JPH03242354A - Laminated heat insulating glass for vehicle - Google Patents

Abstract

PURPOSE:To enable security of a sufficient visual field for a driver, sufficiently penetrate radio waves through the inside and outside of a car and simultaneously form laminated heat insulating glass for vehicles effectively used even for heating and cooling by combining transparent dielectric films having specific different refractive indexes at specific film thicknesses and successively laminating 3 or 5 layers of the thin films. CONSTITUTION:The subject glass is formed by respectively and successively laminating a transparent dielectric film having 1.8-2.5 refractive index to 500-2000Angstrom film thickness as the first layer from the glass surface, a transparent dielectric film having 1.4-1.7 refractive index to 500-2000Angstrom film thickness as the second layer and a transparent dielectric film having 1.8-2.5 refractive index to 500-2000Angstrom film thickness as the third layer on the surface of a transparent glass substrate (or to the fifth layer in the aforementioned procedures). The glass has the following properties. >=70% visible light transmittance, <=15% visible light reflectance, <=60% solar radiation transmittance, >=20% solar radiation reflectance and further >=10kOMEGA/cm<2> surface resistance of the film.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention improves the heating and cooling effect and has a relatively high visible light transmittance, and in particular has a film formed with good transmission of radio waves. Insulating laminated glass for vehicles that is almost equivalent to non-laminated glass substrates and has high solar reflectance and low solar transmittance, especially useful for front windows, rear windows, side windows, sunroofs, etc. Regarding laminated insulating glass for use.

[Conventional technology 1 Conventionally, for example, ZnO/Ag/ZnO1Ti02/Ag/
Transparent dielectric material or transparent conductor 11r as insulating window glass for vehicles such as T+Oz, ITO/Pt/ITO! ! ! /N metal/transparent dielectric or transparent conductive film structure achieves high visible light transmittance, and by making use of the high reflective properties of silver etc., it can be laminated as an insulating glass with low solar transmittance. It is used. However, silver films are weak in abrasion resistance and moisture resistance, and if left untreated on laminated glass, abnormalities will appear in the film within a few days, resulting in discoloration and deterioration of the film, even if you touch it with your hands. This is a very weak phenomenon in which the conductive metal peels off in the visible range, and is effective by utilizing the fact that conductive metals have relatively high transmittance in the visible range and high reflectance in the near-infrared range, and the interference effect. However, these conductive metals are used for example when used together with a glass antenna to receive radio waves from TVs and radios, car phones, etc.
Furthermore, when transmitting and receiving radio waves through window glass, such as when operating a remote control to open and close a shutter, a radio wave shielding effect occurs, reducing performance and making it impossible to obtain sufficient functionality. Therefore, for example, heat ray absorbing glass is used as a heat insulating glass that has radio wave transmission performance, but although these glasses can reduce the direct transmission of heat rays, they re-radiate the heat absorbed by the glass. It flowed into the room in such a way that the heat insulation effect could not be completely eliminated, so it could not be said to be sufficient.

Among these, the present applicant has already proposed a single-pane insulating glass having radio wave transmission performance in Japanese Patent Application No. 1-198303 and Japanese Patent Application No. 1-204354.

[Problems to be Solved by the Invention] As mentioned above, even if the glass antenna performance itself is very good, for example, with multilayer insulating glass having a conductive metal film, it will reflect and absorb, resulting in a very bad antenna. In addition, remote control operations for opening and closing the shutters have negative effects such as poor response and uncertainty, and heat-absorbing glass does not provide sufficient indoor insulation and does not necessarily improve heating and cooling efficiency. Furthermore, the patent application No. 1-1983
Unlike the above-mentioned products, the products described in No. 03 and Japanese Patent Application No. 1-204354 have excellent radio wave transparency, heat insulation, abrasion resistance, durability, chemical resistance, etc. at the same time. However, as insulating laminated glass for vehicles, it has particularly high performance in terms of radio wave transparency and heat insulation, and does not affect the transmission and reception of radio waves, such as car phones, TVs, and remote control operations for opening and closing shutters. Moreover, there is a desire for something with excellent indoor comfort.

Note that many combinations of only transparent oxides have been proposed for non-reflective glass, but these have a visible light reflectance as low as possible in the visible light range, for example, usually a value of about 2% or less. The thickness of the film is limited, so it is not necessary to be an insulating glass, regardless of radio wave transmission, solar radiation characteristics, etc.

[Means for Solving the Problems] The present invention has been made in view of the above-mentioned drawbacks of the conventional art. The present invention provides a laminated insulating glass for vehicles, which is made by laminating five layers of thin films, can secure a sufficient field of view for drivers, etc., can sufficiently transmit radio waves inside and outside the vehicle, and is effective for air conditioning and heating. .

That is, in the present invention, a transparent dielectric film having a refractive index of 1.8 to 2.5 is formed as a first layer on the surface of a transparent glass substrate with a thickness of 500 to 2000 Å, and a second layer has a refractive index of 164 Å. ~1.7 transparent dielectric film with a film thickness of 500 to 2000
Å, The third layer is a transparent dielectric film with a refractive index of 1.8 to 2.5, which is successively laminated with a film thickness of 500 to 2,000 layers, and has a visible light transmittance of 70% or more and a visible light reflectance. is 1
5% or less, solar transmittance is 60% or less, solar reflectance is 20% or more, and the surface resistance of the film is 10KΩ.
/□ or more, and a transparent dielectric film with a refractive index of 1.8 to 2.5 with a thickness of 500 on the surface of the transparent glass substrate as the first layer from the glass surface. ~2000 Å, refractive index as second layer ~1.4
The transparent dielectric film of Nos. 1 and 7 was formed with a thickness of 500 to 2000 Å, and
A transparent dielectric film with a refractive index of 1.8 to 2.5 is used as a layer with a thickness of 500 to 2000 Å, and a fourth layer has a refractive index of 1.4 to 1.
, 7 with a film thickness of 500 to 2000 Å, and a transparent dielectric film with a refractive index of 1.8 to 2.5 as a fifth layer with a film thickness of 500 to 2000 Å.
00 to 2,000 people, and has a visible light transmittance of 70% or more, a visible light reflectance of 15% or less, a solar transmittance of 60% or less, and a solar reflectance of 20% or more, Furthermore, a laminated insulating glass for vehicles characterized in that the surface resistance of the film is 10KΩ/■ or more, and furthermore, in the laminated film formation, 5nOxSTiOx, ZrOx, ,Z
n0x, TaOx, AlNx.

The present invention provides the laminated insulating glass for vehicles, characterized in that SiNx is used, and 5tyx, AlOx, and silicon aluminum alloy oxide are used as transparent dielectric films having a refractive index of 1.4 to 1.7. .

Here, the reason why we decided to use a transparent dielectric film as the heat-insulating multilayer film is that the transmission of radio waves is related to the electrical resistance value of the film, and moreover, it is 10KΩ/■ or more, preferably 100KQ/
To provide a very high electrical resistance value, for example, TiOx%5nOx.

ZrOx, TaOx, Zn0x, AlNx, Si
Nx etc. and 5tyx, AlOx.

It was found that it had to be made of silicon aluminum alloy oxide, etc., and it was not possible to use conventional conductive metals such as Ag.
, TiN, ITO, etc. have a low electrical resistance value and have radio wave shielding performance, and for example, the antenna gain is about 3 dB or more negative compared to the antenna gain on a glass substrate without a laminated film, and the gain is almost unaffected by antenna tuning etc. 2
This is because although it is not possible to achieve a value within minus dB, preferably approximately equivalent to the gain of a glass antenna simply provided on a glass substrate, the above-mentioned transparent dielectric material can be achieved by taking optical characteristics etc. into consideration. These transparent dielectric films have excellent abrasion resistance, chemical resistance, moisture resistance, adhesion, etc., except that the Zn0x film is somewhat inferior in abrasion resistance and chemical resistance.

The present invention uses a dielectric film having a refractive index of 1.8 to 2.5, such as 5nOx (0<x≦2), TiOx (0<x≦
2), TaOx (0<x≦2.5), ZrOx
(0< x≦2) and AINx (0< x≦1)
, 5iNx (0<x≦4/3), etc., and then 1.4 to 1
．． 7, for example SiOx (0<X≦2), Al0x
(0<x≦1.5), silicon aluminum alloy oxide (Al-5iOx: O<x≦7/2),
On top of that, layers with low and high refractive indexes of 1.8 to 2.5 were laminated on the surface of the glass substrate alternately to form a 3- or 5-layer multilayer film. For example, in order to make the light transmittance and reflectance similar to that of a glass substrate on which no film is formed, only the interference effect of the film is used, and in order to increase the interference effect, the glass substrate and film, film and film, etc.
This is because it is necessary to have a large difference in refractive index between the film and the air, and the reason why we set the solar transmittance to 60% or less and the solar reflectance to 20% or more is to further reduce heat re-radiation in the glass and improve the overall effect. This is to improve the insulation effect of the The reason why the thickness of each film in the multilayer film of 3 layers and 5 layers was set to 500 to 2000 people is because the stimulation purity of the reflection is low and the reflected color tends to be a neutral color, and it is difficult to use less than 500 people. It is difficult for the reflectance of solar radiation to exceed 20%, making it difficult to reach a satisfactory value.If the number of workers exceeds 2,000, there will be problems such as a decrease in productivity and distortion due to the thickness. This is because you may end up having problems. Further, by using a silicon aluminum alloy oxide film or the like having a refractive index of about 1.5 and a film thickness of about 500 to 2,000, the film strength can be increased.

Furthermore, as a method for film formation, sputtering method or CV
The D method is necessary for the wear-resistant ring. For example, the deimping method tends to result in very poor wear resistance, so the sputtering method or the CVD method is preferable.

Note that, for example, either the film formation 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 70% or more is to ensure a sufficient field of vision for a driver in a car, for example, and it is preferably 75% 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. In particular, the visible light transmittance or reflectance is more effective at night and during rain. Furthermore, the reason why the solar transmittance is 60% or less and the solar reflectance is 20% or more is that if the solar transmittance exceeds 60% and the reflectance is less than 20%, the cooling and heating effects will be improved;
For example, it cannot be said that it is necessarily useful for improving the livability inside the car, and the effect is small.

Furthermore, the reason why the surface resistance is 10KΩ/■ or more is because the glass antenna gain decreases by about 2 dB compared to a glass substrate without film formation, for example, at a frequency of 100 to 100,100O, especially around 100 to 700MHz. This is necessary in order to avoid blocking radio waves such as TV waves, telephones, and remote control operations for opening and closing shutters, and it is almost equivalent to a glass substrate for radio waves such as TV waves, telephone calls, and remote control operations for opening and closing shutters. Or 1
This is because it is necessary to suppress the decrease to about 2 dB.

Next, as the glass substrate, any transparent glass may be used, but gray, bronze, blue, etc. are particularly preferable, and are more preferable since they can easily obtain a neutral color. It goes without saying that it can be used not only for laminated glass, but also for double-layered or single-paned glass.

[Function] As mentioned above, the laminated insulating glass for vehicles of the present invention has the following effects:
Transparent dielectric films with a specific low and high refractive index are skillfully combined and formed by sputtering or CVD, etc., to form a multilayer film of 3 or 5 layers with a specific film thickness, and the visible light transmittance and visible light By specifying the optical properties such as reflectance, solar transmittance, and solar reflectance, and also specifying the surface resistance, the adhesion of each thin film layer is high, and the abrasion resistance of the entire laminated multilayer film is improved. It has improved corrosion resistance, excellent durability, and is a base plate for laminated glass that can be used as a single sheet.Moreover, it has a moderate interference effect, increases the reflection of sunlight, and reduces the amount of solar energy absorbed by the glass, resulting in higher overall performance. It has a heat insulating function and has a sufficiently low reflectance of visible light to ensure a sufficient field of view.For example, there is almost no mirror effect from inside or outside the vehicle, which does not obstruct the field of view, and provides high safety and livability. In addition, it transmits TV radio waves, etc. on a par with ordinary laminated glass without coating, and can be used as vehicle window glass for front or rear windows without degrading the performance of glass antennas. To provide a laminated insulating glass for a vehicle that does not cause any trouble in remote control operation of opening and closing a garage shutter.

[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 Bronze glass (NFL2.3) with a size of 600 x 60011112 and a thickness of 2.3 mm was rinsed with a neutral detergent and water.
After sequentially washing with isopropyl alcohol and drying, it was set in a vacuum chamber of a magnetron reaction sputtering device so that it could reciprocate above the target of Ti and St%, and then -6 After degassing to about 5 x 10 Torr with a vacuum pump, 02 gas was introduced into the vacuum chamber to maintain the degree of vacuum at about 2 x 10 Torr, and about 2.5 KW of power was applied to the Ti target. During DCC magneto reaction sputtering using 0□ gas (however, the flow rate ratio of Ar and 0□ gas may be in the range of 1:1 to O:1), above the Ti target at a speed of about 1
A TiOx surface film having a thickness of approximately 900 mm was formed as a first layer by transporting the plate glass 9 times back and forth at a speed of 0.0 fi/in. After the film formation is completed, the application to the Ti target is stopped.

Next, while leaving the plate glass in the vacuum chamber, the 5i
Apply a power of about 2.5 to - to the Oz target, and
Approximately 11 cm/in. By conveying at high speed, a second layer of an SiOx thin film having a thickness of approximately 1400 mm was formed and laminated on the TiOx film-formed surface of the plate glass.

Further, in the same manner as in the first layer film formation described above, a film of about 10 mm/layer was formed.
By transporting the glass back and forth 9 times at a speed of
The film was formed and laminated as a layer.

Furthermore, a 30 MTL transparent PVB film and a clear glass 2 am (FL2) were bonded together so that the sputtered surface of the single glass having the three-layer multilayer film thus obtained became the mating surface to obtain a laminated insulating glass for vehicles. Ta.

The obtained laminated insulating glass for vehicles has visible light transmittance (380 to 780 nm) and visible light reflectance (380 to 7
80nm), solar transmittance, solar reflectance (340~
1800nm), a 340 type self-recording spectrophotometer (Hitachi model) and JISZ8722. JISR3106
The optical properties of each were determined using the following methods. Furthermore, regarding surface resistance, four-probe resistance measuring device RT-8 (NAP
For radio wave transmittance, we measured the gain value of laminated glass with a normal glass antenna without film formation, and obtained the gain value for laminated insulating glass for vehicles etc. based on that. The relationship between the surface resistance value and the gain reduction value described above is illustrated by comparing how much the measured gain value has decreased. Then, we found that 10KΩ/□, and 10KΩ/
② or above is marked with an O mark, and below 10KQ10 is marked with an x mark. The above-mentioned measured values are shown in Table 1.

As is clear from Table 1, it has excellent insulation properties and exhibits better livability and safety. For example, the surface resistance is IMQ/
In other words, the gain reduction value is within -0.5 dB, and it is a laminated insulating glass for vehicles that sufficiently transmits radio waves and has antenna reception performance that is the same as that of laminated glass without a sputtered film, and is useful as expected. Obtained.

In addition, regarding the glass substrates in the table, GFL is gray, NFL is bronze, and FL is colorless and transparent normal plate glass.

Examples 2 to 7 In the same manner as in Example 1, the 3-layer and 5-layer laminated multilayer films shown in Table 1 and their respective film thicknesses were obtained, and the film configurations were measured by the measuring method shown in Example 1. The same evaluation method was used and the results are shown in Table 1.

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

Comparative Example 1 A three-layer multilayer film as shown in Table 1 was obtained in the same manner as in Example 1. Regarding Zn0x thin film, Zn
Using a target, vacuum degree 2×3 10 Torr, 0□ gas, applied power IKW, DC? Gnetron reaction sputtering, conveyance speed approximately 200m/wi
n to obtain a thickness of approximately 400 mm, and for Ag thin films, A
Using g target, vacuum level 2.5 x 10 Torr
r.

A thickness of about 150 mm was obtained using Ar gas, applied power IKWSDC magnetron sputtering, and conveyance speed of about 500 am/in.

The membrane structure was evaluated using the same measuring method as shown in Example 1, and the results are shown in Table 1.

Compared to the example, for example, the glass antenna gain exhibits a negative gain reduction value of around 25 dB, which obviously reduces the glass antenna performance and becomes a hindrance, and in any case, it does not necessarily have excellent characteristics. It could hardly be called laminated insulating glass for vehicles.

Comparative Example 2 A laminated glass was obtained by laminating layers with the film structure and film thickness shown in Table 1 by the same method as in each of the above Examples.

The obtained laminated glass was evaluated according to the same measurement method as in the above examples, etc. As shown in Table 1, the transmission of radio waves was good, but the transmission of solar radiation was large and the reflection of solar radiation was small (not necessarily due to insulation). The laminated insulating glass for vehicles did not have good properties (it cannot necessarily be said that it had excellent properties).

Comparative Examples 3 to 4 Single-layer laminated glasses shown in Table 1 were obtained by the same method as in each of the above Examples.

As a result of the same measurement method and evaluation as mentioned above, for example, the gain reduction value mentioned above was about -6 dB, about -10 dB, etc., and as shown in Table 1, it is inferior in terms of radio wave transmittance, solar reflection, etc., and is not necessarily superior. It could hardly be said that the laminated insulating glass for vehicles had such characteristics as expected.

Comparative Examples 5 to 6 Comparative Example 5 is ordinary laminated glass without film formation and naturally has no heat insulating performance, while Comparative Example 6 is heat ray absorbing glass with low solar reflection and overall heat insulating performance. As with the above-mentioned comparative example, it is difficult to say that it is the desired laminated insulating glass for vehicles.

[Effects of the Invention] As described above, the present invention produces a multilayer film by uniquely combining transparent dielectric films with a specific low and high refractive index or film thickness on a specific transparent colored glass substrate or the like using a sputtering method or a CVD method. It is made of laminated glass with a laminated structure, and has specific optical and safety characteristics.It is an insulating glass that has excellent abrasion resistance, corrosion resistance, weather resistance, and extremely good radio wave transmission. This makes it possible to efficiently provide laminated insulating glass for vehicles, which is unique and can be used not only as laminated glass but also as double-glazed glass or single-pane glass, has a neutral color, is comfortable to live in, and is effective and useful even when equipped with glass antennas, etc. It is something.

Claims (3)

[Claims] (1) A transparent dielectric film with a refractive index of 1.8 to 2.5 is applied to the surface of the transparent glass substrate as the first layer from the glass surface to a thickness of 50 mm.
0-2000 Å, refractive index 1.4-1.7 as second layer
A transparent dielectric film with a thickness of 500 to 2000 Å is used as the third layer, and a transparent dielectric film with a refractive index of 1.8 to 2.5 is used as a third layer with a thickness of 500 Å.
~2,000 Å, each having a visible light transmittance of 70% or more, a visible light reflectance of 15% or less, a solar transmittance of 60% or less, a solar reflectance of 20% or more, and a film A laminated insulating glass for vehicles, which has a surface resistance of 10KΩ/□ or more. (2) A transparent dielectric film with a refractive index of 1.8 to 2.5 is applied to the surface of the transparent glass substrate as the first layer from the glass surface to a thickness of 50 mm.
0-2000 Å, refractive index 1.4-1.7 as second layer
A transparent dielectric film with a thickness of 500 to 2000 Å is used as the third layer, and a transparent dielectric film with a refractive index of 1.8 to 2.5 is used as a third layer with a thickness of 500 Å.
~2000 Å, the fourth layer is a transparent dielectric film with a refractive index of 1.4 to 1.7, the thickness is 500 to 2000 Å, and the fifth layer is a transparent dielectric film with a refractive index of 1.8 to 2.5. Thickness 500~
The film has a visible light transmittance of 70% or more, a visible light reflectance of 15% or less, a solar transmittance of 60% or less, and a solar reflectance of 20% or more. A laminated insulating glass for vehicles characterized by a surface resistance of 10KΩ/■ or more. (3) In the laminated film formation, the refractive index is 1.8 to 2.5.
SnO_x, TiO_x, ZrO as a transparent dielectric film
_x, ZnO_x, TaO_x, AlN_x, SiN_
3. The laminated insulating glass for a vehicle according to claim 1, wherein SiO_x, AlO_x, and silicon aluminum alloy oxide are used as the transparent dielectric film having a refractive index of 1.4 to 1.7.