WO2017141643A1 - Heat-shielding glass - Google Patents

Abstract

Provided is a heat-shielding glass that has a glass plate, which has a first and second surface that face each other, and a coating film, which is provided on the first surface of the glass plate, wherein: the coating film has an underlayer and a first and second layer that are disposed above the underlayer; the first layer is disposed between the underlayer and the second layer; one layer from among the first layer and second layer includes antimony-containing tin oxide and the other layer from among the first layer and second layer includes fluorine-containing tin oxide; the total thickness of the first layer and second layer is 340 nm or more; and the average power spectral density at frequencies of 1-2 μm^-1 as measured in an 8 μm × 8 μm region in the coating film-side surface of the heat-shielding glass is 6×10⁶nm⁴ or less.

Description

Thermal barrier glass

The present invention relates to a thermal barrier glass having a coating film.

Due to the recent increase in energy conservation awareness, there are an increasing number of cases in which heat-insulating glass having heat-insulating properties is applied to window glass of buildings and glass members of vehicles. Such a heat insulating glass is configured by, for example, installing a coating film having a heat insulating property on one surface of a glass plate.

More recently, in response to the increasing demand for heat-shielding effects of heat-shielding glass, research and development on heat-shielding glass that exhibits further heat-shielding properties are being promoted.

Generally, it is effective to make the coating film a multi-layer structure in order to improve the heat shielding property of the heat shielding glass. For example, Patent Document 1 describes a thermal barrier glass provided with a multilayer coating film composed of two layers of an antimony-containing tin oxide layer and a fluorine-containing tin oxide layer on a base layer.

JP 2001-199744 A

As described above, it has been reported that the heat shielding property of the heat shielding glass can be improved by forming a multilayer coating film on the glass plate.

However, the heat shielding glass may require various properties in addition to the heat shielding properties. For example, depending on the place of application of the heat shield glass, design properties, transparency, and the like may be required for the heat shield glass.

However, in the heat shielding glass described in Patent Document 1, it is difficult to say that characteristics other than the heat shielding properties are sufficiently considered. For example, the thicker the multilayer coating film, the better the heat shielding property, but in that case, the transparency of the heat shielding glass may decrease and the haze value may increase.

The present invention has been made in view of such a background, and an object of the present invention is to provide a thermal barrier glass having good thermal barrier properties and having a haze value significantly suppressed.

In the present invention,
A heat-shielding glass having a glass plate having first and second surfaces facing each other, and a coating film provided on the first surface of the glass plate,
The coating film includes a base layer, and a first layer and a second layer disposed on the base layer, and the first layer includes the base layer and the second layer. Placed between
Either one of the first layer and the second layer contains tin oxide containing antimony, and the other of the first layer and the second layer contains tin oxide containing fluorine,
The total thickness of the first layer and the second layer is 340 nm or more,
In the coating layer surface of the thermal barrier glass, measured in the region of 8 [mu] m × 8 [mu] m, an average power spectral density between the frequency 1 [mu] m ^-1 ~ 2 [mu] m ^-1 is 6 × ¹⁰ 6 nm ⁴ or less, Thermal barrier glass is provided.

In the present invention, it is possible to provide a heat insulating glass having a good heat insulating property and having a haze value significantly suppressed.

It is sectional drawing which showed roughly the example of 1 structure of the thermal insulation glass by one Embodiment of this invention. It is the graph which compared and showed the evaluation result of the frequency dependence of the power spectrum density in the thermal insulation glass 2 and the thermal insulation glass 7. FIG. It is the graph which showed collectively the relationship between the average P value and haze value which were obtained in each heat insulation glass.

(Thermal shielding glass according to one embodiment of the present invention)
Hereinafter, an embodiment of the present invention will be described with reference to FIG.

FIG. 1 schematically shows a cross section of a heat insulating glass (hereinafter referred to as “first heat insulating glass”) according to an embodiment of the present invention.

As shown in FIG. 1, the first thermal barrier glass 100 has a first side 102 and a second side 104. The first heat shield glass 100 includes a glass plate 110 and a coating film 120. The first side 102 of the first thermal barrier glass 100 corresponds to the glass plate 110 side, and the second side 104 of the first thermal barrier glass 100 corresponds to the coating film 120 side.

The glass plate 110 has a first surface 112 and a second surface 114. The coating film 120 is provided on the first surface 112 side of the glass plate 110.

The coating film 120 is configured by laminating a base layer 130, a first layer 140, and a second layer 150 in this order. However, as will be described later, the coating film 120 is not limited to such a three-layer structure, and may be composed of four or more layers.

The underlayer 130 of the coating film 120 has a layer containing, for example, silicon oxide or tin oxide.

The first layer 140 and the second layer 150 of the coating film 120 are both composed of a layer containing tin oxide.

One of the first layer 140 and the second layer 150 contains tin oxide containing antimony, and the other of the first layer 140 and the second layer 150 contains tin oxide containing fluorine. Moreover, it is preferable that the 1st layer 140 and the 2nd layer 150 contain 50 mass% or more of tin oxides, for example, 60 mass% or more.

Here, the first thermal barrier glass 100 is
The total thickness of the first layer 140 and the second layer 150 is 340 nm or more;
On the second side 104, the average power spectral density between frequencies 1 μm ⁻¹ and 2 μm ⁻¹ (hereinafter referred to as “average P value”) measured in the region of 8 μm × 8 μm is 6 × 10 ⁶ nm ⁴ or less. It has the characteristic that

In the first heat-shielding glass 100, the total thickness of the first layer 140 and the second layer 150 exhibiting heat-shielding properties is sufficiently thick at 340 nm or more. Therefore, the first heat insulating glass 100 can exhibit a sufficient heat insulating property.

Further, in the first heat blocking glass 100, the average P value measured in the region of 8 [mu] m × 8 [mu] m is 6 × ¹⁰ 6 nm ⁴ below. In this case, as will be described in detail later, the first heat-shielding glass 100 is significantly suppressed from being clouded or clouded.

Due to such characteristics, the first heat-insulating glass 100 can provide a heat-insulating glass exhibiting good heat-insulating properties and having a significantly reduced haze value.

(About power spectral density)
Here, the measuring method of the power spectral density (PSD) in this application is demonstrated.

Generally, the surface of the coating film in the heat shielding glass has a form in which fine irregularities are distributed on a two-dimensional plane. Each form of these irregularities can be represented by a two-dimensional function h (x, y) of coordinates (x, y).

When the two-dimensional function h (x, y) is Fourier transformed, a two-dimensional function H (f _x , f _y ) expressed by the following equation (1) is obtained:

ここで、ｆ_ｘおよびｆ_ｙは、それぞれｘ方向およびｙ方向の周波数であり、長さの逆数の次元を有する。また、πは円周率、ｉは虚数単位である（詳細は、ＷＯ２０１４／０９７８０７号参照）。

Here, f _x and f _y are frequency in the x and y directions, respectively, having the dimensions of reciprocal length. In addition, π is a circumference ratio, and i is an imaginary unit (for details, refer to WO2014 / 097807).

A function H ² (f _x , f _y ) obtained by squaring the two-dimensional function H (f _x , f _y ) represented by the expression (1) is also called a two-dimensional power spectrum. This represents the spatial frequency distribution of the unevenness. The unit of the two-dimensional power spectrum is (length) ⁶ , for example, nm ⁶ or the like.

Since the unevenness of the coating film surface is considered to be isotropic, the two-dimensional power spectrum H ² (f _x , f _y ) is dependent on only the distance f from the origin (0, 0). It can be represented by (f). First, the two-dimensional power spectrum H ² (f _x , f _y ) is displayed in polar coordinates based on the equation (2).

　ここでθはフーリエ空間中の偏角である。この極座標表示した二次元パワースペクトルの回転平均を（３）式に基づき計算することで、一次元パワースペクトルＩ（ｆ）を求めることができる。

Here, θ is a declination angle in Fourier space. The one-dimensional power spectrum I (f) can be obtained by calculating the rotational average of the two-dimensional power spectrum displayed in polar coordinates based on the equation (3).

　本願におけるパワースペクトル密度（ＰＳＤ）は、この一次元パワースペクトルＩ（ｆ）を評価対象面積（８μｍ×８μｍ）で除したものであり、従って単位は（長さ）^４、例えばｎｍ^４となる。

The power spectral density (PSD) in the present application is obtained by dividing the one-dimensional power spectrum I (f) by the area to be evaluated (8 μm × 8 μm), and therefore the unit is (length) ⁴ , for example, nm ⁴ .

The two-dimensional function h (x, y) can be measured using a device that can obtain three-dimensional information of the surface shape, such as a confocal microscope, an interference microscope, and an atomic force microscope. Further, the two-dimensional power spectrum H ² (f _x , f _y ) and the one-dimensional power spectrum I (f) are calculated from the measured two-dimensional function h (x, y) using various analysis softwares. Can do. Furthermore, the power spectral density (PSD) can be calculated from the calculated one-dimensional power spectrum I (f).

Alternatively, using the 3D image analysis software installed in various 3D image analyzers such as confocal microscope, atomic force microscope, interference microscope, scanning electron microscope, and scanning transmission electron microscope, the power spectrum The density (PSD) may be calculated.

Examples of such image processing software include, for example, commercially available SPIP (registered trademark) image analysis software (Image Metrology).

In this application, the power spectral density (PSD) of the thermal barrier glass was evaluated using SPIP (registered trademark) image analysis software (version 6.4.2). The average P value was calculated from the obtained PSD-frequency relationship.

(About heat insulation performance of heat insulation glass)
Next, the heat insulation performance of the heat insulation glass will be briefly described.

In general, the heat insulation performance of the heat insulation glass can be expressed by the following equation (4):

SC = g value / 0.88 (4) Formula
Here, the g value is a solar heat gain rate, and the heat directly transmitted to the other side (second side) with respect to the total solar heat incident from one side (first side) of the heat shielding glass ( (Transmission heat) and the heat absorbed in the heat insulating glass and then released to the second side. SC is a shielding coefficient. The g value can be measured according to ISO 9050: 2003.

In the present application, the heat shielding property of the heat shielding glass was evaluated using this shielding coefficient SC.

(Each member that constitutes thermal barrier glass)
Next, each member which comprises the 1st thermal insulation glass 100 which has the above characteristics is demonstrated in detail.

In the following description, for the sake of clarity, reference numerals shown in FIG. 1 are used to represent each member. For the sake of simplification of description, here, as an example, in the first thermal barrier glass 100, the first layer 140 includes antimony-containing tin oxide, and the second layer 150 includes fluorine-containing tin oxide. Assume that

(Glass plate 110)
The glass plate 110 may be made of, for example, soda lime glass, borosilicate glass, non-alkali glass, or aluminosilicate glass.

Further, the glass plate 110 may be transparent or colored. The color of the colored glass plate 110 is not particularly limited, but the color of the glass plate 110 may be, for example, green or blue.

The thickness of the glass plate 110 is not particularly limited, but the thickness is, for example, in the range of 2 mm to 12 mm. The glass plate 110 is preferably a tempered glass, particularly a chemically tempered glass, because the plate thickness can be reduced.

(Coating film 120)
(Underlayer 130)
The underlayer 130 has a role of suppressing diffusion of predetermined elements between the glass plate 110 and the first layer 140 and a role of adjusting the appearance color of the heat shielding glass 100.

The underlayer 130 may be composed of, for example, a layer mainly composed of silicon oxide or a layer mainly composed of tin oxide. Here, in the present application, “the layer mainly composed of the material A” means that the material A is contained in an amount of 50% by mass or more in the target layer.

For example, the underlayer 130 may be silicon oxide (SiO _x ) or tin oxide (SnO _x ). Alternatively, the foundation layer 130 may be made of silicon oxycarbide (SiOC).

The underlayer 130 does not necessarily need to be composed of a single layer, and the underlayer 130 may be composed of two or more layers. For example, the foundation layer 130 may be composed of two layers of tin oxide and silicon oxide.

The thickness of the underlayer 130 is, for example, in the range of 10 nm to 100 nm.

The installation method of the foundation layer 130 is not particularly limited. The underlayer 130 is formed by, for example, physical vapor deposition (for example, vacuum deposition, ion plating, and sputtering), chemical vapor deposition (for example, thermal CVD, plasma CVD, and photo CVD), and the like. You may comprise by the method selected from the ion beam sputtering method etc.

(First layer 140)
The first layer 140 has tin oxide containing antimony. For example, the first layer 140 may be made of tin oxide containing antimony.

When the first layer 140 is composed of antimony-containing tin oxide, the content of antimony with respect to the first layer 140 is, for example, in the range of 1% by mass to 15% by mass, and 6% by mass to 10% by mass. A range is preferable. The amount of doping can be measured by, for example, XRF (fluorescence X-ray analysis).

The thickness of the first layer 140 is, for example, in the range of 50 nm to 500 nm, preferably in the range of 150 nm to 350 nm, and more preferably in the range of 170 nm to 250 nm.

The installation method of the first layer 140 is not particularly limited. The first layer 140 is formed by, for example, physical vapor deposition (for example, vacuum vapor deposition, ion plating, and sputtering), chemical vapor deposition (for example, thermal CVD, plasma CVD, and photo CVD). , And a method selected from ion beam sputtering and the like.

(Second layer 150)
The second layer 150 includes tin oxide containing fluorine. For example, the second layer 150 may be made of tin oxide containing fluorine.

The thickness of the second layer 150 is, for example, in the range of 50 nm to 500 nm, preferably in the range of 150 nm to 350 nm, and more preferably in the range of 170 to 250 nm.

As described above, the total thickness of the first layer 140 and the second layer 150 is 340 nm or more, and preferably 360 nm to 420 nm.

The installation method of the second layer 150 is not particularly limited. The second layer 150 may be formed by, for example, physical vapor deposition (for example, vacuum vapor deposition, ion plating, and sputtering), chemical vapor deposition (for example, thermal CVD, plasma CVD, and photo CVD). , And a method selected from ion beam sputtering and the like.

(First heat shield glass 100)
As described above, the first heat blocking glass 100 is measured in the region of 8 [mu] m × 8 [mu] m on the second side 104, the average power spectrum density between the frequency 1μm ^-1 ~ 2μm ^-1 (average P values) Is 6 × 10 ⁶ nm ⁴ or less.

The haze value measured in the first thermal barrier glass 100 decreases as the average P value decreases. The average P value is preferably 5 × 10 ⁶ nm ⁴ or less.

In addition, the thermal insulation glass whose average P value is 6 × 10 ⁶ nm ⁴ or less is, for example,
(I) When the second layer 150 is formed by the CVD method, the film formation temperature is set to 580 ° C. or less, and (ii) the unevenness of the underlayer 130 is suppressed as much as possible (for example, arithmetic average roughness) Ra <10 nm),
Etc. can be obtained. However, these (i) and (ii) are merely examples, and heat shielding glass having an average P value of 6 × 10 ⁶ nm ⁴ or less can be obtained by other methods.

In the first heat shield glass 100, the haze value is, for example, 0.8% or less. The haze value is preferably 0.7% or less.

Further, in the first heat-shielding glass 100, the shielding coefficient is preferably SC <0.6, and particularly preferably SC <0.55.

However, it should be noted that the shielding coefficient SC can vary greatly depending on whether the glass plate 110 is colored or not. The aforementioned preferred range is a value when the glass plate 110 is uncolored.

Hereinafter, examples of the present invention will be described. In the following description, Examples 1 to 4 are Examples, and Examples 5 to 7 are Comparative Examples.

(Example 1)
Thermal barrier glass was manufactured by the following method.

First, a transparent uncolored glass plate was prepared. Next, a coating film was formed on the surface (first surface) of the glass plate. The coating film has a three-layer structure as shown in FIG.

The underlayer was a SiOC layer (target thickness: 58 nm) and formed by a normal pressure CVD method. The arithmetic average roughness (Ra) of the underlayer after film formation was about 9.3 nm.

Next, a first layer was formed on the base layer. The first layer was an antimony-doped tin oxide layer. The first layer was formed by a normal pressure CVD method. As a raw material gas, a mixture gas obtained by diluting monobutyltin chloride (MBTC), water, and antimony trichloride (SbCl ₃ ) with air was used. The target thickness of the first layer was 185 nm.

Next, a second layer was formed on the first layer. The second layer was a fluorine-doped tin oxide layer. The second layer was formed by a normal pressure CVD method. As a source gas, a gas obtained by diluting a mixed gas obtained by vaporizing monobutyltin chloride (MBTC), water, and hydrogen fluoride with air was used. The temperature of the glass plate in forming the second layer was about 550 ° C.

The target thickness of the second layer was 182 nm. Therefore, the total thickness of the first layer and the second layer is about 367 nm.

Thereby, a thermal barrier glass (hereinafter referred to as thermal barrier glass 1) was produced.

(Example 2 to Example 7)
In the same manner as in Example 1, thermal insulation glass 2 to thermal insulation glass 7 were produced. However, in these examples, the color of the glass plate, the configuration of the coating film, the surface roughness of the underlayer, the film thickness of the first layer and the second layer, and / or the film formation temperature of the second layer The conditions different from those in Example 1 were adopted.

Table 1 below summarizes the manufacturing conditions for each of the heat shield glasses 1-7.

　（評価）
　前述のように製造された各遮熱ガラスを用いて、以下の評価を行った。

(Evaluation)
The following evaluation was performed using each heat-shielding glass manufactured as described above.

(Evaluation of thermal insulation)
About each heat insulation glass, it measured spectrophotometrically using the spectrophotometer Lambda950 made from Perkin Elmer, and the shielding coefficient SC was computed by the method based on ISO9050: 2003.

In addition, this measurement was performed by irradiating light from the glass plate side of each heat shielding glass (that is, the opposite side of the coating film).

In the column of “SC” in Table 2 below, the shielding coefficient SC obtained for each heat shielding glass is shown together.

　（平均Ｐ値の評価）
　各遮熱ガラスについて、コーティング膜側の表面の８μｍ×８μｍの領域において、パワースペクトル密度（ＰＳＤ）の周波数依存性を評価した。また、得られた結果から、周波数１μｍ^－１～２μｍ^－１の間の平均パワースペクトル密度（平均Ｐ値）を算定した。

(Evaluation of average P value)
About each thermal insulation glass, the frequency dependence of power spectral density (PSD) was evaluated in the area | region of 8 micrometers x 8 micrometers of the surface by the side of a coating film. Further, from the obtained results, an average power spectral density (average P value) between frequencies 1 μm ⁻¹ and 2 μm ⁻¹ was calculated.

The frequency dependence of the PSD is evaluated by measuring the surface morphology of each thermal barrier glass using an atomic force microscope and then using SPIP (registered trademark) image analysis software (version 6.4.2). The analysis was carried out. The average P value was calculated from the obtained frequency-PSD relationship.

FIG. 2 shows, as an example, evaluation results of the frequency dependence of PSD in the heat shielding glasses 2 and 6. In FIG. 2, the horizontal axis is frequency, and the vertical axis is PSD.

From such a frequency-PSD relationship, the average power spectral density, that is, the average P value in the frequency region of ¹ μm ⁻¹ to 2 μm ⁻¹ is calculated.

In the column of “average P value” in the above-mentioned Table 2, the results of average P values obtained for each heat shielding glass are shown together.

(Evaluation of haze value)
About each heat insulation glass, the haze value was measured using the haze meter.

In the “Haze value” column in Table 2 above, the haze values obtained for each heat-shielding glass are shown together.

(result)
As shown in Table 2, as a result of the evaluation of the heat shielding property, it was found that the heat shielding glass 5 has a shielding coefficient SC of 0.64, and a very good heat shielding property cannot be obtained. This seems to be because the total thickness of the first layer and the second layer is thinner in the heat shield glass 5 than in other heat shield glasses. That is, it is considered that the heat shielding glass 5 has a total thickness of the first layer and the second layer of only 290 nm, and as a result, sufficient heat shielding properties could not be exhibited. Therefore, in order to obtain a sufficient heat shielding property such that the shielding coefficient SC is less than 0.6, it is considered that the first layer and the second layer need to have a total thickness of 340 nm or more in total.

FIG. 3 collectively shows the relationship between the average P value and the haze value obtained in each heat shielding glass. In FIG. 3, the numbers in the plots represent the numbers of the heat shielding glass.

FIG. 3 shows that the average P value has a positive correlation with the haze value. Further, in the heat glass 7 barrier average P value exceeds 6.0 × ¹⁰ 6 nm ^4, haze value exceeds 0.8%, it is found to have no less good transparency. On the other hand, in the heat shield glasses according to the heat shield glasses 1 to 4, the average P value is suppressed to 6.0 × 10 ⁶ nm ⁴ or less, and further to 5.0 × 10 ⁶ nm ⁴ or less. As a result, it can be seen that the haze value is suppressed to 0.8% or less, and further 0.7 or less.

From these results, it was confirmed that the heat-shielding glass 1 to the heat-shielding glass 4 exhibited good heat-shielding properties and significantly suppressed the haze value.

This application claims priority based on Japanese Patent Application No. 2016-028393 filed on February 17, 2016, the entire contents of which are incorporated herein by reference.

DESCRIPTION OF SYMBOLS 100 1st thermal insulation glass 102 1st side 104 2nd side 110 Glass plate 112 1st surface 114 2nd surface 120 Coating film 130 Underlayer 140 1st layer 150 2nd layer

Claims (7)

A heat-shielding glass having a glass plate having first and second surfaces facing each other, and a coating film provided on the first surface of the glass plate,
The coating film includes a base layer, and a first layer and a second layer disposed on the base layer, and the first layer includes the base layer and the second layer. Placed between
Either one of the first layer and the second layer contains tin oxide containing antimony, and the other of the first layer and the second layer contains tin oxide containing fluorine,
The total thickness of the first layer and the second layer is 340 nm or more,
In the coating layer surface of the thermal barrier glass, measured in the region of 8 [mu] m × 8 [mu] m, an average power spectral density between the frequency 1 [mu] m ^-1 ~ 2 [mu] m ^-1 is 6 × ¹⁰ 6 nm ⁴ or less, Thermal barrier glass. The heat insulating glass according to claim 1, wherein the first layer contains tin oxide containing antimony. The heat shielding glass according to claim 2, wherein the content ratio of antimony in the first layer is in the range of 1% to 15% by mass ratio. The thermal barrier glass according to any one of claims 1 to 3, wherein the underlayer includes silicon oxide. The heat insulating glass according to any one of claims 1 to 4, having a haze value of 0.8% or less. The heat insulating glass according to any one of claims 1 to 4, wherein the haze is 0.7% or less. The heat insulating glass according to any one of claims 1 to 6, wherein the glass plate is colorless.

Images