JPH06329443A - Ultraviolet-screening glass - Google Patents

Abstract

PURPOSE:To produce an ultraviolet-screening glass remarkably useful as automobile glass and capable of preventing sunburn of occupants, softening hot feeling, reducing the load on a cooler and preventing deterioration of interior trims. CONSTITUTION:A glass plate is coated with an SnO2 membrane having 30 to 80nm thickness as the first layer, a TiO2 membrane having 20 to 80nm thickness as the second layer on the first layer and a transparent layer having 10 to 120nm thickness and composed of one component selected from Ta2O5, ZrO2 and SiCxNyOz or a laminate thereof as the third layer on the second layer. A TiSixNyOz [1<=x<=3, 0.5<=y<=3 and (1+x)<z<2(1+x)] membrane having 5 to 80nm thickness is sandwiched between the first layer and the second layer or/and between the second layer and the third layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet heat ray-shielding glass having a high visible light transmittance, and more particularly to an ultraviolet heat ray-shielding glass useful as a window glass for automobiles and buildings.

[0002]

2. Description of the Related Art Conventionally, the following methods have been known as methods for imparting a function of simultaneously cutting ultraviolet rays and infrared rays to glass by surface treatment.

First, there is a multilayer interference film, that is, T
A multilayer interference thin film formed by alternately stacking a high refractive index substance such as iO ₂ and a low refractive index substance such as SiO ₂ is formed on a transparent substrate and reflects ultraviolet rays and infrared rays by a selective reflection function. is there.

Next, there is a multilayer interference film in which a transparent conductive oxide film and a high refractive index transparent dielectric film are alternately laminated in multiple layers on a zinc oxide film. This is a combination of the ultraviolet absorption characteristics of zinc oxide, the selective reflection characteristics of a multilayer film, and the infrared reflection characteristics of a transparent conductive oxide film (JP-A-4-133004).

Further, there is an organic ultraviolet absorber-containing thin film, that is, a coating film in which an organic or inorganic ultraviolet absorber or infrared absorber is dispersed in a transparent organic or inorganic polymer is applied on a glass substrate. It was created (Japanese Patent Laid-Open No. 4-160037).

Furthermore, there is a description using a TiSixNyOz film (Japanese Patent Laid-Open No. 4-285033). Also S
There is also a description regarding the film structure of nO ₂ / TiO ₂ / SnO ₂ (JP-A-3-65531 and JP-A-4-209733).
Issue).

[0007]

When the application to automobile glass is considered, the glass to be coated has a large area, the optical characteristics are visible light transmittance of 70% or more, and the color tone is neutral. In addition, it is required to have durability so as not to deteriorate in a harsh use environment. From this point of view, when the above-mentioned conventional technique is examined, there are the following problems.

[0008] First, for the multilayer film interference method, the sputtering method is considered to be optimal in consideration of the substrate size as a film forming process, but there is a problem that the sputtering rate of TiO ₂ which is a high refractive index material is very slow. It was Further, at the same time, the film thickness of one layer is about 100 nm, and since it becomes a plurality of layers, there is a problem that it takes time to form the film and the cost becomes high.

Next, for a multilayer interference film in which a large number of transparent conductive oxide films and high refractive index transparent dielectric films are alternately laminated on a zinc oxide film, TiO ₂ is used as a high refractive index transparent dielectric film. Since it is used, it has the same problem as the above-mentioned multilayer interference method.

Further, the thin film containing an organic ultraviolet / infrared ray absorbent is inferior in weather resistance and heat resistance since it deteriorates itself while absorbing ultraviolet rays and becomes yellow or brown. There was a problem that it was not suitable.

An object of the present invention is to eliminate the above-mentioned problems, and to provide an ultraviolet heat ray-shielding glass which can be used as a window glass for automobiles and can be manufactured at a relatively low cost.

[0012]

The ultraviolet heat ray-shielding glass according to the present invention has a thickness of 30 to 80 n on a glass plate.
m SnO ₂ film is coated as a first layer, a TiO ₂ film having a thickness of 20 to 80 nm is coated as a second layer on the first layer, and a thickness of 10 to 120 nm is coated on the second layer. A transparent layer made of any one of Ta ₂ O ₅ , ZrO ₂ , and SiCxNyOz or a laminate of these layers is coated as a third layer, and is provided between the first layer and the second layer and the second layer. There is a thickness of 5 between the third layer or both.
˜80 nm TiSixNyOz [1 ≦ x ≦ 3, 0.5
≦ y ≦ 3, (1 + x) <z <2 (1 + x)] film is provided.

The ultraviolet heat ray-shielding glass which is another aspect of the present invention comprises TiS having a thickness of 20 to 100 nm on a glass plate.
ixNyOz [1 ≦ x ≦ 4, 0.5 ≦ y ≦ 3, (1+
x) <z <2 (1 + x)] film is coated as the first layer,
A SnO ₂ film having a thickness of 10 to 90 nm is coated as a second layer on the first layer, and a thickness of 50 to 50 nm is provided on the second layer.
It is characterized in that a SiCxNyOz layer having a refractive index of 100 or less and a wavelength of 632.8 nm of 1.8 or less is coated as the third layer.

In general, the ultraviolet rays reaching the surface of the earth are UV-
B (wavelength: 290 to 320 nm) and UV-A (wavelength: 3
20-600 nm). Both of these affect the human skin, especially UV-B is pigmentation from erythema, UV-
A causes pigmentation.

Recently, in order to ensure the comfort of passengers in automobiles as well, ultraviolet ray blocking glass has been desired. Then, natural materials have come to be used as interior materials for automobiles, and also from this point of view, an ultraviolet ray blocking function is desired.

By the way, when considering the ultraviolet ray shielding in automobile glass, the float glass which is the material is 3
Most of the UV rays of 20 nm or less are absorbed,
It is necessary to block the ultraviolet rays of UV-A.

In order to meet such a demand, the inventors of the present invention have conducted extensive studies and found that the TiSixNyOz film has excellent properties as an ultraviolet absorbing material for automobile glass.

Therefore, the relationship between the composition of the TiSixNyOz film and the ultraviolet absorption characteristics is shown in FIG. 5 and Table 1.

[0019]

[Table 1]

According to these, it is understood that when the ratio of oxygen is low, the ultraviolet ray blocking property is good, but the absorption reaches the visible range, so that the visible light transmittance is lowered and the absorption color is generated.

It is presumed that such characteristics are largely due to the TiN structure existing in the film. Also, when the proportion of oxygen increases, the absorption start end shifts to the short wavelength side,
The ultraviolet blocking property is deteriorated. Such a change in characteristics is S
It is presumed that it is due to iN, SiO ₂ , and TiO ₂ .

Due to these facts, the TiSi of the present invention is
The composition of the xNyOz film is as follows in order to transmit visible light and block ultraviolet rays.

X is in the range of 1≤x≤4. Because
This is because if the amount of Si is larger than Ti in this range as compared with Ti, the characteristics of SiNxOy will result. That is, SiNxO
This is because y gives a transparent film regardless of whether nitrogen or oxygen is used. On the other hand, when the amount of Si is small, T
This is because the characteristic becomes iNxOy. Preferably 1.0 ≦ x ≦ 2.5.

Further, y and z determine the oxynitriding degree of TiSi metal, y is 0.5 ≦ y ≦ 3, and z is (1
+ X) <z <2 (1 + x).

The ultraviolet heat ray-shielding glass of the present invention is a laminated body having a constitution of glass / first layer (SnO ₂ ) / second layer (TiO ₂ ) / third layer, wherein the first layer and the second layer Between
The above-mentioned TiSixNyOz film is provided between the second layer and the third layer, or both of them.

In the present invention, the glass plate is preferably a glass plate made of float glass or the like, and may be colored if necessary as long as it has a required visible light transmittance. The thickness of the glass plate can be arbitrarily selected according to the application, but generally speaking, it is 1 to 8 mm, preferably 3 to 5 mm.

The film thickness of SnO ₂ which is the first layer of the present invention is
30-80 nm. When the film thickness is out of this range, the transmittance is lowered and the color tone is not neutral, which is not desirable. It is preferably 50 to 80 nm.

The TiO ₂ film which is the second layer of the present invention is 20
~ 80 nm. When the film thickness is out of this range, the transmittance is lowered and the color tone is not neutral, which is not desirable. It is preferably 30 to 50 nm.

If the thickness of the third layer of the present invention is less than 10 nm, the abrasion resistance and chemical resistance of the coating layer are deteriorated, and if it exceeds 120 nm, the color tone of the coating film becomes noticeable, which is not preferable as a window glass. Within the thickness range of 10 to 120 nm, abrasion resistance and chemical resistance are ensured to have practical strength, and the transmission color is 3 or less in Hunter chromaticity coordinates and the reflection color is 5 or less (7 of the original). Z) whose refractive index can be 1.8 to 2.1 in order to obtain a glass whose color tone (described on the page) is inconspicuous.
If a rO ₂ film or a Ta ₂ O ₅ film is used, it is 20 to 4
Thickness range of 0 nm, SiCxN that can be smaller than 1.8
When using the yOz film, the thickness is preferably 40 to 90 nm.

The film thickness of the TiSixNyOz film of the present invention is 5
~ 80 nm. If the film thickness is out of this range, the effect of blocking ultraviolet rays is weakened and the visible light transmittance is lowered, which is not desirable. It is preferably 20 to 70 nm.

Another ultraviolet heat ray-shielding glass of the present invention is a laminated body composed of glass / first layer (TiSixNyOz) / second layer (SnO ₂ ) / third layer.

In the present invention, the glass plate is as described above.

TiSixNyOz which is the first layer of the present invention
The film thickness of the film is 20 to 100 nm. If the film thickness deviates from this range, the ultraviolet ray cutting effect is particularly weakened and the visible light transmittance is lowered, which is not desirable. When the nitrogen content in the film is relatively lower than the oxygen content, that is, when the light absorption is low and the transmittance is high, the thickness is preferably 50 to 90 nm, and is relatively lower than the nitrogen content in the film. It is preferably 20 to 50 nm when the light absorption is large.

The thickness of the SnO ₂ film which is the second layer of the present invention is 10 to 90 nm. When the film thickness is out of this range, the transmittance is lowered and the color tone is not neutral, which is not desirable. It is preferably 20 to 70 nm.

The third layer of the present invention has a refractive index of 1.8 or less at a wavelength of 632.8 nm and a thickness of 50-1.
It is a SiCxNyOz layer with a thickness of 00 nm. Z in this layer
A rO ₂ layer, a Ta ₂ O ₅ layer, or a layer of this mixture can be laminated in a range in which the total thickness thereof does not exceed 20 nm to form a multilayer film having two or more layers.

With such a constitution, the ultraviolet heat ray-shielding glass of the present invention has a visible light transmittance of 70% or more, an ultraviolet light transmittance of 40% or less, and a reduction rate of solar radiation transmittance from the substrate. In addition to being 8% or more, both the transmitted color and the reflected color have a characteristic of being a neutral color.

The change from the substrate color in Hunter chromaticity coordinates is as follows. Transmission color: | Δa | ≦ 3 | Δb | ≦ 3 Reflection color: | Δa | ≦ 5 | Δb | ≦ 5

The UV heat ray-shielding glass of the present invention comprises the first to third layers on the glass plate surface, or TiSi between them.
The xNyOz film can be easily manufactured by sequentially forming the xNyOz film by a conventional method such as a sputtering method.

The present invention will be described in more detail below by showing Examples and Comparative Examples.

Examples 1 to 8 and Comparative Examples 1 to 3 SZ35 (manufactured by Nippon Sheet Glass Co., Ltd., safety bronze, 3.5 mm) was used as a glass substrate, and a DC sputtering device was used as a film forming device. Film formation was performed under the film formation conditions shown in the table, and samples of Examples of the present invention and Comparative Examples were prepared.

[0041]

[Table 2]

The samples (Examples 1 to 8 and Comparative Examples 1 to 3) thus obtained were evaluated for optical characteristics, abrasion resistance and chemical resistance. The results are shown in Table 3.

The evaluation was carried out by the following method. Optical characteristics: Spectrophotometer Hitachi U-3400 Abrasion resistance: Taber abrasion tester condition 500g × 1000 rotation evaluation Transmittance change Chemical resistance: 1N H ₂ SO ₄ 24 hours immersion 1N NaOH 24 hours immersion

[0044]

[Table 3]

In each of the examples, the visible light transmittance is 70.
% Or more, and both the ultraviolet ray transmittance and the solar radiation transmittance are small. Further, since the color tone is neutral and the durability is excellent, it can be seen that the present invention is extremely suitable for automobile glass.

In Comparative Example 1, in Comparative Example 1, SnO ₂ ,
TiO ₂ and SnO ₂ are laminated in this order,
It can be seen that the solar radiation transmittance and the color tone are good, but the ultraviolet transmittance is large.

In Comparative Example 2, the film thickness of each layer was precisely adjusted by setting the film forming conditions of the TiSixNyOz film in the constitution of the example of the present invention to N ₂ 100%, and both the transmitted color and the reflected color were colored. It can be seen that it cannot be used as a glass for automobiles due to its design.

In Comparative Example 3, the TiSixNyOz film in the structure of Example 5 of the present invention was formed under the conditions of O ₂ 10%, but it is apparent from the table that it cannot be used as glass for automobiles.

[0049]

As described in detail above, the ultraviolet heat ray-shielding glass of the present invention has a visible light transmittance of 70% or more, an ultraviolet light transmittance of 40% or less, and a solar radiation transmittance reduction ratio of 8% or more. Moreover, since the transmitted and reflected color tones are neutral and the durability is excellent, it is extremely useful as glass for automobiles, preventing sunburn of passengers, reducing heat and heat feeling, reducing cooler load, interior decoration. It has various effects of preventing material deterioration.

[0050]

[Brief description of drawings]

FIG. 1 is a vertical cross-sectional view showing an embodiment of an ultraviolet heat ray-shielding glass which is one of the present invention.

FIG. 2 is a vertical cross-sectional view showing an embodiment of the ultraviolet ray blocking glass which is one of the present invention.

FIG. 3 is a vertical cross-sectional view showing an embodiment of the ultraviolet ray blocking glass which is one of the present invention.

FIG. 4 is a vertical sectional view showing an ultraviolet heat ray-shielding glass which is another embodiment of the present invention.

FIG. 5 is a diagram showing an extinction coefficient of TiSixNyOz.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hidemi Nakai, 3-5-11 Doshomachi, Chuo-ku, Osaka-shi, Osaka, Japan Nippon Sheet Glass Co., Ltd.

Claims (3)

[Claims] 1. An S having a thickness of 30 to 80 nm on a glass plate.
The nO ₂ film is coated as the first layer, the TiO ₂ film having a thickness of 20 to 80 nm is coated as the second layer on the first layer, and the Ta ₂ having a thickness of 10 to 120 nm is coated on the second layer.
A transparent layer made of any one of O ₅ , ZrO ₂ , and SiCxNyOz or a laminate of these layers is coated as a third layer, and is provided between the first layer and the second layer and between the second layer and the second layer. The thickness is 5 to 80 between the three layers or both of them.
nm TiSixNyOz [1 ≦ x ≦ 3, 0.5 ≦ y ≦
3, (1 + x) <z <2 (1 + x)] film is provided. 2. A TiSixNyOz [1 ≦ x ≦ 4, 0.5 ≦ y ≦ 3 having a thickness of 20 to 100 nm on a glass plate,
(1 + x) <z <2 (1 + x)] film is coated as the first layer, and SnO having a thickness of 10 to 90 nm is formed on the first layer.
₂ films are coated as a second layer, a SiCxNyOz layer having a thickness of 50 to 100 nm and a refractive index of 1.8 or less at a wavelength of 632.8 nm is coated on the second layer as a third layer. A glass that blocks UV heat rays. 3. The SiCxNyOz layer has at least one layer of ZrO ₂ or Ta ₂ O _{5 having} a total thickness of 20 n.
The ultraviolet heat ray-shielding glass according to claim 2, wherein the third layer is formed by laminating it in a range not exceeding m.