JP2017014024A - Heat-shielding glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat-shielding glass that has designability and has good heat-shielding properties.SOLUTION: In a heat-shielding glass having a glass plate and a heat-shielding coating film provided on a first surface of the glass plate, the heat-shielding coating film is constructed from three or more layers including a conductive tin oxide-containing layer, and the heat-shielding glass has suppressed yellowness and redness. When a spectral reflectance spectrum curve is primarily differentiated in the wavelength range of 380 to 550 nm, the spectrum curve being measured in a state in which the heat-shielding coating film side is brought into contact with an integrating sphere detector and the glass plate side is brought into contact with white paper, and in a state in which the glass plate side is brought into contact with an integrating sphere detector and the heat-shielding coating film side is brought into contact with white paper, the heat-shielding glass has a maximum of one location where the sign of the primary differentiation thus obtained changes from positive to negative.SELECTED DRAWING: Figure 4

Description

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

  Due to the recent increase in energy saving awareness, there are increasing examples of applying heat-shielding glass having heat-shielding properties to window glass of buildings and glass members of vehicles.

  Such a thermal barrier glass is constituted by, for example, coating one surface of a glass plate with a thermal barrier coating film.

  In recent years, the demand for the heat-shielding effect by the heat-shielding glass has been increasing. For this reason, research and development on a thermal barrier coating film having further thermal barrier performance has been advanced.

  In general, in order to improve the thermal barrier performance of the thermal barrier coating film, it is effective to make the thermal barrier coating film a multilayer structure.

  However, when the thermal barrier coating film has a multilayer structure, the color tone is deteriorated or it is difficult to adjust the color tone due to an undesirable light interference action between the glass plate and / or each layer used. The problem can arise.

  In particular, in recent years, the design of the thermal barrier glass has been required in response to the increasing awareness of the viewer's aesthetics. For example, recently, as a color tone felt from the heat shielding glass, a reddish or yellowish color or an unclear color tone tends to be avoided.

  However, when the thermal barrier coating film provided on the thermal barrier glass has a multilayer structure of three or more layers, it becomes more difficult to adjust the color tone, and it becomes difficult to obtain a desired color tone and a preferable aesthetic feeling.

  This invention is made | formed in view of such a background, and it aims at providing the thermal insulation glass which has favorable design property and has favorable thermal insulation in this invention.

The thermal barrier glass according to one embodiment of the present invention is
A glass plate having first and second surfaces facing each other;
A thermal barrier coating film provided on the first surface of the glass plate;
Have
The thermal barrier coating film is a thermal barrier glass composed of three or more layers including a conductive tin oxide-containing layer,
Yellowness index YI E313 reflection color C _g from the side of the reflection color C _f and the glass plate from the side of the thermal barrier coating film are both lower than -5,
CIE 1976 L ^* : a ^* : b ^* The color coordinates of the reflected color C _f from the thermal barrier coating film side and the reflected color C _g from the glass plate side expressed in the color system are a ^* <0,
Spectral reflection spectrum curve in a wavelength range of 380 nm to 550 nm, measured with the thermal barrier glass in contact with an integrating sphere detector on the thermal barrier coating film side and in contact with white paper on the glass plate side. There is a maximum of one place where the sign of the obtained first derivative B1 changes from positive to negative when
Spectral reflection spectrum curve in the wavelength range of 380 nm to 550 nm, measured with the heat shielding glass in contact with an integrating sphere detector on the glass plate side and in contact with the white paper on the heat shielding coating film side. There is a maximum of one place where the sign of the obtained primary differentiation B2 changes from positive to negative.

  In the present invention, it is possible to provide a heat-shielding glass having preferable design properties and good heat-shielding properties.

It is the figure which showed schematically the structure of the apparatus for evaluating the dull feeling received from heat insulation glass. It is the figure which showed roughly an example of operation for determining the number of the peaks contained in the spectrum waveform of the reflectance R of thermal insulation glass. It is the figure which showed roughly an example of operation for determining the number of the peaks contained in the spectrum waveform of the reflectance R of thermal insulation glass. 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 figure which showed one structural example of the thermal barrier coating film schematically. It is the figure which showed schematically another structural example of the thermal barrier coating film. It is the figure which showed schematically the further another structural example of the thermal barrier coating film. It is the figure which showed schematically the further another structural example of the thermal barrier coating film. It is the figure which showed the spectrum waveform of the reflected light obtained in the thermal insulation glass which concerns on Example 1. FIG. It is the figure which showed the spectrum waveform of the reflected light obtained in the thermal insulation glass which concerns on Example 3. FIG. It is the figure which showed the spectrum waveform of the reflected light obtained in the thermal insulation glass which concerns on Example 8. FIG. It is the figure which showed the spectrum waveform of the reflected light obtained in the thermal insulation glass which concerns on Example 10. FIG.

  Hereinafter, an embodiment of the present invention will be described with reference to the drawings.

In the present invention,
A glass plate having first and second surfaces facing each other;
A thermal barrier coating film provided on the first surface of the glass plate;
Have
The thermal barrier coating film is a thermal barrier glass composed of three or more layers including a conductive tin oxide-containing layer,
Yellowness index YI E313 reflection color C _g from the side of the reflection color C _f and the glass plate from the side of the thermal barrier coating film are both lower than -5,
CIE 1976 L ^* : a ^* : b ^* The color coordinates of the reflected color C _f from the thermal barrier coating film side and the reflected color C _g from the glass substrate side, which are represented by the color system, are a ^* <0,
Spectral reflection spectrum curve in a wavelength range of 380 nm to 550 nm, measured with the thermal barrier glass in contact with an integrating sphere detector on the thermal barrier coating film side and in contact with white paper on the glass plate side. There is a maximum of one place where the sign of the obtained first derivative B1 changes from positive to negative when
Spectral reflection spectrum curve in the wavelength range of 380 nm to 550 nm, measured with the heat shielding glass in contact with an integrating sphere detector on the glass plate side and in contact with the white paper on the heat shielding coating film side. There is provided a thermal barrier glass in which there is at most one place where the sign of the obtained first derivative B2 changes from positive to negative when the first derivative is first differentiated.

  As described above, when a thermal barrier glass is formed by coating a glass plate with a thermal barrier coating film, when the thermal barrier coating film has a multilayer structure, the glass plate and / or the thermal barrier coating film used is configured. There is often a problem in that the color tone is deteriorated or it is difficult to adjust the color tone due to an unfavorable light interference action between the respective layers. And while the consciousness about design property is increasing, such a problem may become more remarkable in the future.

  However, the thermal barrier glass according to the present invention can provide a good color tone and a clean impression even though the thermal barrier coating film is composed of three or more layers. More specifically, in the heat-shielding glass according to the present invention, redness and yellowness contained in the reflected color are significantly suppressed, it is difficult for the viewer to feel uncomfortable, and mixing of a plurality of colors is significantly suppressed. Therefore, it can give a clean impression without dullness.

  Here, in this application, in order to quantitatively evaluate the redness and yellowness of the colors included in the color reflected from the heat-shielding glass, and the “dullness” received from the heat-shielding glass (an index opposite to the “clean feeling”). The following indicators are adopted.

(Redness of colors included in the reflected color)
The redness of the color included in the reflected color from the heat shielding glass can be evaluated by measuring the reflected color of the heat shielding glass using a general spectroscopic measurement device. More specifically, the evaluation can be performed by calculating a CIE 1976 L ^* : a ^* : b ^* color system based on a spectral spectrum measured by a measuring device having an integrating sphere detector. As a measurement method, the heat shield glass is set in the above-described measurement apparatus so that the heat shield coating film of the heat shield glass is on the integrating sphere detector side, and the reflection spectrum is measured. Alternatively, the heat shield glass is set in the measuring device so that the glass surface of the heat shield glass is on the integrating sphere detector side, and the reflection spectrum is measured.

Based on the measured reflection spectrum, CIE 1976 L ^* : a ^* : b ^* color system is calculated. In this color system, when the color coordinates of the reflected color are a ^* ≧ 0, it is determined that the reflected color from the heat shielding glass is reddish, and when the color coordinates are a ^* <0, It is determined that the reflected color of the image has no redness.

(Yellowness of colors included in the reflected color)
The yellowness of the color included in the color reflected from the heat-shielding glass can be evaluated as a yellowness index YI E313 based on the ASTM E131 standard from the chromaticity based on JIS Z7701: 1990. The evaluation is based on the reflection color (referred to as “reflection color C _f ”) obtained from the side of the thermal insulation coating film of the thermal insulation glass and the reflection color obtained from the side of the glass plate of the thermal insulation glass (“reflection color C _g ”). The yellowness index YI E313 is calculated.

As a result, in any C _f and C _g , when the yellowness index YI E313 is less than −5, it is determined that the reflected color from the heat shielding glass is not yellowish. Further, when the yellowness index YI E313 is −5 or more in at least one of C _f and C _g , it is determined that the reflected color from the heat shielding glass is yellowish.

(Dullness of thermal insulation glass)
In determining the color tone of the heat-shielding glass, in many cases, the glass is placed on white paper and an observer visually observes it from the front. The light visually observed by this observation method is a superposition of a component in which incident light transmitted through the glass is reflected on the paper surface and a reflection component from the front and back surfaces of the glass including the coating. The inventors have devised a method for evaluating dullness using a reflectance measurement spectrum in accordance with such an observation method.

  The dull feeling received from the heat shielding glass is evaluated as follows using the reflection spectrum included in the reflected light from the heat shielding glass.

  In FIG. 1, the structure of the apparatus for evaluating the dull feeling received from heat insulation glass is shown roughly.

  As shown in FIG. 1, the apparatus 1 includes an integrating sphere detector 5 and white paper 30. As the white paper 30, high-quality paper (for example, Toppan Multi Cut Paper White PPCA4XW) having a reflectance of about 80% is used.

  When measuring the dullness of the thermal barrier glass, first, a thermal barrier glass sample 10 to be evaluated is installed in the apparatus 1.

  In the first evaluation (first evaluation), as shown in FIG. 1, the sample 10 is placed so that the glass plate 12 is on the paper 30 side and the thermal barrier coating film 15 is on the integrating sphere detector 5 side. The

In the first evaluation, the sample 10 is irradiated with light from the entrance 6 of the integrating sphere detector 5 in an angular range of 8 °, and the reflectance R _f of the sample 10 is measured.

The dull feeling is evaluated from the waveform of the obtained reflectance _Rf . Specifically, in the spectrum waveform of the reflectance R _{f in} the wavelength range of 380 nm to 540 nm, when there is at least one peak, the sample 10 viewed from the thermal barrier coating film 15 has no dullness. If two or more peaks are determined, it is determined that the sample 10 viewed from the thermal barrier coating film 15 has a dull feeling.

  The dull feeling is judged in this way because the human eye tends to feel a dull feeling when two or more colors are mixed in a spectral waveform compared to a single color light. .

  Next, a second evaluation is performed. In the second evaluation, the sample 10 is installed in the apparatus 1 in the opposite direction. That is, the sample 10 is arranged such that the glass plate 12 is on the integrating sphere detector 5 side and the thermal barrier coating film 15 is on the paper 30 side.

In the second evaluation, was measured in the same way as in the first evaluation, the reflectivity R _g of the sample 10 is measured. Then, in the spectrum waveform of the resulting reflectance R _g, when the peak is only present one at most, the sample 10 as viewed from the glass plate 12, it is determined that there is no feeling of dullness, peaks are present two or more In this case, it is determined that the sample 10 viewed from the glass plate 12 has a dull feeling.

  As a result, in both the first and second evaluations, if there is only one or less peak, it is determined that the sample 10 has no dull feeling (that is, has a clean feeling).

Note that the spectral waveform of the reflectivity R _f and R _g is obtained by the above measurement, since there are various forms, often it may be difficult number of determination of the peak. Therefore, in the present application, the number of peaks is determined based on a change in the first derivative value of the measured spectral waveform of the reflectances _Rf and _Rg . Hereinafter, this operation will be described with reference to FIGS.

  2 and 3 show an example of an operation for determining the number of peaks included in the spectral waveform of the reflectance R. FIG.

  First, as shown in FIG. 2A, consider a case where the spectral waveform S of the reflectance R has a single peak P1. In this case, the primary differential value B of the spectrum waveform S is approximately a waveform as shown in FIG.

  That is, the primary differential value B exhibits behavior as shown in the region (i) to the region (iii) from the side where the wavelength λ is small. In the first region (i), the primary differential value B increases monotonously with the wavelength λ, and in the next region (ii), the primary differential value B decreases monotonously with the wavelength λ and changes from a positive value to a negative value. In the next region (iii), the primary differential value B begins to increase monotonically with the wavelength λ. Therefore, in this case, there is only one point Q (a point where B <0 from B> 0 to B = 0 after the first differential value B changes from positive to negative).

  Next, consider the case where the spectral waveform S of the reflectance R has two peaks P1 and P2, as shown in FIG. In this case, the first-order differential value B of the spectrum waveform S is approximately a waveform as shown in FIG.

  That is, the primary differential value B exhibits the behavior as shown in the region (i) to the region (v) from the side where the wavelength λ is small. The primary differential value B increases monotonously with the wavelength λ in the first region (i), decreases monotonously with the wavelength λ in the next region (ii), and changes from a positive value to a negative value in the next region (iii). Then, it turns monotonically with wavelength λ, and in the next region (iv), it decreases monotonically again with wavelength λ and becomes a positive to negative value, and in the next region (v), it begins to monotonously increase with wavelength λ again. . Accordingly, in this case, there are two places Q where the primary differential value B changes from positive to negative (a place where B <0 from a point where B> 0 to B = 0).

  Thus, it can be seen that the number of peaks included in the spectrum waveform S of the reflectance R can be determined by the number of locations Q where the primary differential value B turns from positive to negative.

  In the above operation, the minimum pitch of the wavelength λ is set to 5 nm so as not to include a small variation in the primary differential value B due to an error.

In the present application, in each spectrum waveform of the reflectances R _f and R _g obtained by the apparatus 1 for measuring the dullness as described above, the number of locations Q where the primary differential value B turns from positive to negative is 1 or less. In this case, it is determined that the peak included in the spectrum waveform is 0 or 1, and therefore it is determined that there is no dullness. Conversely, the respective spectral waveforms of reflection R _f and R _g, when the primary differential value B number of places Q to turn from positive to negative is 2 or more, peaks included in the spectrum waveform is 2 or more Therefore, it is determined that there is a dull feeling.

  By such a method, the dull feeling of the heat shielding glass can be determined quantitatively.

(Thermal shielding glass according to one embodiment of the present invention)
Next, with reference to FIG. 4, an example of a specific configuration of the heat shielding glass according to the embodiment of the present invention will be described.

  In FIG. 4, the cross section of the heat insulation glass (henceforth "1st heat insulation glass") by one Embodiment of this invention is shown typically.

  As shown in FIG. 4, the first thermal barrier glass 100 includes a glass plate 110 and a thermal barrier coating film 130. The glass plate 110 has a first surface 112 and a second surface 114. The thermal barrier coating film 130 is provided on the first surface 112 side of the glass plate 110.

  The thermal barrier coating film 130 is composed of at least three layers including a conductive tin oxide-containing layer. For example, in the example shown in FIG. 4, the thermal barrier coating film 130 has three layers of the first layer 140 to the third layer 150, and the conductive tin oxide-containing layer is formed as the second layer 145. Has been.

  Here, the “conductive tin oxide-containing layer” means a conductive layer containing 50 wt% or more of tin oxide.

First heat blocking glass 100 is characterized as described above, i.e., the reflection color _{C f} from the side of the thermal barrier coating layer 130, and yellowness index YI E313 reflection color _{C g} from the side of the glass plate 110 , Both are less than -5,
CIE 1976 L ^* : a ^* : b ^* The color coordinates of the reflected color C _f from the side of the thermal barrier coating film 130 and the reflected color C _g from the side of the glass substrate 110 represented by the color system are a ^* <0,
In the spectral reflection spectrum curve measured from either side of the glass plate 110 and the thermal barrier coating film 130 in the wavelength range of 380 nm to 550 nm, the location Q where the sign of the primary differential value B changes from positive to negative is a maximum of 1. It has the feature that there are places.

  In such 1st heat insulation glass 100, while the redness and yellowishness of the color contained in reflected color are suppressed, a dull feeling can be suppressed. Therefore, in the 1st heat insulation glass 100, it is hard for a viewer to feel unpleasant feeling, and it can obtain the refreshing impression without a dull feeling.

  In the first thermal barrier glass 100, the thermal barrier coating film 130 is composed of at least three layers including the conductive tin oxide-containing layer 145. For this reason, in the 1st thermal insulation glass 100, favorable thermal insulation performance and favorable durability performance can be exhibited.

(About heat insulation performance of heat insulation glass)
In general, the heat shielding performance of the heat shielding glass can be expressed by the following formula (1):

SC = g value / 0.88 (1) 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 first thermal barrier glass 100, the shielding coefficient SC <0.7 is more preferable, and SC <0.6 is particularly preferable.

(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, the reference numerals shown in FIG. 4 are used to represent each member for the sake of clarity.

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

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

(Thermal barrier coating film 130)
The thermal barrier coating film 130 is composed of three or more layers including a conductive tin oxide-containing layer.

  Hereinafter, several configuration examples of the thermal barrier coating film 130 will be described with reference to FIGS. However, these are merely examples, and the thermal barrier coating film 130 may have other configurations.

(Configuration example of thermal barrier coating film 1: first thermal barrier coating film)
FIG. 5 schematically shows a first configuration example of the thermal barrier coating film.

  As shown in FIG. 5, in this configuration, the first thermal barrier coating film 530 is composed of three layers: an undercoat layer 540, a conductive tin oxide-containing layer 545, and a high refractive index layer 550. Here, the high refractive index layer means a generic name of layers having a refractive index larger than 2.

  The undercoat layer 540 has a role of suppressing diffusion of predetermined elements between the glass plate 110 and the conductive tin oxide-containing layer 545. Moreover, the undercoat layer 540 reduces incident light reflection at the interface between this layer and the conductive tin oxide-containing layer 545. Thereby, the in-plane distribution of the reflected color caused by the film thickness distribution of the conductive tin oxide-containing layer can be suppressed. The undercoat layer 540 is made of, for example, a material mainly composed of silica or a material 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.

The undercoat layer 540 may be silicon oxide (SiO _x ).

  The thickness of the undercoat layer 540 is, for example, in the range of 10 nm to 100 nm.

  The conductive tin oxide-containing layer 545 may be made of tin oxide doped with antimony or fluorine. The doping amount is, for example, preferably in the range of 0.0 to 0.1 in the weight ratio Sb / Sn of antimony and tin in the film measured by XRF (fluorescence X-ray analysis), and 0.02 to 0.06. The range is more preferable, and the range of 0.03 to 0.05 is more preferable.

  For example, the thickness of the conductive tin oxide-containing layer 545 is preferably in the range of 50 nm to 500 nm, more preferably in the range of 150 nm to 350 nm, and still more preferably in the range of 200 to 280 nm.

  The high refractive index layer 550 has a role of adjusting the reflection characteristics of light incident on the thermal barrier coating film 530. The high refractive index layer 550 may be made of, for example, titanium oxide.

  The thickness of the high refractive index layer 550 is, for example, preferably in the range of 10 nm to 70 nm, more preferably in the range of 20 nm to 50 nm, and still more preferably in the range of 35 nm to 45 nm.

  The total thickness of the first thermal barrier coating film 530 is, for example, in the range of 70 nm to 670 nm, preferably in the range of 100 nm to 500 nm, more preferably in the range of 200 nm to 450 nm, and further in the range of 300 nm to 400 nm. preferable.

  The method for forming the first thermal barrier coating film 530 is not particularly limited. The first thermal barrier coating film 530 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). Etc.) and a method selected from an ion beam sputtering method and the like.

  Alternatively, the first thermal barrier coating film 530 may be formed by, for example, an online CVD method.

  Here, “on-line” means a method of forming a film on the surface of the glass during the glass manufacturing process. More specifically, when glass is manufactured, glass ribbon is moved on the molten tin bath and then slowly cooled to manufacture glass continuously. In the method), a film is formed on the upper surface of the glass ribbon during the movement 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.

  When the first thermal barrier coating film 530 is formed by an on-line CVD method, manufacturing costs can be suppressed, which is preferable.

(Configuration example 2 of thermal barrier coating film: second thermal barrier coating film)
FIG. 6 schematically shows a second configuration example of the thermal barrier coating film.

  As shown in FIG. 6, in this configuration, the second thermal barrier coating film 630 includes a first undercoat layer 640, a second undercoat layer 641, a conductive tin oxide-containing layer 645, and a high refractive index layer. It consists of four layers of 650.

  When such a plurality of undercoat layers 640 and 641 are applied to the second thermal barrier coating film 630, the reflection of incident light at the interface between the undercoat layer 641 and the conductive tin oxide-containing layer 645 is reduced. Is possible. Thereby, the in-plane distribution of the reflected color caused by the film thickness distribution of the conductive tin oxide-containing layer can be suppressed.

For the first undercoat layer 640 and the second undercoat layer 641, a tin oxide-containing layer and a silicon oxide (SiO ₂ ) layer can be used, respectively. In addition, examples of the thicknesses of the first undercoat layer 640 and the second undercoat layer 641 are 10 nm to 50 nm (first) and 25 nm to 50 nm (second), respectively.

  In the second thermal barrier coating film 630, as the configurations of the conductive tin oxide-containing layer 645 and the high refractive index layer 650, the description relating to the first thermal barrier coating film 530 described above can be referred to, and thus the description thereof will be given here. Is omitted.

(Configuration Example 3 of Thermal Barrier Coating Film: Third Thermal Barrier Coating Film)
FIG. 7 schematically shows a third configuration example of the thermal barrier coating film.

  As shown in FIG. 7, in this configuration, the third thermal barrier coating film 730 includes the first undercoat layer 740, the second undercoat layer 741, the first conductive tin oxide-containing layer 745, and the first 2 conductive tin oxide-containing layers 746.

  The first conductive tin oxide-containing layer 745 and the second conductive tin oxide-containing layer 746 can be the same as the conductive tin oxide-containing layer 545 of the first thermal barrier coating film 530 described above. For example, the first conductive tin oxide-containing layer 745 may be composed of tin oxide doped with antimony, and the second conductive tin oxide-containing layer 746 may be composed of tin oxide doped with fluorine. . Or the reverse may be sufficient.

  In addition, examples of the thicknesses of the first conductive tin oxide-containing layer 745 and the second conductive tin oxide-containing layer 746 are 110 nm to 210 nm (first) and 160 nm to 300 nm (second), respectively. When the first conductive tin oxide-containing layer 745 is tin oxide doped with antimony and the second conductive tin oxide-containing layer 746 is tin oxide doped with fluorine, only the doped elements are different. Therefore, there is a possibility that the layer boundary cannot be clearly identified. In that case, it has a region doped with antimony and a region doped with fluorine, and if the total film thickness is in the range of 270 nm to 510 nm, tin oxide doped with antimony and tin oxide doped with fluorine It may be interpreted that it is a laminated layer.

In the third thermal barrier coating film 730, as the configurations of the first and second undercoat layers 740 and 741, the description relating to the second thermal barrier coating film 630 can be referred to. And a silicon oxide (SiO ₂ ) layer can be used. Moreover, the example of the thickness of the 1st undercoat layer 740 and the 2nd undercoat layer 741 is 10 nm-50 nm (1st) and 25 nm-50 nm (2nd), respectively.

(Configuration Example 4 of Thermal Barrier Coating Film: Fourth Thermal Barrier Coating Film)
FIG. 8 schematically shows a fourth configuration example of the thermal barrier coating film.

  As shown in FIG. 8, in this configuration, the fourth thermal barrier coating film 830 includes an undercoat layer 840, a first conductive tin oxide-containing layer 845, and a second conductive tin oxide-containing layer 846. Composed of layers.

  Here, with regard to the configuration of the undercoat layer 840, the description relating to the first thermal barrier coating film 530 can be referred to. For the configurations of the first conductive tin oxide-containing layer 845 and the second conductive tin oxide-containing layer 846, the description regarding the third thermal barrier coating film 730 can be referred to.

  Thus, the thermal barrier coating film 130 can be implemented by combining various configurations such as a 4-layer configuration in addition to a 3-layer configuration.

  In addition, it is preferable that the heat insulation glass of this embodiment has a haze of less than 0.8%. In order to reduce haze, it is considered important to improve the flatness of the surface of the conductive tin oxide layer. As an example of a method for improving the surface flatness of the conductive tin oxide layer, the film formation temperature of the conductive tin oxide layer is kept as low as possible to suppress the enlargement of the conductive tin oxide crystal grains. It can be considered to be composed of fine particles.

  Examples of the present invention will be described below. In the following description, Examples 1 to 6 are examples, and Examples 7 to 14 are comparative examples.

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

  First, a thermal barrier coating film was formed on the surface of the glass plate by a normal pressure CVD method.

  The thermal barrier coating film has a three-layer structure as shown in FIG. The undercoat layer was a SiOx layer (target thickness 55 nm). The conductive tin oxide-containing layer was an antimony-doped tin oxide layer (target thickness 260 nm). The high refractive index layer was a titanium oxide layer (target thickness 40 nm).

The temperature of the glass plate during the formation of the SiOx layer was about 670 ° C. The antimony-doped tin oxide layer is obtained by diluting a mixed gas obtained by vaporizing a raw material of monobutyltin chloride (MBTC), water, and antimony trichloride (SbCl ₃ ) with air as a raw material gas at about 590 ° C. The film was formed. Further, the titanium oxide layer was formed at about 540 ° C. using tetratitanium isopropoxide (TTIP), a mixed gas obtained by vaporizing MBTC raw material, diluted with nitrogen as a raw material.

  After the formation of the thermal barrier coating film, the glass plate is cooled and cut to obtain a thermal barrier glass including a glass plate (transparent color) having dimensions of 300 mm in length, 300 mm in width, and 5 mm in thickness (hereinafter referred to as Example 1). Called thermal barrier glass).

(Examples 2 to 6)
In the same manner as in Example 1, a heat insulating glass (hereinafter referred to as “heat insulating glass according to Examples 2 to 6”) was produced. However, in these examples, the type (color) and thickness of the glass plate were changed from those in Example 1.

(Example 7)
In the same manner as in Example 1, a heat shield glass (hereinafter referred to as “heat shield glass according to Example 7”) was produced. However, in this Example 7, a thermal barrier coating film having a four-layer structure as shown in FIG. 7 was used. The first undercoat layer was a SnO ₂ layer having a thickness of 19 nm, and the second undercoat layer was a SiO ₂ layer having a thickness of 38 nm. The first conductive tin oxide-containing layer was an antimony-doped tin oxide layer having a thickness of 162 nm, and the second conductive tin oxide-containing layer was a fluorine-doped tin oxide layer having a thickness of 230 nm.

  In Example 7, a transparent plate glass having a thickness of 6 mm was used as the glass plate.

(Examples 8 to 10)
In the same manner as in Example 7, heat insulating glass (hereinafter referred to as “heat insulating glass according to Examples 8 to 10”) was produced. However, in these examples, the type (color) and thickness of the glass plate were changed from those in Example 7.

(Example 11)
In the same manner as in Example 1, a heat insulating glass (hereinafter referred to as “heat insulating glass according to Example 11”) was produced. However, in Example 11, a four-layer structure as shown in FIG. 6 was used as the thermal barrier coating film. The first undercoat layer was a SnO ₂ layer having a thickness of 19 nm, and the second undercoat layer was a SiO ₂ layer having a thickness of 38 nm. The conductive tin oxide-containing layer was a 260 nm thick fluorine-doped tin oxide layer, and the high refractive index layer was a 37 nm thick titanium oxide layer.

(Example 12)
A heat shield glass (hereinafter referred to as “heat shield glass according to Example 12”) was produced in the same manner as in Example 11. However, in Example 12, 6 mm thick glass colored with a green color (high heat shielding Green glass) was used as the glass plate.

(Example 13)
In the same manner as in Example 1, a heat insulating glass (hereinafter referred to as “heat insulating glass according to Example 13”) was produced. However, in Example 13, the thermal barrier coating film having a three-layer structure as shown in FIG. 5 was used. The undercoat layer was a SnO ₂ layer having a thickness of 55 nm. The conductive tin oxide-containing layer was an antimony-doped tin oxide layer having a thickness of 310 nm, and the high refractive index layer was a titanium oxide layer having a thickness of 40 nm.

(Example 14)
In the same manner as in Example 13, a thermal barrier glass (hereinafter referred to as “thermal barrier glass according to Example 14”) was produced. However, in Example 14, 6 mm thick glass (BNFL) colored blue-green was used as the glass plate.

  In the following Table 1, the structure of the thermal insulation glass which concerns on each Example 1-14 was shown collectively.

（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 heat insulation performance)
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 implemented by irradiating light from the glass plate side of each thermal barrier glass (that is, the opposite side of the thermal barrier coating film).

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

この結果から、例１〜例６に係る遮熱ガラスでは、ＳＣが０．６未満となっており、良好な遮熱性能を有することがわかった。

From this result, in the thermal insulation glass which concerns on Examples 1-6, SC became less than 0.6, and it turned out that it has favorable thermal insulation performance.

(Evaluation of redness of reflected color)
Each heat shield glass, the redness of colors included in the reflected color C _f and C _g from shielding heat glass was evaluated by the method described above.

In the column of “reflective color coordinates” in Table 2, the color coordinates of the CIE 1976 L ^* : a ^* : b ^* color system of the reflected colors C _f and C _g measured in each heat shielding glass. The a ^* values of are shown.

From this result, the heat shield glasses according to Examples 1 to 6, both has a a ^{* <0,} it was found that contains almost no redness reflection color C _f and C _g.

(Evaluation of yellow reflection)
Each heat shield glass, yellowish color included in the reflected color C _f and C _g from shielding heat glass was evaluated by the method described above.

In the column of “YI E313” in Table 2 above, the values of YI E313 of the reflection colors C _f and C _g measured in each of the heat shielding glasses are shown.

From this result, the heat shield glasses according to Examples 1 to 6, _{C f} and _{C g} has a YI E313 <-5, it was found that contains almost no yellowing in reflected color.

(Evaluation of dullness of thermal barrier glass)
About each heat insulation glass, the dull feeling was evaluated by the above-mentioned method.

  FIGS. 9-12 shows an example of the spectrum waveform of the reflected light obtained in some thermal insulation glass. FIG. 9 shows the results obtained for the thermal insulation glass according to Example 1, FIG. 10 shows the results obtained for the thermal insulation glass according to Example 3, and FIG. 11 relates to Example 8. The result obtained in the heat insulation glass is shown, and FIG. 12 shows the result obtained in the heat insulation glass according to Example 10.

Each figure shows the respective spectrum waveforms of the reflectance R _f (that is, the result on the thermal barrier coating film side) and the reflectance R _g (that is, the result on the glass plate side).

These results, for example, in the case of thermal barrier glass according to Example 1, as shown in FIG. 9, in any of the reflectivity _{R f} and reflectance _{R g} is also in the wavelength range of 380Nm～540nm, even at the peak maximum You can see that there is only one. As shown in FIG. 10, the same applies to the case of the heat shielding glass according to Example 3.

On the other hand, in the case of the thermal barrier glass according to Example 8, as shown in FIG. 11, two distinct peaks (peak wavelengths are about 420 nm and 520 nm) are observed in the spectrum of the reflectance _Rf. . In the case of the spectral reflectance _{R g,} the low wavelength region of wavelength 400nm~440nm is, there are "shoulder", therefore, at first glance, it is difficult to determine one or two or the number of peaks. However, the “shoulder portion” is not regarded as a peak according to the determination criterion based on the number of places where the primary differential value changes from positive to negative as described above. Therefore, the peak of the spectral reflectance R _g is, becomes one.

As a result, the thermal barrier glass according to Example 8, the spectral reflectance R _g, although peaks have only a single, because the spectrum of reflectance R _f, which peaks are present two, dull feeling It is judged that there is (that is, a clean impression cannot be obtained).

Furthermore, in the case of the heat shielding glass according to Example 10, two distinct peaks (peak wavelengths are about 420 nm and 520 nm) are observed in the spectrum of the reflectance R _f as shown in FIG. Similarly, the spectral reflectance _{R g,} two distinct peaks (peak wavelength of about 420nm and 520 nm) is observed.

Accordingly, the thermal barrier glass according to Example 10 has a dull feeling (that is, a clean impression cannot be obtained) because there are two peaks in any spectrum of the reflectance _Rg and the reflectance _Rf. It is judged.

The “number of peaks” column in the above-mentioned Table 2 shows the number of peaks observed in the reflectance R _g and the reflectance R _f in each thermal barrier glass.

From this result, it can be seen that the thermal barrier glass according to Examples 1 to 6 includes only one peak in the spectrum of the reflectance _Rg and the reflectance _Rf . From this, it was found that the thermal insulation glass according to Examples 1 to 6 provided a clean impression even when viewed from either side of the thermal insulation coating film and the glass plate.

  The present invention can be used for thermal barrier glass and the like.

DESCRIPTION OF SYMBOLS 1 Apparatus 5 Integrating sphere detector 10 Sample 12 Glass plate 15 Thermal barrier coating film 30 White paper 100 Thermal barrier glass 110 Glass plate 112 First surface 114 Second surface 130 Thermal barrier coating film 140 First layer 145 Second layer Layer (Conductive tin oxide-containing layer)
150 Third layer 530 First thermal barrier coating film 540 Undercoat layer 545 Conductive tin oxide-containing layer 550 High refractive index layer 630 Second thermal barrier coating film 640 First undercoat layer 641 Second undercoat Layer 645 Conductive tin oxide-containing layer 650 High refractive index layer 730 Third thermal barrier coating film 740 First undercoat layer 741 Second undercoat layer 745 First conductive tin oxide-containing layer 746 Second conductivity Conductive tin oxide-containing layer 830 Fourth thermal barrier coating film 840 First undercoat layer 841 Second undercoat layer 845 First conductive tin oxide-containing layer 846 Second conductive tin oxide-containing layer

Claims (7)

A glass plate having first and second surfaces facing each other;
A thermal barrier coating film provided on the first surface of the glass plate;
Have
The thermal barrier coating film is a thermal barrier glass composed of three or more layers including a conductive tin oxide-containing layer,
Yellowness index YI E313 reflection color C _g from the side of the reflection color C _f and the glass plate from the side of the thermal barrier coating film are both lower than -5,
CIE 1976 L ^* : a ^* : b ^* The color coordinates of the reflected color C _f from the thermal barrier coating film side and the reflected color C _g from the glass plate side expressed in the color system are a ^* <0,
Spectral reflection spectrum curve in a wavelength range of 380 nm to 550 nm, measured with the thermal barrier glass in contact with an integrating sphere detector on the thermal barrier coating film side and in contact with white paper on the glass plate side. There is a maximum of one place where the sign of the obtained first derivative B1 changes from positive to negative when
Spectral reflection spectrum curve in the wavelength range of 380 nm to 550 nm, measured with the heat shielding glass in contact with an integrating sphere detector on the glass plate side and in contact with the white paper on the heat shielding coating film side. When the glass is first differentiated, there is a maximum of one place where the sign of the obtained first derivative B2 changes from positive to negative. When the solar heat acquisition rate is g value and the value expressed by the following formula (1) is the shielding coefficient SC,

SC = g value / 0.88 (1) Formula

The heat shielding glass according to claim 1, wherein the shielding coefficient SC is less than 0.7.   The heat-shielding glass according to claim 1, wherein the conductive tin oxide-containing layer has tin oxide doped with antimony or fluorine.   The thermal barrier glass according to any one of claims 1 to 3, wherein the thermal barrier coating film includes a titanium oxide layer on the conductive tin oxide-containing layer.   The thermal barrier coating film according to any one of claims 1 to 4, wherein the thermal barrier coating film has an undercoat layer having a silicon oxide layer and / or a tin oxide layer under the conductive tin oxide-containing layer. Glass.   The thermal barrier glass according to claim 5, wherein the undercoat layer is composed of two layers.   7. The heat shield according to claim 1, wherein the conductive tin oxide-containing layer has a two-layer structure of a tin oxide layer doped with antimony and a tin oxide layer doped with fluorine. Glass.

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