and Example 1 and Comparative Examples 1 and 23 in terms of radio wave shielding effect.

Claims (2)

[Claims] (1) Sputtering or CVD a transparent dielectric film with a refractive index of 1.9 to 2.4 on the surface of a transparent colored glass substrate with visible light transmittance of 65% or more and solar radiation transmittance of 75% or less. A film formed by a method with an optical thickness of 2200 to 3100 Å, which has a visible light transmittance of 65% or more, a visible light reflectance of 15% or less, and a solar transmittance of 5% or more compared to the transparent colored glass substrate. In addition, in the Taber test using CS-10F, the change in transmittance and haze after 1000 rotations was 10% compared to before the test.
A single-pane insulating glass characterized by a surface volume resistance of 100 Ω・CM or more. (2) In the film formation, the refractive index is 1.9 to 2.4.
SnO_x, ZrO_x, TiO as a transparent dielectric film
The single-pane insulating glass according to claim 1, characterized in that _x and TaO_x are used.