JP7156312B2 - heat insulating glass - Google Patents

Description

The present invention relates to heat insulating glass.

Due to the recent heightened awareness of energy conservation, the number of cases where heat insulating glass is applied to the window glass of buildings is increasing.

Heat-shielding glass is also called heat-reflecting glass, and is formed, for example, by placing a laminated film having heat-reflecting properties on the surface of a glass substrate (eg, Patent Document 1).

When such a heat insulating glass is applied to a window glass so that the laminated film side faces the indoor side, heat rays irradiated from the outside to the heat insulating glass are reflected by the laminated film. Therefore, heat rays are suppressed from entering the room, and the heat shielding property of the window glass can be enhanced.

WO2016/060082

In conventional heat shield glass, heat rays from the outside enter from the outside (first surface) of the glass substrate, pass through the inside of the glass substrate, and pass through the inside of the glass substrate (second surface). It is reflected by the film and radiated outdoors.

In this case, the heat ray passes through the inside of the glass substrate twice (for one round trip). Therefore, part of the heat rays is absorbed by the glass substrate, thereby locally increasing the temperature of the glass substrate. If the tendency of the glass substrate to absorb heat rays increases, a temperature difference may occur in the glass substrate, resulting in the problem of thermal cracking. On the other hand, when the laminated film contains a metal nitride having high heat absorption properties, the temperature difference is more likely to occur in the glass substrate compared to the laminated film containing a metal oxide, increasing the risk of thermal cracking.

In particular, in the future, in order to achieve even better heat shielding properties, there will be a growing trend in heat shielding glass to combine a glass substrate with a low energy transmittance Te ₀ and a laminated film containing a metal nitride with high heat absorption. is expected. However, when such heat insulating glass is used, more heat is absorbed by the glass substrate, which can result in a more pronounced risk of thermal cracking.

The present invention has been made in view of such a background, and an object of the present invention is to provide a heat insulating glass that has good heat insulating properties and is less prone to thermal cracking.

In the present invention, the heat insulating glass is
a glass substrate having a first surface;
a laminated film disposed on the first surface;
has
The glass substrate has an energy transmittance Te ₀ of less than 70%,
The laminated film has a conductive layer and an outermost layer in order of proximity to the glass substrate,
the conductive layer comprises a metal nitride;
The outermost layer is composed of an oxide containing Si and Zr,
The heat insulating glass is provided, wherein the laminated film is provided on the outdoor side of the heat insulating glass.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a heat shielding glass that has good heat shielding properties and is less prone to thermal cracking.

1 is a cross-sectional view schematically showing heat insulating glass according to an embodiment of the present invention; FIG. FIG. 4 is a cross-sectional view schematically showing another heat insulating glass according to one embodiment of the present invention; FIG. 4 is a cross-sectional view schematically showing still another heat insulating glass according to one embodiment of the present invention;

In the present invention, the thickness of the glass substrate and the thickness of each layer constituting the laminated film are geometrical thicknesses. In addition, "-" indicating a numerical range means that the numerical values described before and after it are included as the lower limit and the upper limit.

An embodiment of the present invention will be described in more detail below.

As described above, in conventional heat shield glass, thermal cracking is likely to occur, especially when a glass substrate with a low energy transmittance Te ₀ is used in combination with a laminated film containing a metal nitride with high heat absorption. There is a concern that

The inventors of the present application have made intensive studies in order to deal with such problems. As a result, the inventors of the present application have found that the problem of thermal cracking can be improved by using heat insulating glass in such a manner that the laminated film is on the outdoor side. This is because when the laminated film is placed on the outdoor side, the heat rays incident on the heat insulating glass from the outside are reflected by the laminated film before entering the glass substrate.

However, in conventional heat insulating glass, it is difficult to provide practical heat insulating glass simply by setting the laminated film on the outdoor side. This is because, in such a mode of use, the heat shield glass may not have good heat shielding properties, and the environmental resistance may be lowered.

Based on these considerations, the inventors of the present application have made intensive research and development efforts to find a heat shielding glass that has heat shielding properties that are comparable to those of conventional heat shielding glass and that has excellent environmental resistance. The invention of the present application has been achieved.

That is, in one embodiment of the invention,
heat insulating glass,
a glass substrate having a first surface;
a laminated film disposed on the first surface;
has
The glass substrate has an energy transmittance Te ₀ of less than 70%,
The laminated film has a conductive layer and an outermost layer in order of proximity to the glass substrate,
the conductive layer comprises a metal nitride;
The outermost layer is composed of an oxide containing Si and Zr,
The heat insulating glass is provided, wherein the laminated film is provided on the outdoor side of the heat insulating glass.

Such heat shield glass uses a laminated film containing a glass substrate having an energy transmittance Te ₀ of less than 70% and a metal nitride with high heat absorption, but is configured so that the laminated film is on the outdoor side. Therefore, the risk of thermal cracking can be significantly reduced.

Further, in the heat insulating glass according to one embodiment of the present invention, the laminated film has a conductive layer containing metal nitride and an outermost layer made of an oxide containing Si and Zr. According to the inventors of the present application, it has been confirmed that such a laminated film exhibits good shielding properties against heat rays.

Furthermore, in the heat insulating glass according to one embodiment of the present invention, the outermost layer of the laminated film is composed of an oxide containing Si and Zr. Experiments by the inventors of the present application have shown that such oxides have good environmental resistance. Furthermore, the heat insulating glass has excellent heat resistance. Specifically, physical strengthening treatment such as air cooling strengthening (for example, treatment held in an air atmosphere at 680 ° C. for 20 minutes) and laminated film curing treatment (for example, treatment held in an air atmosphere at 500 ° C. for 20 minutes). The heat insulating glass can maintain good heat insulating properties and durability even after the heat treatment. Therefore, in the heat insulating glass according to one embodiment of the present invention, deterioration can be significantly suppressed even if the laminated film is installed on the outdoor side.

Due to these characteristics, in one embodiment of the present invention, although a glass substrate and a laminated film that relatively easily absorb heat rays are used, good heat shielding properties and durability are obtained, and thermal cracking is achieved. It is possible to provide a heat insulating glass that is less likely to cause

(Heat shield glass according to one embodiment of the present invention)
A heat insulating glass according to an embodiment of the present invention will be described below with reference to the drawings.

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

As shown in FIG. 1 , the first heat insulating glass 100 has a glass substrate 110 and a laminated film 120 .

The glass substrate 110 has an energy transmittance Te ₀ of less than 70%. Here, the energy transmittance means the energy transmittance measured according to ISO9050:2003.

The glass substrate 110 has a first surface 112 and a second surface 114 and the laminate film 120 is placed on the first surface 112 of the glass substrate 110 .

Laminated film 120 has at least two layers, conductive layer 130 and outermost layer 150 . Among them, the conductive layer 130 is placed closer to the glass substrate 110 , and the outermost layer 150 is placed on the conductive layer 130 .

The conductive layer 130 forming the laminated film 120 is made of a metal nitride such as chromium nitride (CrN). Also, the outermost layer 150 is composed of an oxide containing silicon (Si) and zirconium (Zr).

A first thermal barrier glass 100 has a first side 102 and a second side 104 and a laminate 120 is disposed on the first side 102 .

Here, when the first heat insulating glass 100 is applied as a window glass, the first side 102 corresponds to the outdoor side and the second side 104 corresponds to the indoor side. Therefore, in an actual usage mode, the laminated film 120 is arranged so as to be on the outdoor side. On the other hand, the second surface 114 of the glass substrate 110 is arranged to face the room.

In the first heat shield glass 100 having such a configuration, the laminated film 120 is arranged on the first side 102 . Therefore, the first heat shield glass 100 can significantly reduce the risk of thermal cracking. Furthermore, in the first heat shield glass 100, the reflected color when viewed from the outdoor side can be easily adjusted by the laminated film.

The first heat insulating glass 100 also includes the laminated film 120 having the conductive layer 130 and the outermost layer 150 configured as described above. Such a laminated film 120 exhibits good shielding properties against heat rays. Also, the outermost layer 150 exhibits good environmental resistance and heat resistance.

Due to these characteristics, the first heat shield glass 100 does not suffer from thermal cracking even though the glass substrate 110 with a low energy transmittance Te ₀ and a laminated film containing a metal nitride with high heat ray absorption are used. can significantly reduce the risk of In addition, it is possible to easily adjust the reflected color when viewed from the outdoor side. Furthermore, the first heat shielding glass 100 can exhibit good heat shielding properties and durability.

(Each component of the heat insulating glass according to one embodiment of the present invention)
Here, each constituent member included in the first heat insulating glass 100 will be described in more detail.

(Glass substrate 110)
As mentioned above, the glass substrate 110 has an energy transmittance Te ₀ of less than 70%. The energy transmittance Te ₀ is preferably 60% or less, more preferably 50% or less. Since the first heat shield glass 100 reduces the risk of thermal cracking, even the glass substrate 110 having such a low energy transmittance Te ₀ can be used properly. The energy transmittance Te ₀ is preferably 10% or more, more preferably 20% or more.

Further, by using a glass substrate with a Te ₀ of less than 70%, it is possible to widen the adjustment range of the reflected color of the first heat shield glass 100 when viewed from the outdoor side.

The thickness of the glass substrate 110 is preferably 0.5 to 12 mm. More preferably, the thickness is 1 mm or more, and more preferably 2 mm or more. More preferably, the thickness is 10 mm or less, and even more preferably 9 mm or less.

The glass substrate 110 may be colored.

Further, the glass substrate 110 may or may not be subjected to strengthening treatment such as air-cooling strengthening.

(Conductive layer 130)
Conductive layer 130 includes a metal nitride, as previously described. The metal contained in the metal nitride may be, for example, at least one of chromium (Cr), titanium (Ti), zirconium (Zr), niobium (Nb), tantalum (Ta), and hafnium (Hf). . The metal contained in the metal nitride is preferably at least one of chromium, titanium and zirconium.

Conductive layer 130 is preferably composed of chromium nitride (CrN), titanium nitride (TiN), or zirconium nitride (ZrN), among others. When the conductive layer 130 is made of these materials, the heat shielding properties of the first heat shielding glass 100 can be easily enhanced.

The conductive layer 130 preferably has an extinction coefficient k of 0.5 or more at a wavelength of 1000 nm. When the extinction coefficient k of the conductive layer 130 at a wavelength of 1000 nm is 0.5 or more, the heat ray absorbing property is enhanced, so that excellent heat shielding properties can be obtained. The extinction coefficient k is more preferably 1 or more, and even more preferably 2 or more. The extinction coefficient k is preferably 10 or less, more preferably 8 or less. When the extinction coefficient k of the conductive layer 130 is 10 or less, heat rays are not excessively absorbed, so the risk of thermal cracking can be reduced. Since the first heat shield glass 100 reduces the risk of thermal cracking, even a glass substrate provided with such a highly heat-absorbing laminated film can be properly used.

The thickness of the conductive layer 130 is preferably in the range of 5 nm to 50 nm. When the thickness of the conductive layer 130 is 5 nm or more, the heat shielding properties of the first heat shielding glass 100 can be easily enhanced. When the thickness of the conductive layer 130 is 50 nm or less, the outdoor reflection color of the first heat shield glass 100 can be easily adjusted to light blue. More preferably, the thickness is in the range of 5 nm to 30 nm, even more preferably in the range of 5 nm to 25 nm.

A method for forming the conductive layer 130 is not particularly limited. The conductive layer 130 is formed by, for example, a vacuum deposition method, an ion plating method, a sputtering method, a chemical vapor deposition (CVD) method (thermal CVD method, plasma CVD method, and optical CVD method), and an ion beam sputtering method. may be formed.

(Outermost layer 150)
The outermost layer 150 is formed of an oxide containing Si and Zr, as described above.

The content of ZrO ₂ in the outermost layer 150 is preferably in the range of 10mol% to 90mol%. The content of ZrO ₂ is more preferably in the range of 20 mol % to 50 mol %, still more preferably in the range of 25 mol % to 35 mol %.

On the other hand, the content of SiO ₂ in the outermost layer 150 is preferably in the range of 10 mol % to 90 mol %. The content of SiO ₂ is more preferably in the range of 50 mol % to 80 mol %, even more preferably in the range of 65 mol % to 75 mol %.

The carbon content in the outermost layer 150 is preferably 1 atomic % or less. The carbon content in the outermost layer 150 can be measured by XPS. When the carbon content in the outermost layer 150 is 1 at% or less, physical strengthening treatment such as air cooling strengthening (for example, treatment of holding in an air atmosphere at 680 ° C. for 20 minutes) or curing treatment of the laminated film (for example, 500 ° C. The heat insulating glass can maintain good heat insulating properties and durability even after being subjected to heat treatment such as holding in an air atmosphere for 20 minutes. The carbon content in the outermost layer 150 is more preferably 0.5 at % or less, particularly preferably 0.3 at % or less.

The thickness of the outermost layer 150 is preferably in the range of 5 nm to 60 nm. When the thickness of the outermost layer 150 is in the range of 5 nm to 60 nm, the reflected color of the first heat shield glass 100 can be easily adjusted. More preferably, the thickness of the outermost layer 150 is in the range of 8 nm to 40 nm, and even more preferably in the range of 10 nm to 30 nm.

The outermost layer 150 may have a refractive index in the range of 1.55 to 2.20 for light with a wavelength of 632 nm. When the refractive index of the outermost layer 150 is in the range of 1.55 to 2.20, the reflected color of the first heat shield glass 100 can be easily adjusted. The refractive index of the outermost layer 150 is preferably in the range of 1.60 to 1.90, more preferably in the range of 1.65 to 1.80.

A method for forming the outermost layer 150 is not particularly limited. The outermost layer 150 is formed by, for example, a vacuum deposition method, an ion plating method, a sputtering method, a chemical vapor deposition (CVD) method (thermal CVD method, plasma CVD method, and optical CVD method), and an ion beam sputtering method. may be formed.

(Characteristics of first heat shield glass 100)
The first heat insulating glass 100 may have the following properties:
(1) Shielding coefficient SC≤0.4,
(2) selectivity Se≧0.9,
(3) Energy absorption rate Ae ≤ 65%,
(4) outdoor reflectance Rv≦30%,
(5) Outdoor reflection color a ^* <5, b ^* <5,
(6) Yellowness index of transmitted light YI<5.

Of these, the shielding coefficient SC can be obtained from the following formula (1) in accordance with ISO9050:2003:

SC = (g / 100) / 0.88 (1) formula

Here, g (%) is also called the solar heat gain rate, and is the total solar heat incident from the outdoor side of the heat shielding glass (the first side 102 in the case of the first heat shielding glass 100). The sum of the heat (transmitted heat) that is directly transmitted (in the case of the first heat shield glass 100, the second side 104) and the heat that is absorbed inside the heat shield glass and then released into the room. Expressed as a percentage.

The shielding coefficient SC is an index representing the heat shielding performance of the heat shielding glass, and it can be said that the smaller the value, the higher the heat shielding performance of the heat shielding glass. When the first heat shielding glass 100 has a shielding coefficient SC of 0.4 or less, good heat shielding properties can be exhibited. The heat shield coefficient SC is more preferably 0.38 or less, even more preferably 0.36 or less.

On the other hand, the selectivity Se is an index related to heat insulation, and is represented by the following formula (2):

Se=Tv/g Formula (2)

Here, Tv (%) is the visible light transmittance (%) from the outdoor side of the heat insulating glass.

In heat shield glass, the higher the visible light transmittance Tv (%) and the lower the solar heat gain g (%), that is, the higher the selectivity Se, the higher the heat insulating properties of the heat shield glass.

Therefore, in the first heat insulating glass 100, when the selectivity Se exceeds 90%, good heat insulating properties can be exhibited. More preferably, the selectivity Se is over 100%, and even more preferably over 110%.

In addition, the energy absorption rate Ae is an index relating to the absorption rate of heat rays in heat insulating glass, and is represented by the following formula (3):

Ae = 100 (%) - Te (%) - Re (%) (3) formula

Here, Te is the energy transmittance from the outdoor side of the heat insulating glass, and Re is the energy reflectance from the outdoor side of the heat insulating glass.

When the energy absorption rate Ae of the first heat insulating glass 100 is 65% or less, heat absorption to the inside is suppressed, and thermal cracking can be further suppressed. The energy absorption rate Ae is more preferably 60% or less, even more preferably 55% or less, and particularly preferably 50% or less.

The outdoor reflectance Rv represents the reflectance of visible light reflected on the outdoor side of the heat shield glass. When the outdoor reflectance Rv of the first heat shield glass 100 is 30% or less, glare due to reflected light can be significantly suppressed. The outdoor reflectance Rv is more preferably 28% or less, and even more preferably 26% or less.

In addition, a ^* and b ^* , which are indicators of the color of the outdoor reflected color, are obtained when the reflected light on the outdoor side of the heat shield glass is represented by CIE1976L ^* a ^* b ^* chromaticity coordinates ^. means the value of b ^* .

In general, from an aesthetic point of view, light blue is preferred as the outdoor reflection color of heat shield glass, and red to yellow tend to be avoided. In the first heat insulating glass 100 having a ^* and b ^* within the above ranges, the outdoor reflection color can be in a pale blue region. a ^* is more preferably 3 or less, even more preferably 1 or less. b ^* is more preferably 3 or less, even more preferably 1 or less.

Also, the yellowness index YI is an index that quantifies the yellowness of visible light that has passed through the heat shield glass. A color tone that exaggerates yellowishness when the outside is visually recognized from inside the room through the heat insulating glass is not preferable. When the yellowness index YI of the first heat shield glass 100 is less than 5, transmitted light with little yellowness can be obtained. The yellowness index YI is more preferably 1 or less, and even more preferably -5 or less.

The yellowness index YI can be obtained by converting the chromaticity of transmitted light obtained in accordance with JIS Z7701:1990 by a method in accordance with the ASTM E131 standard.

In the configuration of the heat insulating glass shown in FIG. 1, it may be difficult to exhibit one or more of the characteristics (1) to (6). However, in the configuration of the heat insulating glass described below, the characteristics (1) to (6) can be more easily realized.

(Another heat insulating glass according to an embodiment of the present invention)
Next, another heat insulating glass according to one embodiment of the present invention will be described with reference to FIG.

FIG. 2 schematically shows a cross section of another heat insulating glass (hereinafter referred to as "second heat insulating glass") according to one embodiment of the present invention.

As shown in FIG. 2 , the second heat insulating glass 200 has a glass substrate 210 and a laminated film 220 .

The glass substrate 210 has the same features as the glass substrate 110 in the first heat insulating glass 100 described above. Therefore, it will not be described further here.

On the other hand, unlike the laminated film 120 in the first heat insulating glass 100 described above, the laminated film 220 has a conductive layer 230, an outermost layer 250, and a color tone correction layer. For example, the laminated film 220 has a first color tone correction layer 260 , a conductive layer 230 , a second color tone correction layer 265 and an outermost layer 250 from the side closer to the glass substrate 210 .

The first color tone correction layer 260 and the second color tone correction layer 265 are provided to adjust reflected light and/or transmitted light generated in the second heat shield glass 200 to a desired color. For example, a bluish tint is generally preferred as the outdoor reflection color of window glass. By using the first color tone correction layer 260 and the second color tone correction layer 265, it is possible to easily express such color.

The first color tone correction layer 260 is an insulating layer and is made of, for example, silicon-containing nitride (SiN). The first tone correction layer 260 may be composed of a nitride containing silicon and aluminum (SiAlN). Alternatively, the first tone correction layer 260 may be composed of a nitride containing silicon and zirconium (SiZrN). When the first color tone correction layer 260 is made of SiAlN, the AlN content is preferably in the range of 1 mol % to 20 mol %, more preferably in the range of 2 mol % to 18 mol %, and 2 mol %. More preferably ~16 mol%. On the other hand, when the first color tone correction layer 260 is made of SiZrN, the content of ZrN is preferably in the range of 1 mol % to 40 mol %, more preferably in the range of 2 mol % to 35 mol %. It is more preferably 2 mol % to 30 mol %.

The thickness of the first color tone correction layer 260 is preferably in the range of 5 nm to 100 nm, more preferably in the range of 5 nm to 80 nm, even more preferably in the range of 5 nm to 60 nm.

The same can be said for the second color tone correction layer 265 . The first color tone correction layer 260 and the second color tone correction layer 265 may be made of the same material or different materials.

The first color tone correction layer 260 and the second color tone correction layer 265 can be formed by, for example, a sputtering method.

The configuration and characteristics of the conductive layer 230 and the outermost layer 250 included in the laminated film 220 are as described above. Therefore, it will not be described further here.

A second thermal barrier glass 200 has a first side 202 and a second side 204 and a laminate 220 is disposed on the first side 202 . Also, when the second heat insulating glass 200 is used, the first side 202 corresponds to the exterior side and the second side 204 corresponds to the interior side.

The second heat shield glass 200 having such a configuration can also achieve the effects described above. That is, in the second heat shield glass 200, although the glass substrate 210 with a low energy transmittance Te ₀ and the laminated film 220 containing a metal nitride with high heat ray absorption are used, there is no risk of thermal cracking. can be significantly suppressed. Further, with the second heat insulating glass 200, it is possible to easily adjust the reflected color when viewed from the outdoor side. Furthermore, the second heat shielding glass 200 can exhibit good heat shielding properties and durability.

(Still another heat insulating glass according to an embodiment of the present invention)
Next, still another heat insulating glass according to one embodiment of the present invention will be described with reference to FIG.

FIG. 3 schematically shows a cross section of yet another heat insulating glass (hereinafter referred to as "third heat insulating glass") according to one embodiment of the present invention.

As shown in FIG. 3 , the third heat insulating glass 300 has a glass substrate 310 and a laminated film 320 .

The glass substrate 310 has the same features as the glass substrate 110 in the first heat insulating glass 100 described above. Therefore, it will not be described further here.

On the other hand, the laminated film 320 has a first conductive layer 330, an outermost layer 350, a color tone correction layer and a second conductive layer 370, unlike the laminated film 120 in the first heat insulating glass 100 described above. For example, the laminated film 320 includes, from the side closer to the glass substrate 310, a first color tone correction layer 360, a first conductive layer 330, a second color tone correction layer 365, a second conductive layer 370, a third color tone correction layer. It has a layer 375 and an outermost layer 350 .

The first color tone correction layer 360, the second color tone correction layer 365, and the third color tone correction layer 375 adjust the reflected light and/or transmitted light generated in the third heat shield glass 300 to a desired color. is installed to

Each of the color tone correction layers 360, 365 and 375 is an insulating layer.

As described above, the first color correction layer 360 may be composed of a nitride containing silicon (SiN), a nitride containing silicon and aluminum (SiAlN), a nitride containing silicon and zirconium (SiZrN), or the like. Also good. The thickness of the first color tone correction layer 360 is preferably in the range of 5 nm to 100 nm, more preferably in the range of 5 nm to 80 nm, even more preferably in the range of 5 nm to 60 nm.

The same can be said for the second color tone correction layer 365 and the third color tone correction layer 375 .

Each color tone correction layer 360, 365, 375 may be composed of the same material, or may be composed of mutually different materials.

Second conductive layer 370, on the other hand, includes a metal nitride. The metal contained in the metal nitride may be, for example, at least one of chromium (Cr), titanium (Ti), zirconium (Zr), niobium (Nb), tantalum (Ta), and hafnium (Hf). . The metal contained in the metal nitride is preferably at least one of chromium, titanium and zirconium.

Second conductive layer 370 is preferably composed of chromium nitride (CrN), titanium nitride (TiN), or zirconium nitride (ZrN), among others.

The second conductive layer 370 preferably has an extinction coefficient k of 0.5 or more, more preferably 1 or more, and even more preferably 2 or more at a wavelength of 1000 nm. When the extinction coefficient k at a wavelength of 1000 nm is 0.5 or more, the heat ray absorbing property is enhanced, so that excellent heat shielding properties can be obtained. The extinction coefficient k is preferably 10 or less, more preferably 8 or less.

The thickness of the second conductive layer 370 is preferably in the range of 5 nm to 50 nm. When the thickness of the second conductive layer 370 is 5 nm or more, the heat shielding properties of the third heat shielding glass 300 can be easily enhanced. When the thickness of the second conductive layer 370 is 50 nm or less, the outdoor reflection color of the third heat shield glass 300 can be easily adjusted to light blue. More preferably, the thickness is in the range of 5 nm to 30 nm, even more preferably in the range of 5 nm to 25 nm.

A method for forming the second conductive layer 370 is not particularly limited. The second conductive layer 370 may be formed by, for example, vacuum deposition, ion plating, sputtering, chemical vapor deposition (CVD) (thermal CVD, plasma CVD, and optical CVD), and ion beam sputtering. It may be formed by a law or the like.

The second conductive layer 370 may be composed of the same material as the first conductive layer 330, or may be composed of a different material. Also, the second conductive layer 370 may have the same thickness as the first conductive layer 330 or may have a different thickness.

The configuration and features of the outermost layer 350 included in the laminated film 320 are as described above. Therefore, it will not be described further here.

A third thermal barrier glass 300 has a first side 302 and a second side 304 and a laminate 320 is disposed on the first side 302 . Also, when the third heat insulating glass 300 is used, the first side 302 corresponds to the exterior side and the second side 304 corresponds to the interior side.

The third heat shield glass 300 having such a configuration can also achieve the effects described above. That is, the third heat shield glass 300 uses a glass substrate 310 with a low energy transmittance Te ₀ and a laminated film 320 containing a metal nitride with high heat absorption, but there is a risk of thermal cracking. can be significantly suppressed. Further, with the third heat insulating glass 300, it is possible to easily adjust the reflected color when viewed from the outdoor side. Furthermore, the third heat shielding glass 300 can exhibit good heat shielding properties and durability.

An example of the configuration of the heat insulating glass according to one embodiment of the present invention has been described above with reference to FIGS. 1 to 3. FIG. However, these are merely examples, and it is obvious to those skilled in the art that the heat insulating glass of the present invention may have other configurations.

For example, in the first heat insulating glass 100, the conductive layer 130 may be composed of a multilayer film. The same applies to the second heat shield glass 200 and the third heat shield glass 300 . In addition, in the third heat insulating glass 300, the laminated film 320 is composed of six layers. However, the laminated film may be composed of more layers. In addition to this, various modifications are possible.

Next, examples of the present invention will be described. In the following description, Examples 1 to 6 are examples, and Examples 11 to 17 are comparative examples.

(Example 1)
A heat insulating glass was produced by the following method.

First, a green-colored glass substrate (GNFL: manufactured by Asahi Glass Co., Ltd.) having a length of 25 mm, a width of 50 mm, and a thickness of 6 mm was prepared.

The energy transmittance Te ₀ of this glass substrate is 41%. For the measurement of the energy transmittance Te ₀ of the glass substrate, a spectrophotometer (U4100: manufactured by Hitachi Ltd.) was used, and the wavelength of light was in the range of 300 nm to 2500 nm. Measurements were carried out according to ISO9050:2003.

Next, by a sputtering method, a laminated film consisting of a total of four layers of a first color tone correction layer, a conductive layer, a second color tone correction layer, and an outermost layer was formed on one surface (first surface) of this glass substrate. formed. The laminated film has the following layer structure from the side closer to the glass substrate:
First tone correction layer: 67 mol% SiN-33 mol% ZrN layer with a thickness of 14 nm;
Conductive layer: 7.6 nm thick CrN layer,
Second tone correction layer: 90 mol% SiN-10 mol% AlN layer with a thickness of 2.5 nm,
Outermost layer: 67 mol% SiO ₂ -33 mol% ZrO ₂ layer with a thickness of 15 nm.

Of these, the first color tone correction layer uses 67 at% Si-33 at% Zr (manufactured by AGC Ceramics Co., Ltd.) as a target, and is formed by a sputtering method in an Ar + N ₂ atmosphere (N ₂ = 40% by volume). did. The sputtering pressure was set to 0.3 Pa.

The conductive layer was formed by sputtering in an Ar+N ₂ atmosphere (N ₂ =11% by volume) using a Cr target as a target. The sputtering pressure was set to 0.2 Pa.

The second color tone correction layer was formed by sputtering in an Ar+N ₂ atmosphere (N ₂ =40% by volume) using 10 at % Al-90 at % Si as a target. The sputtering pressure was set to 0.3 Pa.

The outermost layer was formed by sputtering in an Ar+O ₂ atmosphere (O ₂ =60% by volume) using 67 at % Si-33 at % Zr (manufactured by AGC Ceramics Co., Ltd.) as a target. The sputtering pressure was set to 0.3 Pa.

As a result, heat insulating glass (hereinafter referred to as "heat insulating glass according to Example 1") was manufactured.

In addition, in the heat insulating glass according to Example 1, the laminated film is on the outdoor side.

(Example 2)
A heat insulating glass (hereinafter referred to as "heat insulating glass according to Example 2") was produced in the same manner as in Example 1.

However, in this example 2, the laminated film had the following configurations in order of proximity from the glass substrate:
First tone correction layer: 67 mol% SiN-33 mol% ZrN layer with a thickness of 22 nm;
Conductive layer: 22 nm thick TiN layer,
Second color tone correction layer: 90 mol% SiN-10 mol% AlN layer with a thickness of 5 nm,
Outermost layer: 67 mol% SiO ₂ -33 mol% ZrO ₂ layer with a thickness of 16.5 nm.

The conductive layer was formed by sputtering in an Ar+N ₂ atmosphere (N ₂ =11% by volume) using a Ti target as a target. The sputtering pressure was set to 0.2 Pa.

In addition, in the heat insulating glass according to Example 2, the laminated film is on the outdoor side.

(Example 3)
A heat insulating glass (hereinafter referred to as "heat insulating glass according to Example 3") was produced in the same manner as in Example 1.

However, in Example 3, the laminated film had the following configurations in order from the glass substrate:
First tone correction layer: 67 mol% SiN-33 mol% ZrN layer with a thickness of 28.5 nm;
Conductive layer: 15 nm thick ZrN layer,
Second color tone correction layer: 90 mol% SiN-10 mol% AlN layer with a thickness of 5 nm,
Outermost layer: 67 mol% SiO ₂ -33 mol% ZrO ₂ layer with a thickness of 19.2 nm.

The conductive layer was formed by sputtering in an Ar+N ₂ atmosphere (N ₂ =11% by volume) using a Zr target as a target. The sputtering pressure was set to 0.2 Pa.

In addition, in the heat insulating glass according to Example 3, the laminated film is on the outdoor side.

(Example 4)
A heat insulating glass (hereinafter referred to as "heat insulating glass according to Example 4") was produced in the same manner as in Example 1.

However, in Example 4, a green-colored glass substrate (GNFL: manufactured by Asahi Glass Co., Ltd.) having a thickness of 2 mm was used as the glass substrate. The energy transmittance Te ₀ of this glass substrate is 67%.

In addition, the laminated film had the following configurations in order of proximity from the glass substrate:
First tone correction layer: 67 mol% SiN-33 mol% ZrN layer with a thickness of 24 nm;
Conductive layer: 24 nm thick TiN layer,
Second color tone correction layer: 90 mol% SiN-10 mol% AlN layer with a thickness of 5 nm,
Outermost layer: 67 mol% SiO ₂ -33 mol% ZrO ₂ layer with a thickness of 12.5 nm.

In addition, in the heat insulating glass according to Example 4, the laminated film is on the outdoor side.

(Example 5)
A heat insulating glass (hereinafter referred to as "heat insulating glass according to Example 5") was produced in the same manner as in Example 1.

However, in Example 5, a blue-colored glass substrate (DHFL: manufactured by Asahi Glass Co., Ltd.) having a thickness of 6 mm was used as the glass substrate. The energy transmittance Te ₀ of this glass substrate is 44.5%.

In addition, the laminated film had the following configurations in order of proximity from the glass substrate:
First tone correction layer: 67 mol% SiN-33 mol% ZrN layer with a thickness of 22 nm;
Conductive layer: 22 nm thick TiN layer,
Second color tone correction layer: 90 mol% SiN-10 mol% AlN layer with a thickness of 5 nm,
Outermost layer: 67 mol% SiO ₂ -33 mol% ZrO ₂ layer with a thickness of 16.5 nm.

In addition, in the heat insulating glass according to Example 5, the laminated film is on the outdoor side.

(Example 6)
A heat insulating glass (hereinafter referred to as "heat insulating glass according to Example 6") was produced in the same manner as in Example 1.

However, in Example 6, the laminated film had the following six-layer structure in order from the glass substrate:
First color tone correction layer: 90 mol% SiN-10 mol% AlN layer with a thickness of 56 nm,
a first conductive layer: a TiN layer with a thickness of 7 nm;
Second tone correction layer: 67 mol% SiN-33 mol% ZrN layer with a thickness of 70 nm;
Second conductive layer: 16 nm thick TiN layer,
Third color tone correction layer: 90 mol% SiN-10 mol% AlN layer with a thickness of 5 nm,
Outermost layer: 67 mol% SiO ₂ -33 mol% ZrO ₂ layer with a thickness of 15 nm.

In addition, in the heat insulating glass according to Example 6, the laminated film is on the outdoor side.

Also, the carbon content of the outermost layer was 0.5 atomic %. The carbon content of the outermost layer was measured using XPS (PHI 5000 VersaProbe II, manufactured by ULVAC-PHI).

(Example 11)
A heat insulating glass was produced by the following method.

First, a transparent glass substrate (Clear: manufactured by Asahi Glass Co., Ltd.) having a length of 25 mm, a width of 50 mm, and a thickness of 6 mm was prepared.

The energy transmittance Te ₀ of this glass substrate is 82%.

Next, a laminated film consisting of a total of three layers, a first layer, a second layer and an outermost layer, was formed on one surface (first surface) of the glass substrate by sputtering. The laminated film has the following layer structure from the side closer to the glass substrate:
First layer: 67 mol% SiN-33 mol% ZrN layer with a thickness of 20 nm;
the second layer: a CrN layer with a thickness of 10 nm;
Outermost layer: 90 mol % SiN-10 mol % AlN layer with a thickness of 20 nm.

As a result, heat insulating glass (hereinafter referred to as "heat insulating glass according to Example 11") was manufactured.

In addition, in the heat insulating glass according to Example 11, the laminated film is on the outdoor side.

(Example 12)
A heat insulating glass (hereinafter referred to as "heat insulating glass according to Example 12") was produced in the same manner as in Example 11.

However, in this example 12, a green-colored glass substrate (GNFL: manufactured by Asahi Glass Co., Ltd.) having a thickness of 6 mm was used as the glass substrate. The energy transmittance Te ₀ of this glass substrate is 41%.

In addition, the laminated film had the following configurations in order of proximity from the glass substrate:
First layer: 67 mol% SiN-33 mol% ZrN layer with a thickness of 14 nm;
Second layer: a CrN layer with a thickness of 7.6 nm;
Outermost layer: 90 mol % SiN-10 mol % AlN layer with a thickness of 14 nm.

In addition, in the heat insulating glass according to Example 12, the laminated film is on the outdoor side.

(Example 13)
A heat insulating glass (hereinafter referred to as "heat insulating glass according to Example 13") was produced in the same manner as in Example 11.

However, in this example 12, a green-colored glass substrate (GNFL: manufactured by Asahi Glass Co., Ltd.) having a thickness of 6 mm was used as the glass substrate. The energy transmittance Te ₀ of this glass substrate is 41%.

In addition, the laminated film had the following configurations in order of proximity from the glass substrate:
First layer: 90 mol % SiN-10 mol % AlN layer with a thickness of 10 nm;
the second layer: a CrN layer with a thickness of 15 nm;
Outermost layer: 90 mol % SiN-10 mol % AlN layer with a thickness of 20 nm.

In addition, in the heat insulating glass according to Example 13, the laminated film is on the indoor side.

(Example 14)
A heat insulating glass (hereinafter referred to as "heat insulating glass according to Example 14") was produced in the same manner as in Example 11.

However, in Example 14, a green-colored glass substrate (GNFL: manufactured by Asahi Glass Co., Ltd.) having a thickness of 1.2 mm was used as the glass substrate. The energy transmittance Te ₀ of this glass substrate is 76%.

In addition, the laminated film had the following four-layer structure in order from the glass substrate:
First layer: 67 mol% SiN-33 mol% ZrN layer with a thickness of 24 nm;
Second layer: 24 nm thick TiN layer,
Third layer: 90 mol % SiN-10 mol % AlN layer with a thickness of 5 nm;
Outermost layer: 67 mol% SiO ₂ -33 mol% ZrO ₂ layer with a thickness of 12.5 nm.

In addition, in the heat insulating glass according to Example 14, the laminated film is on the outdoor side.

(Example 15)
A heat insulating glass (hereinafter referred to as "heat insulating glass according to Example 15") was produced in the same manner as in Example 11.

However, in Example 15, a green-colored glass substrate (GNFL: manufactured by Asahi Glass Co., Ltd.) having a thickness of 6 mm was used as the glass substrate. The energy transmittance Te ₀ of this glass substrate is 41%.

In addition, the laminated film had the following four-layer structure in order from the glass substrate:
First layer: 67 mol% SiN-33 mol% ZrN layer with a thickness of 14 nm;
Second layer: a TiN layer with a thickness of 7.6 nm,
Third layer: 90 mol% SiN-10 mol% AlN layer with a thickness of 2.5 nm;
Outermost layer: 16 nm thick _SiO2 layer.

In addition, in the heat insulating glass according to Example 15, the laminated film is on the outdoor side.

(Example 16)
A heat insulating glass (hereinafter referred to as "heat insulating glass according to Example 16") was produced in the same manner as in Example 11.

However, in Example 16, a green-colored glass substrate (GNFL: manufactured by Asahi Glass Co., Ltd.) having a thickness of 6 mm was used as the glass substrate. The energy transmittance Te ₀ of this glass substrate is 41%.

In addition, the laminated film had the following four-layer structure in order from the glass substrate:
First layer: 67 mol% SiN-33 mol% ZrN layer with a thickness of 24 nm;
Second layer: 24 nm thick TiN layer,
Third layer: 90 mol % SiN-10 mol % AlN layer with a thickness of 5 nm;
Outermost layer: 9 nm thick _TiO2 layer.

In addition, in the heat insulating glass according to Example 16, the laminated film is on the outdoor side.

(Example 17)
A heat insulating glass (hereinafter referred to as "heat insulating glass according to Example 17") was produced in the same manner as in Example 11.

However, in Example 17, a green-colored glass substrate (Evergreen) having a thickness of 6 mm was used as the glass substrate. The energy transmittance Te ₀ of this glass substrate is 34.5%.

In addition, the laminated film had the following four-layer structure in order from the glass substrate:
_First layer: 27 nm thick SnO2 layer,
Second layer: 17 nm thick _SiO2 layer,
Third layer: 210 nm thick fluorine ₍ F) doped SnO2 layer,
Outermost layer: 30 nm thick _TiO2 layer.

Laminated films were sequentially formed by an online CVD method.

Here, "on-line (film-forming method)" means a method of forming a film on the surface of the glass during the manufacturing process of the glass. More specifically, in the production of glass, glass is continuously produced by moving a glass ribbon over a molten tin bath and then slowly cooling it. )” deposits a film on the upper surface of the glass ribbon. That is, in the "on-line (film-forming method)", the glass manufacturing process and the film-forming process are continuously performed.

In addition, in the heat insulating glass according to Example 17, the laminated film is on the outdoor side.

Table 1 below summarizes the schematic configuration of the heat insulating glass according to each example.

（評価）
得られた遮熱ガラスを用いて、以下の評価を実施した。

(evaluation)
The following evaluations were carried out using the obtained heat insulating glass.

(Evaluation of heat shielding performance)
The heat shielding glass was used to evaluate the shielding coefficient SC, selectivity Se, energy absorption Ae, and outdoor reflectance Rv.

Of these, the shielding coefficient SC and the selectivity Se were calculated from the above-described equations (1) and (2), respectively.

The visible light transmittance Tv (%) from the outdoor side of the heat shield glass, the outdoor reflectance Rv (%), the energy transmittance Te, the energy reflectance Re on the outdoor side of the heat shield glass, and the solar heat gain rate A spectrophotometer (U4100: manufactured by Hitachi, Ltd.) was used to measure g (%), and the wavelength of light was in the range of 300 nm to 2500 nm. Measurements were carried out according to ISO9050:2003.

Also, the energy absorption rate Ae was calculated from the above equation (3).

For the heat shield glasses other than the heat shield glass according to Example 13, the measurement was performed in the direction from the laminated film side toward the exposed surface (second surface) of the glass substrate. On the other hand, for the heat insulating glass according to Example 13, the measurement was performed in the direction from the exposed surface side of the glass substrate toward the laminated film side.

(Evaluation of color tone)
The chromaticity of the outdoor reflected color was measured using a heat-shielding glass. Also, the yellowness index YI of transmitted light was evaluated.

A chromaticity meter was used to evaluate the chromaticity of the outdoor reflection color. Reflected light on the outdoor side of the heat insulating glass was expressed in CIE1976L ^* a ^* b ^* chromaticity coordinates, and the values of a ^* and b ^* were calculated.

As described above, the yellowness index YI was calculated by converting the chromaticity of visible light transmitted from the indoor side to the outdoor side of the heat shield glass by a method conforming to the ASTM E131 standard.

(Evaluation of durability)
Durability was evaluated using each heat insulating glass. The durability of the heat insulating glass was evaluated by the following method.

First, using a spectrophotometer, the transmittance of the heat shield glass in the direction from the outdoor side to the indoor side (hereinafter referred to as “initial transmittance T _initial ”) is measured in each wavelength region of visible light.

Next, the heat insulating glass is immersed in an NaOH aqueous solution heated to 90° C. and having a concentration of 0.1 kmol/m ³ . The immersion time is 2 hours. After that, the heat insulating glass is taken out, washed and dried. The transmittance (hereinafter referred to as “post-treatment transmittance T _treated ”) of the heat shield glass after the immersion treatment is measured again by the method described above.

From the obtained results, the transmittance difference ΔT (%) is obtained by the following equation (4):

Transmittance difference ΔT (%) = |T _treated -T _initial | (4) formula

Thermal insulating glass with a transmittance difference ΔT (%) of 1% or less was judged to have good durability (○), and thermal insulating glass with a transmittance difference ΔT (%) of more than 1% was judged to have good durability. It was judged as not good (x).

(result)
The evaluation results obtained for each heat insulating glass are summarized in Table 2 below.

この結果から、例１～例６に係る遮熱ガラスでは、遮蔽係数ＳＣが０．４以下、セレクティビティＳｅが０．９以上となっており、良好な遮熱性能および断熱性能を示すことがわかる。また、例１～例６に係る遮熱ガラスでは、エネルギー吸収率Ａｅは、６５％以下となっており、熱割れのリスクを有意に軽減できる。

From these results, the heat shielding glasses according to Examples 1 to 6 have a shielding coefficient SC of 0.4 or less and a selectivity Se of 0.9 or more, indicating good heat shielding performance and heat insulation performance. Recognize. Further, the heat shield glasses according to Examples 1 to 6 have an energy absorption rate Ae of 65% or less, which can significantly reduce the risk of thermal cracking.

On the other hand, the heat shielding glasses according to Examples 11, 14, and 17 have a shielding coefficient SC of more than 0.4, indicating that they do not exhibit very good heat shielding performance. In addition, the heat shield glasses according to Examples 11 and 13 have a selectivity Se of less than 0.9, indicating that they do not exhibit very good heat insulation performance. Moreover, it can be said that the heat insulating glass according to Example 13 has a high energy absorption rate Ae and has a risk of thermal cracking.

Further, in the heat shield glasses according to Examples 1 to 6, the outdoor reflectance Rv is suppressed to a low level of 30% or less.

Further, in the heat shield glasses according to Examples 1 to 6, a ^* and b ^* of the reflected light are less than 5. Therefore, it is expected that the heat shield glasses according to Examples 1 to 6 will provide reflected light with a good color close to blue. Furthermore, the heat shield glasses according to Examples 1 to 6 all have a yellowness index YI of less than 5. Therefore, the heat shield glasses according to Examples 1 to 6 can significantly suppress the transmitted light from appearing yellowish.

Furthermore, it can be seen that the heat shield glasses according to Examples 1 to 6 have good durability.

Thus, it was confirmed that the heat shield glasses according to Examples 1 to 6 have good heat shield properties and durability, and that the risk of thermal cracking is significantly reduced.

In addition, this application claims priority based on Japanese Patent Application No. 2017-244163 filed on December 20, 2017, and the entire contents of the same Japanese application are incorporated herein by reference.

100 first heat shield glass 102 first side 104 second side 110 glass substrate 112 first surface 114 second surface 120 laminated film 130 conductive layer 150 outermost layer 200 second heat shield glass 202 first side Side 204 Second side 210 Glass substrate 212 First surface 214 Second surface 220 Laminated film 230 Conductive layer 250 Outermost layer 260 First color correction layer 265 Second color correction layer 300 Third heat shield glass 302 First Side 304 Second Side 310 Glass Substrate 312 First Surface 314 Second Surface 320 Laminated Film 330 First Conductive Layer 350 Outermost Layer 360 First Color Correction Layer 365 Second Color Correction Layer 370 Second 2 conductive layer 375 third color tone correction layer

Claims (8)

heat insulating glass,
a glass substrate having a first surface;
a laminated film disposed on the first surface;
has
The glass substrate has an energy transmittance Te ₀ of less than 70%,
The laminated film has a conductive layer and an outermost layer in order of proximity to the glass substrate,
the conductive layer comprises a metal nitride;
The outermost layer is composed of an oxide containing Si and Zr,
The laminated film is installed on the outdoor side of the heat insulating glass ,
The metal nitride is a nitride containing at least one of Cr, Ti, Zr, Nb, Ta, and Hf,
a first color correction layer between the glass substrate and the conductive layer;
a second color correction layer between the conductive layer and the outermost layer;
each of the first and second color tone correction layers is composed of a nitride containing Si and Al or a nitride containing Si and Zr;
When the first and second color tone correction layers are composed of a nitride containing Si and Al, the content of AlN is in the range of 1 mol% to 20 mol%,
The thermal insulating glass , wherein the content of ZrN is in the range of 1 mol % to 40 mol % when the first and second color tone correction layers are composed of nitrides containing Si and Zr . 2. The heat shield glass according to claim 1 , wherein the outermost layer has a refractive index in the range of 1.55 to 2.20 for light with a wavelength of 632 nm. The heat shield glass according to claim 1 or 2 _, wherein the outermost layer contains 10mol% to 90mol% ZrO2. The heat shield glass according to any one of claims 1 to 3 , wherein the outermost layer has a carbon content of 1 at% or less. The heat shield glass according to any one of claims 1 to 4 , wherein the heat shield glass has a shielding coefficient SC measured from the side of the laminated film of 0.4 or less. The heat shield glass according to any one of claims 1 to 5 , wherein the heat shield glass has an energy absorption rate Ae measured from the side of the laminated film of 65% or less. The heat shield glass according to any one of claims 1 to 6 , wherein the heat shield glass has a visible light reflectance Rv measured from the laminated film side of 30% or less. 8. The heat shield glass according to claim 1, wherein said first color tone correction layer and said second color tone correction layer are made of different materials.

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