Layered film–coated glass plate, window glass for vehicle, laminated glass for vehicle, and laminated glass for vehicle roof

Abstract

One aspect of the present invention is a layered film–coated glass plate (100) that includes: a glass plate (10) that has a first principal surface (11) and a second principal surface (12); and a layered film (20) that is on the first principal surface (11). The layered film (20) has, in order from the first principal surface (11) side, a first dielectric layer (21), a first functional layer (22), a second dielectric layer (23), a second functional layer (24), and a third dielectric layer (25). The first functional layer (22) and the second functional layer (24) contain at least one of titanium nitride, chromium nitride, zirconium nitride, and tantalum nitride, and the first dielectric layer (21), the second dielectric layer (23), and the third dielectric layer (25) contain silicon nitride or aluminum nitride. The first dielectric layer (21) has a film thickness of 60–150 nm and a visible light transmittance of no more than 8%. The visible light transmittance on the second principal surface (12) side is no more than 35%.

Description

Glass sheet with laminated film, window glass for vehicle, laminated glass for vehicle, and laminated glass for vehicle roof

[0001] The present invention relates to a laminated film-coated glass sheet, a vehicle window glass, a vehicle laminated glass, and a vehicle roof laminated glass.

[0002] A technique for improving the heat-shielding and heat-insulating properties of glass sheets by applying a heat-shielding film and a heat-insulating film to the glass sheets is known. While heat-shielding films made of Ag-based materials are generally used, development of Ag-free heat-shielding films is underway from the viewpoints of improving durability and reducing coating costs.

[0003] For example, Patent Document 1 discloses a technique for applying a laminated film (heat-shielding film) having a functional layer containing TiN to glass for buildings.

[0004] International Publication No. 2018 / 129135

[0005] Glass used as window glass for vehicles such as automobiles is desirably provided with heat shielding properties and heat insulating properties. Furthermore, vehicle window glass is sometimes subjected to bending processing at high temperatures. Therefore, when a laminated film-coated glass sheet is used as a vehicle window glass, it is desirably provided with durability against high-temperature bending processing.

[0006] For example, simply using a material with a high thermal expansion coefficient can be expected to alleviate film stress using a metal-based material, but in a thin film state, thermal instability and aggregation can easily cause film degradation, leading to new issues such as increased material costs. Furthermore, methods that reduce the thickness of the glass itself can impair mechanical durability, such as static load, and raise concerns about product reliability. Furthermore, attempts to increase stress resistance by thickening the functional layer in the laminated film can result in reduced productivity, and optical properties such as visible light transmittance, reflectance, and color tone may no longer meet the desired specifications, or angle dependence may worsen. Furthermore, lowering the processing temperature itself must be considered, as it can be difficult to form the glass into the desired shape. Therefore, conventional methods have been unable to simultaneously satisfy durability, heat insulation, and productivity under high-temperature bending processing.

[0007] In view of the above problems, an object of the present invention is to provide a laminated film-coated glass sheet, a vehicle window glass, a vehicle laminated glass, and a vehicle roof laminated glass that combine durability, heat insulation properties, and productivity.

[0008] A laminated film-coated glass plate, a vehicle window glass, a vehicle laminated glass, and a vehicle roof laminated glass according to one embodiment of the present disclosure have the following configuration.

[0009] [1] A laminated film-coated glass plate comprising: a glass plate having a first main surface and a second main surface; and a laminated film on the first main surface, wherein the laminated film comprises, in order from the first main surface side, a first dielectric layer, a first functional layer, a second dielectric layer, a second functional layer, and a third dielectric layer, wherein the first functional layer and the second functional layer contain at least one of titanium nitride, chromium nitride, zirconium nitride, and tantalum nitride, and the first dielectric layer, the second dielectric layer, and the third dielectric layer contain silicon nitride or aluminum nitride, the film thickness of the first dielectric layer is 60 nm or more and 150 nm or less, the visible light transmittance is 8% or less, and the visible light reflectance on the second main surface side is 35% or less.

[0010] [2] The glass plate with a laminate film according to [1], wherein the laminate film has an underlayer containing zirconium nitride between the second dielectric layer and the second functional layer.

[0011] [3] The laminated film-coated glass plate according to [1] or [2], wherein the laminated film has: a first base layer containing zirconium nitride between the first dielectric layer and the first functional layer; and a second base layer containing zirconium nitride between the second dielectric layer and the second functional layer.

[0012] [4] The laminated film-coated glass plate according to any one of [1] to [3], wherein the total thickness of the first functional layer and the second functional layer is 0.4 or more and 3.3 or less in terms of thickness ratio to the thickness of the first dielectric layer, the total thickness of the first functional layer and the second functional layer is 0.1 or more and 2.1 or less in terms of thickness ratio to the thickness of the second dielectric layer, and the total thickness of the first functional layer and the second functional layer is 0.5 or more and 12.5 or less in terms of thickness ratio to the thickness of the third dielectric layer.

[0013] [5] The laminated film-coated glass plate according to [2], wherein the thickness of the underlayer is 0.1 or less in terms of thickness ratio to the thickness of the second dielectric layer.

[0014] [6] The glass plate with a laminate film according to [3], wherein the thickness of the first base layer is 0.1 or less in terms of thickness ratio to the thickness of the first dielectric layer, and the thickness of the second base layer is 0.1 or less in terms of thickness ratio to the thickness of the second dielectric layer.

[0015] [7] The film thickness of the first dielectric layer is 80 nm or more and 100 nm or less, The film thickness of the first functional layer is 50 nm or more and 65 nm or less, The film thickness of the second dielectric layer is 35 nm or more and 60 nm or less, The film thickness of the underlayer is 2 nm or more and 10 nm or less, The film thickness of the second functional layer is 45 nm or more and 65 nm or less, The film thickness of the third dielectric layer is 25 nm or more and 50 nm or less, The energy reflectance on the second main surface side is 30% or more and 50% or less, The visible light transmittance on the second main surface side is 6% or less, The color tone of the reflected light on the second main surface side is L standardized by CIE. ＊ a ＊ b ＊ Color coordinates a defined by the display system ＊ and b ＊ The laminated film-coated glass plate according to [2], wherein the value of the σ is −5 or more and 5 or less.

[0016] [8] The film thickness of the first dielectric layer is 80 nm or more and 100 nm or less, The film thickness of the first functional layer is 70 nm or more and 90 nm or less, The film thickness of the second dielectric layer is 10 nm or more and 30 nm or less, The film thickness of the underlayer is 3 nm or more and 10 nm or less, The film thickness of the second functional layer is 75 nm or more and 95 nm or less, The film thickness of the third dielectric layer is 20 nm or more and 30 nm or less, The energy reflectance on the second main surface side is 32% or more and 50% or less, The visible light transmittance on the second main surface side is 2% or less, The color tone of the reflected light on the second main surface side is L standardized by CIE. ＊ a ＊ b ＊ Color coordinates a defined by the display system ＊ The laminated film-coated glass plate according to [2], wherein the value of the refractive index is −5 or more and 10 or less.

[0017] [9] The first dielectric layer has a thickness of 90 nm or more and 110 nm or less, The first underlayer has a thickness of 1 nm or more and 5 nm or less, The first functional layer has a thickness of 50 nm or more and 70 nm or less, The second dielectric layer has a thickness of 50 nm or more and 70 nm or less, The second underlayer has a thickness of 3 nm or more and 10 nm or less, The second functional layer has a thickness of 25 nm or more and 45 nm or less, The third dielectric layer has a thickness of 10 nm or more and 30 nm or less, The energy reflectance on the second main surface side is 30% or more and 50% or less, The visible light transmittance on the second main surface side is 7% or less, The color tone of the reflected light on the second main surface side is 100% or more and 110 nm or less as specified by CIE. ＊ a ＊ b ＊ Color coordinates a defined by the display system ＊ is between -5 and 5, and the color coordinate b ＊ The laminated film-coated glass plate according to [3], wherein the value of the σ is −10 or more and 10 or less.

[0018]

[10] The first dielectric layer has a thickness of 95 nm or more and 115 nm or less, The first underlayer has a thickness of 1 nm or more and 5 nm or less, The first functional layer has a thickness of 80 nm or more and 100 nm or less, The second dielectric layer has a thickness of 50 nm or more and 70 nm or less, The second underlayer has a thickness of 3 nm or more and 10 nm or less, The second functional layer has a thickness of 25 nm or more and 45 nm or less, The third dielectric layer has a thickness of 10 nm or more and 30 nm or less, The energy reflectance on the second main surface side is 30% or more and 50% or less, The visible light transmittance on the second main surface side is 3% or less, The color tone of the reflected light on the second main surface side is 100% or more and 115 nm or less as specified by CIE. ＊ a ＊ b ＊ Color coordinates a defined by the display system ＊ The laminated film-coated glass plate according to [3], wherein the value of the film thickness is −5 or more and 5 or less.

[0019]

[11] The film thickness of the first dielectric layer is 80 nm or more and 100 nm or less, The film thickness of the first functional layer is 80 nm or more and 100 nm or less, The film thickness of the second dielectric layer is 10 nm or more and 30 nm or less, The film thickness of the second functional layer is 5 nm or more and 15 nm or less, The film thickness of the third dielectric layer is 70 nm or more and 90 nm or less, The energy reflectance on the second main surface side is 35% or more and 70% or less, The visible light transmittance on the second main surface side is 7% or less, The color tone of the reflected light on the second main surface side is L standardized by CIE. ＊ a ＊ b ＊ Color coordinates a defined by the display system ＊ The laminated film-coated glass plate according to [1], wherein the value of the σ is −5 or more and 10 or less.

[0020]

[12] The laminated film-coated glass plate according to any one of [1] to

[11] , wherein the total thickness of the first functional layer and the second functional layer is 10 nm or more and 185 nm or less.

[0021]

[13] The laminated film-coated glass plate according to any one of [1] to

[12] , wherein the first functional layer and the second functional layer have an extinction coefficient k of 1 or more at 550 nm.

[0022]

[14] The laminated film-coated glass plate according to any one of [1] to

[13] , wherein the laminated film has an outermost layer on the third dielectric layer, and the outermost layer has a film thickness of 1 nm or more and 10 nm or less.

[0023]

[15] The outermost layer contains a metal oxide, and the metal oxide is SnO ｘ , TiO ｘ , SiO ｘ and TZO, and X is a number of 0.9 or more and 2.1 or less. The laminated film-coated glass plate according to

[14] .

[0024]

[16] The visible light transmittance on the second principal surface side is 8% or less, and the color tone of the reflected light on the second principal surface side is L standardized by CIE. ＊ a ＊ b ＊ Color coordinates a defined by the display system ＊ is between -5 and 5, and the color coordinate b ＊ A window glass for a vehicle using the laminated film-coated glass sheet according to any one of [1] to

[15] , wherein the value of the laminated film is -10 or more and 10 or less.

[0025]

[17] The visible light transmittance on the second principal surface side is 3% or less, and the color tone of the reflected light on the second principal surface side is L as specified by CIE. ＊ a ＊ b ＊ Color coordinates a defined by the display system ＊ is between -5 and 5, and the color coordinate b ＊ A window glass for a vehicle using the laminated film-coated glass sheet according to any one of [1] to

[15] , wherein the value of the laminated film is -10 or more and 10 or less.

[0026]

[18] A laminated glass for a vehicle having a first glass plate, an interlayer film, and a second glass plate in this order, wherein the first glass plate is the laminated film-coated glass plate according to any one of [1] to

[15] , and the interlayer film is disposed on the first main surface side of the first glass plate.

[0027]

[19] A laminated glass for a vehicle roof, comprising a first glass plate, an interlayer film, and a second glass plate in this order, wherein the first glass plate is the laminated film-coated glass plate according to any one of [1] to

[15] , and the interlayer film is disposed on the first main surface side of the first glass plate.

[0028] According to the present invention, it is possible to provide a laminated film-coated glass sheet, a vehicle window glass, a vehicle laminated glass, and a vehicle roof laminated glass that combine durability, heat insulation properties, and productivity.

[0029] Fig. 1 is a cross-sectional view showing an example of the configuration of a laminated film-coated glass plate according to embodiment 1. Fig. 2 is a cross-sectional view showing an example of the configuration of a laminated film-coated glass plate according to embodiment 2. Fig. 3 is a cross-sectional view showing an example of the configuration of a laminated film-coated glass plate according to embodiment 3. Fig. 4 is a cross-sectional view showing an example of the configuration of a laminated glass according to embodiment 4.

[0030] Hereinafter, embodiments of the present invention will be described with reference to the drawings. In each drawing, the same or corresponding elements are designated by the same reference numerals, and for clarity of explanation, duplicate explanations will be omitted as necessary. Furthermore, in this specification, the numerical range indicated by "to" includes the numerical values ​​before and after it as the lower and upper limits.

[0031] <Embodiment 1> Fig. 1 is a cross-sectional view showing an example of the configuration of a laminated film-coated glass sheet according to Embodiment 1. As shown in Fig. 1, the laminated film-coated glass sheet according to Embodiment 1 includes a glass sheet 10 and a laminated film 20. The glass sheet 10 includes a first main surface 11 and a second main surface 12. The laminated film 20 is a film including a plurality of layers provided on the first main surface of the glass sheet 10. The laminated film 20 functions as a heat-shielding film.

[0032] The laminated film-coated glass sheet 100 is suitable for use as a window glass for vehicles such as automobiles due to its excellent durability. The laminated film-coated glass sheet 100 is particularly suitable for use as a window glass for a vehicle roof due to its low visible light transmittance. The laminated film-coated glass sheet 100 may also be combined with an interlayer and another glass sheet to be used as laminated glass. When the laminated film-coated glass sheet 100 is used as a vehicle window glass, it is attached to a vehicle body so that the first main surface 11 faces the vehicle interior and the second main surface 12 faces the vehicle exterior, for example.

[0033] The glass plate 10 is a glass plate. The type of glass constituting the glass plate 10 is not particularly limited and may be, for example, soda-lime glass, quartz glass, borosilicate glass, alkali-free glass, or UV-cut glass. The visible light transmittance of the glass plate 10 may be, for example, 50% or more, 60% or more, 70% or more, or 80% or more. The visible light transmittance of the glass plate 10 may be, for example, 95% or less, 90% or less, 80% or less, or 50% or less. The visible light transmittance is a value measured by a measurement method in accordance with JIS R3106. The shape of the glass plate 10 does not necessarily have to be flat, and the glass plate 10 may be curved. The glass plate 10 may be colorless or colored. The thickness of the glass plate 10 may be, for example, 0.5 mm or more, 1 mm or more, or 2 mm or more. The thickness of the glass plate 10 may be, for example, 10 mm or less, 6 mm or less, or 5 mm or less.

[0034] From the viewpoint of improving the ability to wipe off dirt, the surface roughness Ra of the laminated film 20 may be, for example, 30 nm or less, 25 nm or less, 20 nm or less, or 15 nm or less. The surface roughness Ra of the laminated film 20 may be, for example, 0.1 nm or more, 0.5 nm or more, 1 nm or more, 2 nm or more, or 3 nm or more. The surface roughness Ra is a value measured by a method conforming to JIS B0601:2001 (ISO4287:1997).

[0035] The visible light transmittance Tv (%) on the second main surface 12 side of the laminated film-coated glass sheet 100 is, for example, 8% or less, 7% or less, 6% or less, 5% or less, 4% or less, 3% or less, 2% or less, or 1% or less. The visible light transmittance Tv (%) is a value obtained by measuring the spectral transmission spectrum of the laminated film-coated glass sheet 100 using a spectrophotometer and calculating the visible light transmittance Tv in accordance with JIS R3106 using the obtained spectral spectrum. The visible light transmittance Tv (%) of a vehicle roof window glass, for example, in a laminated glass state, is preferably approximately 1% to 7%. When an Ag-based heat-shielding film is provided, the visible light transmittance of the laminated glass is usually adjusted using expensive materials such as a dark interlayer film or a gray substrate. On the other hand, in the laminated film-coated glass sheet 100 according to the present disclosure, the visible light transmittance of the laminated film-coated glass sheet 100 itself has a value of the above-mentioned level, eliminating or reducing the need to adjust the visible light transmittance using an interlayer film and a glass substrate.

[0036] The energy reflectance Re (%) on the second main surface 12 side of the laminated film-coated glass sheet 100 is, for example, 20% or more, 25% or more, 27% or more, 28% or more, 29% or more, 30% or more, 31% or more, 32% or more, 33% or more, 34% or more, 35% or more, 36% or more, 37% or more, or 38% or more. The energy reflectance Re (%) on the second main surface 12 side of the laminated film-coated glass sheet 100 is, for example, 70% or less, 50% or less. The energy reflectance Re (%) is calculated in accordance with JIS R3106. For example, the energy reflectance Re (%) is a value obtained by measuring the spectral reflectance spectrum of the laminated film-coated glass sheet 100 in the range of 300 nm to 2500 nm using a spectrophotometer (U-4100: manufactured by Hitachi Ltd.), and calculating the visible light reflectance Re in accordance with JIS R3106 using the obtained spectral spectrum.

[0037] The visible light reflectance Rgv (%) on the second main surface 12 side of the laminated film-coated glass sheet 100 is, for example, 35% or less, preferably 30% or less, from the viewpoint of reducing the glare of reflected light received by people outside the vehicle when the laminated film-coated glass sheet 100 is used as a vehicle windowpane. The lower limit of the visible light reflectance Rgv (%) is not particularly limited, and the visible light reflectance Rgv (%) may be, for example, 5% or more, 10% or more, 15% or more, or 20% or more. The visible light reflectance Rgv (%) is calculated in accordance with JIS R3106. For example, the visible light reflectance Rgv (%) is calculated in accordance with JIS R3106 using the spectral reflectance spectrum of the laminated film-coated glass sheet 100 measured in the range of 300 nm to 2500 nm using a spectrophotometer (U-4100: manufactured by Hitachi).

[0038] The visible light reflectance Rfv (%) on the first main surface 11 side of the laminated film-coated glass sheet 100 is, for example, 35% or less, preferably 30% or less, more preferably 20% or less, and particularly preferably 10% or less, from the viewpoint of reducing reflections inside the vehicle when the laminated film-coated glass sheet 100 is used as a window glass for a vehicle. The lower limit of the visible light reflectance Rfv (%) is not particularly limited, and the visible light reflectance Rfv (%) may be, for example, 1% or more, 2% or more, or 3% or more. The visible light reflectance Rfv (%) is calculated in accordance with JIS R3106. For example, the visible light reflectance Rfv (%) is determined by measuring the spectral reflectance spectrum of the laminated film-coated glass sheet 100 in the range of 300 nm to 2500 nm using a spectrophotometer (U-4100: manufactured by Hitachi, Ltd.), and calculating the visible light reflectance Rfv in accordance with JIS R3106 using the obtained spectral spectrum.

[0039] The color tone of the reflected light on the second main surface 12 side of the laminated film-coated glass plate 100 is set to the L standard of CIE from the viewpoint of making the color tone closer to a neutral color. ＊ a ＊ b ＊ Color coordinates a defined by the display system ＊is, for example, −10 or more, −5 or more, or 0 or more, and 10 or less, 5 or less, or 0 or less. In addition, the color tone of the reflected light on the second main surface 12 side of the laminated film-coated glass plate 100 is set to be equal to or less than the L ＊ a ＊ b ＊ Color coordinates b defined by the display system ＊ is, for example, -15 or more, -10 or more, -5 or more, 0 or more, and 15 or less, 10 or less, 5 or less, 0 or less. ＊ and b ＊ For example, the spectral transmittance spectrum is measured using a spectrophotometer (U-4100: manufactured by Hitachi Ltd.), and the obtained spectral transmittance is calculated according to CIE 1976 L ＊ a ＊ b ＊ The values ​​are expressed in color space (D65 light source, 2° observer).

[0040] As shown in FIG. 1 , the laminate film 20 includes, in order from the first main surface 11 side, a first dielectric layer 21, a first functional layer 22, a second dielectric layer 23, a second functional layer 24, and a third dielectric layer 25. The thickness of each layer in the laminate film 20 was determined by cutting the laminate-coated glass plate 100 in the thickness direction and directly examining the cross section using a scanning electron microscope (SEM, Hitachi, Ltd.'s "SU 70") to image the cross section. When the interface had irregularities, the thickness of each layer was determined using the midpoint between the horizontal lines of the lowest valley and the highest peak as a guide. A too low magnification for the observation magnification results in insufficient film thickness measurement accuracy, while a too high magnification can reveal localized irregularities, potentially preventing the thickness of each layer from being accurately determined. Therefore, an appropriate range of magnification is required. Therefore, as a guideline for observation conditions, for example, an electron gun of 1.5 kV, a working distance of 2.4 mm, and a magnification of 50,000x are used.

[0041] The materials contained in each layer of the laminated film 20 are measured by XPS measurement. Specifically, for example, in the XPS measurement, a scanning X-ray photoelectron spectrometer (PHI 5000 VersaProbe, manufactured by ULVAC-PHI, Inc.) may be used with a beam diameter of 100 μm to analyze the atomic concentration in the thickness direction from the surface of the laminated film 20 to the interface between the laminated film 20 and the glass plate 10. At this time, argon gas is used as the etching gas, and the gas pressure is 1.5×10 －２ The pressure is set to Pa, the acceleration voltage is set to 1 kV, and the ion beam diameter is set to 2×2 mm.

[0042] The first dielectric layer 21 contains silicon nitride or aluminum nitride. The silicon nitride may be doped with boron, aluminum, titanium, nickel, zinc, molybdenum, tin, tungsten, zirconium, or niobium. The aluminum nitride may be doped with boron, silicon, titanium, nickel, zinc, molybdenum, tin, tungsten, zirconium, or niobium. From the viewpoint of improving moisture resistance, the first dielectric layer 21 is preferably made of silicon nitride (Si) doped with aluminum. １－α N ｙ ・Al α (where α is equal to or greater than 0.03 and equal to or less than 0.50, and y is equal to or greater than 1.0 and equal to or less than 2.0). The first dielectric layer 21 may contain impurities such as carbon atoms and oxygen atoms that are inevitably introduced during film formation. The first dielectric layer 21 may be a single layer, or may be a combination of two or more different types of layers.

[0043] When the laminated film-coated glass sheet 100 is used as a window glass for a vehicle, it may be bent at high temperatures (approximately 650°C). From the viewpoint of suppressing cracks occurring in the laminated film 20 when the laminated film-coated glass sheet 100 is bent at high temperatures, the film thickness of the first dielectric layer 21 is, for example, 60 nm or more, 65 nm or more, 70 nm or more, 75 nm or more, 80 nm or more, 85 nm or more, 90 nm or more, 95 nm or more, or 100 nm or more. Furthermore, from the viewpoint of improving productivity, i.e., reducing costs, the film thickness of the first dielectric layer 21 is, for example, 150 nm or less, 145 nm or less, 140 nm or less, 135 nm or less, 130 nm or less, 125 nm or less, 120 nm or less, 115 nm or less, 110 nm or less, 100 nm or less, or 95 nm or less. The upper and lower limits of the thickness of the first dielectric layer 21 may be a combination of the above, for example, 60 nm to 95 nm, 70 nm to 100 nm, or 90 nm to 120 nm.

[0044] The first functional layer 22 has a heat ray reflection function and contains at least one of titanium nitride, chromium nitride, zirconium nitride, and tantalum nitride. The first functional layer 22 preferably contains titanium nitride. The first functional layer 22 may contain impurities, such as carbon atoms, oxygen atoms, and other metal atoms, that are inevitably introduced during film formation. From the viewpoint of improving heat shielding properties, the film thickness of the first functional layer 22 is 10 nm or more, 30 nm or more, 45 nm or more, 50 nm or more, 55 nm or more, 60 nm or more, 65 nm or more, 70 nm or more, 75 nm or more, 80 nm or more, 85 nm or more, 90 nm or more, or 95 nm or more. From the viewpoint of improving productivity, the film thickness of the first functional layer 22 is 110 nm or less, 105 nm or less, 100 nm or less, 95 nm or less, 90 nm or less, 85 nm or less, 80 nm or less, 75 nm or less, 70 nm or less, 65 nm or less, 60 nm or less, or 55 nm or less. The upper and lower limits of the thickness of the first functional layer 22 may be a combination of the above, for example, 10 nm or more and 55 nm or less, 55 nm or more and 95 nm or less, or 95 nm or more and 110 nm or less.

[0045] The second dielectric layer 23 is formed using the same material as the first dielectric layer 21. From the viewpoint of color tone, the thickness of the second dielectric layer 23 is, for example, 5 nm or more, 10 nm or more, 15 nm or more, 20 nm or more, 25 nm or more, 30 nm or more, 35 nm or more, 40 nm or more, 45 nm or more, 50 nm or more, 55 nm or more, or 60 nm or more. From the viewpoint of improving productivity, the thickness of the second dielectric layer 23 is, for example, 110 nm or less, 100 nm or less, 90 nm or less, 80 nm or less, 75 nm or less, 70 nm or less, 65 nm or less, 60 nm or less, 55 nm or less, 50 nm or less, 45 nm or less, 40 nm or less, 35 nm or less, 30 nm or less, 25 nm or less, or 20 nm or less. The upper and lower limits of the thickness of the second dielectric layer 23 may be a combination of the above, for example, 10 nm or more to 40 nm or less, 40 nm or more to 70 nm or less, or 70 nm or more to 110 nm or less.

[0046] The second functional layer 24 is formed using the same material as the first functional layer 22. From the viewpoint of improving heat shielding properties, the film thickness of the second functional layer 24 is 5 nm or more, 10 nm or more, 15 nm or more, 20 nm or more, 25 nm or more, 45 nm or more, 50 nm or more, 55 nm or more, 60 nm or more, 65 nm or more, 70 nm or more, 75 nm or more, 80 nm or more, 85 nm or more, 90 nm or more, or 95 nm or more. From the viewpoint of improving productivity, the film thickness of the second functional layer 24 is 110 nm or less, 105 nm or less, 100 nm or less, 95 nm or less, 90 nm or less, 85 nm or less, 80 nm or less, 75 nm or less, 70 nm or less, 65 nm or less, 60 nm or less, 55 nm, 50 nm or less, 45 nm or less, 40 nm or less, 35 nm or less, 30 nm or less, 25 nm or less, 20 nm or less, 15 nm or less, or 10 nm or less. The upper and lower limits of the thickness of the second functional layer 24 may be a combination of the above, for example, 5 nm to 40 nm, 40 nm to 70 nm, or 70 nm to 100 nm.

[0047] The third dielectric layer 25 is formed using the same material as the first dielectric layer 21. The thickness of the third dielectric layer 25 is, for example, 5 nm or more, 10 nm or more, 15 nm or more, 20 nm or more, 25 nm or more, 30 nm or more, 35 nm or more, 40 nm or more, 45 nm or more, 50 nm or more, 55 nm or more, 60 nm or more, 65 nm or more, 70 nm or more, 75 nm or more, or 80 nm or more from the viewpoint of protecting the first functional layer 22 and the second functional layer 24 from deterioration due to oxygen and moisture and from abrasion. The thickness of the second dielectric layer 23 is, for example, 100 nm or less, 95 nm or less, 90 nm or less, 85 nm or less, 80 nm or less, 75 nm or less, 70 nm or less, 65 nm or less, 60 nm or less, 55 nm or less, 50 nm or less, 45 nm or less, 40 nm or less, 35 nm or less, 30 nm or less, 25 nm or less, or 20 nm or less from the viewpoint of improving productivity. The upper and lower limits of the thickness of the third dielectric layer 25 may be a combination of the above, for example, 10 nm to 40 nm, 40 nm to 70 nm, or 70 nm to 100 nm.

[0048] The laminated film 20 may further have a top layer (not shown) on the third dielectric layer 25. The top layer may be SnO ｘ , TiO ｘ , SiO ｘ and TZO. Here, TZO is zinc oxide containing titanium. X is a number between 0.9 and 2.1. The thickness of the outermost layer is, for example, 0.5 nm or more, 1 nm or more, or 2 nm or more. The thickness of the outermost layer is, for example, 15 nm or less, 10 nm or less, or 8 nm or less.

[0049] From the viewpoint of achieving thermal barrier performance without PEM (Plasma Emission Monitoring) control, the total thickness of the first functional layer 22 and the second functional layer 24 is, for example, 10 nm or more, 65 nm or more, 70 nm or more, 75 nm or more, 80 nm or more, 85 nm or more, 90 nm or more, 195 nm or less, 190 nm or less, 185 nm or less, 180 nm or less, 175 nm or less, 170 nm or less, 110 nm or less, or 65 nm or less. The total thickness of the first functional layer 22 and the second functional layer 24 may be a combination of the above, for example, 10 nm or more and 65 nm or less, 65 nm or more and 110 nm or less, or 110 nm or more and 180 nm or less. Here, PEM control is a system that monitors plasma emission intensity during film formation and provides high-speed feedback to control the process gas flow rate in real time. This precise control enables the formation of the highest-performance film near the transition region between nitride mode and metal mode, thereby achieving thin films. However, the introduction of this system is costly, making it difficult to implement. However, since the present invention is based on the premise of depositing a thick, low-quality functional layer, it can be fabricated without the introduction of a costly PEM control system.

[0050] The extinction coefficient k at 550 nm of the first functional layer 22 and the second functional layer 24 is, for example, 1 or more from the viewpoint of reducing the visible light transmittance of the laminated film-coated glass plate 100. The extinction coefficient k is determined, for example, by measuring the spectroscopic spectrum (reflection and transmission) of the laminated film-coated glass plate 100 using a spectrophotometer (U-4100: manufactured by Hitachi Ltd.) and fitting an optical model using the obtained spectroscopic spectrum.

[0051] The laminated film-coated glass sheet 100 may also have a self-cleaning film on the second main surface 12. The self-cleaning film is a film that inhibits adhesion of organic and inorganic substances to the surface, or a film that has the effect of allowing the adhesion of organic and inorganic substances to be easily removed by cleaning, such as wiping, even if they are attached to the surface. From the viewpoint of obtaining the above-mentioned effect, the self-cleaning film is preferably formed on the outermost surface on the second main surface 12 side of the laminated film-coated glass sheet 100. The self-cleaning film is not particularly limited as long as it can impart self-cleaning properties, and may be, for example, a fluorine-containing organosilicon compound coating obtained by curing a fluorine-containing organosilicon compound by a hydrolysis and condensation reaction.

[0052] When the self-cleaning film is a fluorine-containing organosilicon compound coating, the film thickness is preferably 2 to 20 nm, more preferably 2 to 15 nm, and even more preferably 2 to 10 nm. If the self-cleaning film has a film thickness of 2 nm or more, the glass substrate is uniformly covered with the self-cleaning film, making it practically usable in terms of abrasion resistance. Furthermore, if the self-cleaning film has a film thickness of 20 nm or less, the optical properties of the self-cleaning film formed are good.

[0053] When the laminated film-coated glass sheet 100 is used as a vehicle window glass in the state of a single glass sheet, for example, the visible light transmittance Tv on the second main surface 12 side is 8% or less, and the color coordinate a of the reflected light on the second main surface 12 side is ＊ is -5 to 5, b ＊ may be −10 to 10. The laminated film-coated glass sheet 100 that satisfies this condition is applied to a transparent vehicle window glass. When the laminated film-coated glass sheet 100 is applied to a vehicle window glass in the state of a single glass sheet, for example, the visible light transmittance Tv on the second main surface 12 side is 3% or less, and the color coordinate a of the reflected light on the second main surface 12 side is ＊ is -5 to 5, b ＊ may be −10 to 10. The laminated film-coated glass sheet 100 that satisfies this condition is used as a dark-tinted window glass for a vehicle.

[0054] When the objective is to bring the color tone closer to a neutral color, the laminated film-coated glass plate 100 may be configured to satisfy all of the following conditions, for example: The ratio of the total thickness of the first functional layer 22 and the second functional layer 24 to the thickness of the first dielectric layer 21 is 0.4 or more and 3.3 or less. The ratio of the total thickness of the first functional layer 22 and the second functional layer 24 to the thickness of the second dielectric layer 23 is 0.1 or more and 2.1 or less. The ratio of the total thickness of the first functional layer 22 and the second functional layer 24 to the thickness of the third dielectric layer 25 is 0.5 or more and 12.5 or less.

[0055] When the objective is to bring the color tone closer to a neutral color and to improve the heat shielding properties, the laminated film-coated glass plate 100 may be configured to satisfy all of the following conditions, for example: The film thickness of the first dielectric layer 21 is 80 nm or more and 100 nm or less. The film thickness of the first functional layer 22 is 80 nm or more and 100 nm or less. The film thickness of the second dielectric layer 23 is 10 nm or more and 30 nm or less. The film thickness of the second functional layer 24 is 5 nm or more and 15 nm or less. The film thickness of the third dielectric layer 25 is 70 nm or more and 90 nm or less. The energy reflectance Re on the second main surface 12 side is 35% or more. The visible light transmittance Tv on the second main surface 12 side is 7% or less. The color tone of the reflected light on the second main surface 12 side is expressed by a color coordinate a ＊ is between -5 and 10.

[0056] <Embodiment 2> The laminate film may include at least one base layer. In Embodiment 2, a case where the laminate film includes one base layer will be described. FIG. 2 is a cross-sectional view showing an example of the configuration of a laminate film-coated glass plate 200 according to Embodiment 2. The laminate film-coated glass plate 200 shown in FIG. 2 differs from the laminate film-coated glass plate 100 described with reference to FIG. 1 in that the laminate film 30 includes a base layer 31 between the second dielectric layer 23 and the second functional layer 24. The laminate film-coated glass plate 200 is otherwise similar in configuration to the laminate film-coated glass plate 100, and therefore description thereof will be omitted.

[0057] The underlayer 31 contains zirconium nitride and improves the crystallinity of a specific metal nitride contained in the functional layer formed directly thereon. By providing the underlayer 31, the film quality of the functional layer can be improved, so that the heat-shielding performance of the laminated film 30 can be sufficiently ensured even if the functional layer is made thin. The zirconium nitride contained in the underlayer 31 is ZrN ｘ where x is greater than 1.2 and equal to or less than 2.0. ｘ is preferably present in the base layer 31 in a portion that contacts the functional layer. When x exceeds 1.2, the effect of improving the crystallinity of the specific metal nitride contained in the functional layer is exerted. x is preferably 1.28 or more, more preferably 1.35 or more. The upper limit of x is 2, which is the theoretical value based on the chemical composition. The value of x can be adjusted by controlling the film formation conditions such as the temperature of the transparent substrate, the pressure during film formation, the composition of the introduced gas, the power supply power during film formation, the target composition, and the post-heat treatment temperature. The base layer 31 may contain impurities such as carbon atoms, oxygen atoms, and other metal atoms that are inevitably introduced during film formation.

[0058] The thickness of the underlayer 31 is, for example, 1 nm or more, 2 nm or more, 3 nm or more, 4 nm or more, or 5 nm or more from the viewpoint of sufficiently ensuring the heat-shielding performance of the laminated film 30. The thickness of the underlayer 31 is, for example, 12 nm or less, 11 nm or less, 10 nm or less, 9 nm or less, 8 nm or less, 7 nm or less, 6 nm or less, 5 nm or less, or 4 nm or less from the viewpoint of improving productivity.

[0059] To make the color tone closer to a neutral color, i.e., the color coordinate a ＊ and b ＊ When the objective is to make all of these values ​​close to 0, the laminated film-coated glass plate 200 may be configured to satisfy all of the following conditions, for example: The ratio of the total thickness of the first functional layer 22 and the second functional layer 24 to the thickness of the first dielectric layer 21 is 0.4 or more and 3.3 or less. The ratio of the total thickness of the first functional layer 22 and the second functional layer 24 to the total thickness of the second dielectric layer 23 and the base layer 31 is 0.1 or more and 2.1 or less. The ratio of the total thickness of the first functional layer 22 and the second functional layer 24 to the thickness of the third dielectric layer 25 is 0.5 or more and 12.5 or less. The ratio of the thickness of the base layer 31 to the thickness of the second dielectric layer 23 is 0.1 or less.

[0060] When the objective is to bring the color tone closer to a neutral color and to improve the heat shielding properties, the laminated film-coated glass plate 200 may be configured to satisfy all of the following conditions, for example: The film thickness of the first dielectric layer 21 is 80 nm or more and 100 nm or less. The film thickness of the first functional layer 22 is 50 nm or more and 65 nm or less. The film thickness of the second dielectric layer 23 is 35 nm or more and 60 nm or less. The film thickness of the underlayer 31 is 2 nm or more and 10 nm or less. The film thickness of the second functional layer 24 is 45 nm or more and 65 nm or less. The film thickness of the third dielectric layer 25 is 25 nm or more and 50 nm or less. The energy reflectance Re on the second main surface 12 side is 30% or more. The visible light transmittance Tv on the second main surface 12 side is 6% or less. The color tone of the reflected light on the second main surface 12 side is expressed by a color coordinate a ＊ and b ＊ is between -5 and 5.

[0061] When the objective is to increase both the energy reflectance and the heat shielding property, the laminated film-coated glass plate 200 may be configured to satisfy all of the following conditions, for example. The film thickness of the first dielectric layer 21 is 80 nm or more and 100 nm or less. The film thickness of the first functional layer 22 is 70 nm or more and 90 nm or less. The film thickness of the second dielectric layer 23 is 10 nm or more and 30 nm or less. The film thickness of the underlayer 31 is 3 nm or more and 10 nm or less. The film thickness of the second functional layer 24 is 75 nm or more and 95 nm or less. The film thickness of the third dielectric layer 25 is 20 nm or more and 30 nm or less. The energy reflectance Re on the second main surface 12 side is 32% or more. The visible light transmittance Tv on the second main surface 12 side is 2% or less. The color tone of the reflected light on the second main surface 12 side is expressed by a color coordinate a ＊ is between -5 and 10.

[0062] In the example shown in Figure 2, the base layer 31 is provided between the second dielectric layer 23 and the second functional layer 24, but the base layer 31 may also be provided between the first dielectric layer 21 and the first functional layer 22.

[0063] <Embodiment 3> The laminate film may include a base layer below each of the two functional layers. In Embodiment 3, a case where a base layer is provided below each of the two functional layers is described. FIG. 3 is a cross-sectional view showing an example of the configuration of a laminate film-coated glass plate 300 according to Embodiment 3. The laminate film-coated glass plate 300 shown in FIG. 3 differs from the laminate film-coated glass plate 100 described with reference to FIG. 1 in that the laminate film 40 includes a first base layer 41 between the first dielectric layer 21 and the first functional layer 22 and a second base layer 42 between the second dielectric layer 23 and the second functional layer 24. The laminate film-coated glass plate 300 is otherwise similar in configuration to the laminate film-coated glass plate 100, and therefore description thereof will be omitted. The first base layer 41 and the second base layer 42 are made of the same material as the base layer 31 described with reference to FIG. 2, and their properties, such as film thickness, are also similar.

[0064] When the objective is to bring the color tone closer to a neutral color, the laminated film-coated glass plate 300 may be configured to satisfy all of the following conditions, for example: The ratio of the total thickness of the first functional layer 22 and the second functional layer 24 to the total thickness of the first dielectric layer 21 and the first base layer 41 is 0.4 or more and 3.3 or less. The ratio of the total thickness of the first functional layer 22 and the second functional layer 24 to the total thickness of the second dielectric layer 23 and the second base layer 42 is 0.1 or more and 2.1 or less. The ratio of the total thickness of the first functional layer 22 and the second functional layer 24 to the thickness of the third dielectric layer 25 is 0.5 or more and 12.5 or less. The ratio of the thickness of the first base layer 41 to the thickness of the first dielectric layer 21 is 0.1 or less. The ratio of the thickness of the second base layer 42 to the thickness of the second dielectric layer 23 is 0.1 or less.

[0065] When the objective is to bring the color tone closer to a neutral color and to improve the heat shielding properties, the laminated film-coated glass plate 300 may be configured to satisfy all of the following conditions, for example: The film thickness of the first dielectric layer 21 is 90 nm or more and 110 nm or less. The film thickness of the first base layer 41 is 1 nm or more and 5 nm or less. The film thickness of the first functional layer 22 is 50 nm or more and 70 nm or less. The film thickness of the second dielectric layer 23 is 50 nm or more and 70 nm or less. The film thickness of the second base layer 42 is 3 nm or more and 10 nm or less. The film thickness of the second functional layer 24 is 25 nm or more and 45 nm or less. The film thickness of the third dielectric layer 25 is 10 nm or more and 30 nm or less. The energy reflectance Re on the second main surface 12 side is 30% or more. The visible light transmittance Tv on the second main surface 12 side is 7% or less. The color tone of the reflected light on the second main surface 12 side is expressed by the color coordinate a ＊ is greater than or equal to -5 and less than or equal to 5, and b ＊ is between -10 and 10.

[0066] When the objective is to increase both the energy reflectivity and the heat shielding property, the laminated film-coated glass plate 300 may be configured to satisfy all of the following conditions, for example: The film thickness of the first dielectric layer 21 is 95 nm or more and 115 nm or less. The film thickness of the first base layer 41 is 1 nm or more and 5 nm or less. The film thickness of the first functional layer 22 is 80 nm or more and 100 nm or less. The film thickness of the second dielectric layer 23 is 50 nm or more and 70 nm or less. The film thickness of the base layer 31 is 3 nm or more and 10 nm or less. The film thickness of the second functional layer 24 is 25 nm or more and 45 nm or less. The film thickness of the third dielectric layer 25 is 10 nm or more and 30 nm or less. The energy reflectivity Re on the second main surface 12 side is 30% or more. The visible light transmittance Tv on the second main surface 12 side is 3% or less. The color tone of the reflected light on the second main surface 12 side is expressed by the color coordinate a ＊ is between -5 and 5.

[0067] Fourth Embodiment A laminated film-coated glass sheet according to the present disclosure may be used as a glass sheet included in laminated glass. FIG. 4 is a cross-sectional view showing an example of the configuration of a laminated glass 400 according to the fourth embodiment. As shown in FIG. 4, the laminated glass 400 is a laminated glass having a first glass sheet (a laminated film-coated glass sheet) 300, an interlayer film 60, and a second glass sheet 70, in this order. The second glass sheet 70 may be made of the same material as the glass sheet 10 and may have similar characteristics, such as thickness. The second glass sheet 70 may further include a functional film or coating having various functions. The functional film may be a single layer or multiple layers. An example of a functional film is a low-emissivity film such as a low-E (low emissivity) film. Here, low emissivity refers to reducing heat transfer due to radiation. The low-emissivity film ensures thermal insulation by suppressing heat transfer due to radiation. The low-emissivity film is formed, for example, on the surface of the second glass sheet that is not on the interlayer film 60 side.

[0068] The Low-E film may have any configuration, but may include, for example, an alkali barrier film, a first transparent dielectric film, a transparent conductive film, a second transparent dielectric film, and a hard coat film, in this order from the second glass plate 70 side. ２ , SiOC, and TZO. The alkali barrier film may have a thickness of 0 to 10 nm. The first transparent dielectric film may contain one selected from the group consisting of SiO ２ The first transparent dielectric film may have a thickness of 10 to 200 nm. The transparent conductive film may contain ITO, SnO ２ , ZnO. The transparent conductive film may have a thickness of 50 to 200 nm. The second transparent dielectric film may contain one selected from the group consisting of SiO ２ The second transparent conductive film may have a thickness of 10 to 200 nm. The hard coat film may contain SiZrO, TiO ２ , ZrO, SiO ２ The hard coat film may contain one selected from the group consisting of: The film thickness of the hard coat film may be 1 to 50 nm.

[0069] The Low-E film may include, for example, an alkali barrier film, a first transparent dielectric film, an infrared reflective film, a second transparent dielectric film, an optical adjustment film, a third transparent dielectric film, and a hard coat film, in this order from the second glass plate 70 side. ２ , SiOC, and TZO. The alkali barrier film may have a film thickness of 0 to 10 nm. The first transparent dielectric film may contain SiAlN. The film thickness of the first transparent dielectric film may be 1 to 20 nm. The infrared reflective film may contain TiN. The film thickness of the infrared reflective film may be 10 to 100 nm. The second transparent dielectric film may contain SiAlN. The film thickness of the second transparent conductive film may be 10 to 50 nm. The optical adjustment film may contain a metal nitride. The film thickness of the optical adjustment film may be 1 to 20 nm. The third transparent dielectric film may contain SiAlN. The film thickness of the third transparent conductive film may be 30 to 100 nm. The hard coat film may contain SiZrO, TiO ２ , ZrO, SiO ２ The hard coat film may contain one selected from the group consisting of: The film thickness of the hard coat film may be 1 to 100 nm.

[0070] The Low-E film may be, for example, a laminated film including, from the second glass plate 70 side, a first transparent dielectric film, a transparent conductive film, and a second transparent dielectric film in this order. The first transparent dielectric film, the transparent conductive film, and the second transparent dielectric film may each be composed of a single layer or multiple layers. The first transparent dielectric film and the second transparent dielectric film may contain an oxide or oxynitride of at least one metal selected from the group consisting of Ti, Nb, Ta, Zn, Al, In, Si, and Zr. The film thickness of the first transparent dielectric film may be 3 to 50 nm. The film thickness of the second transparent dielectric film may be 50 to 120 nm. The transparent conductive film may be an ITO (tin-doped indium tin oxide) layer, a tin oxide layer, a fluorine-doped tin oxide layer, an antimony-doped tin oxide layer, a silver layer, a zirconium nitride layer, a titanium nitride layer, or a chromium nitride layer. When the transparent conductive film is a silver layer, the film thickness of the transparent conductive film may be 5 to 100 nm. Here, one or more transparent conductive films may be formed between the transparent dielectric films.

[0071] The interlayer film 60 is provided on the first main surface 11 side of the laminated film-coated glass plate 300, i.e., on the laminated film 40 side. The interlayer film 60 bonds the first glass plate 300 and the second glass plate 70. The interlayer film 60 may be made of, for example, a transparent resin. Examples of the resin constituting the interlayer film 60 include polyvinyl butyral (PVB), polyvinyl chloride, ethylene vinyl acetate (EVA), cycloolefin polymer, urethane resin, and polyvinylidene fluoride (PVDF). The lower limit of the thickness of the interlayer film 60 is, for example, 0.1 mm, 0.2 mm, or 0.3 mm. The upper limit of the thickness of the interlayer film 60 may be, for example, 2.0 mm, 1.0 mm, or 0.7 mm. The interlayer film 60 may be colorless or colored. The interlayer film 60 may be colored, for example, by being made of a resin containing a colorant such as a pigment.

[0072] The laminated glass 400 may be used, for example, as a vehicle windowpane, and particularly as a vehicle roof windowpane. The normal emissivity of the interior side of the laminated glass 400, i.e., the side (fourth side) of the second glass sheet 70 opposite the interlayer 60 side, may be, for example, 0.3 or less, from the viewpoint of suppressing the release of warm air from heating to the outside of the vehicle in winter. Here, the normal emissivity is a value measured, for example, using an emissivity measuring instrument TSS-5X manufactured by Japan Sensor Co., Ltd. The visible light transmittance of the laminated glass 400 may be, for example, 0.1% or more, from the viewpoint of natural lighting. Furthermore, the visible light transmittance of the laminated glass 400 may be 7% or less, from the viewpoint of light blocking. Here, the visible light transmittance of the laminated glass 400 is a value obtained by measuring the spectral transmission spectrum using a spectrophotometer (U-4100: manufactured by Hitachi) and calculating the visible light transmittance in accordance with JIS R3106 using the obtained spectral spectrum. There is no particular lower limit for the visible light reflectance on the fourth surface of laminated glass 400, but it may be, for example, 0.2% or more. Furthermore, from the viewpoint of suppressing glare, the visible light reflectance on the fourth surface of laminated glass 400 may be 3.8% or less. Here, the visible light reflectance on the fourth surface of laminated glass 400 is a value obtained by measuring the spectral transmission spectrum using a spectrophotometer (U-4100: manufactured by Hitachi) and calculating the visible light transmittance in accordance with JIS R3106 using the obtained spectral spectrum.

[0073] Next, examples of the present invention will be described. As samples according to the examples, samples of glass sheets with laminated films were prepared by the following method. The glass sheets used for each sample were float glass sheets (manufactured by AGC Inc.) with a thickness of 2 mm.

[0074] Glass samples with laminated films were prepared by forming laminated films under predetermined conditions on glass plates. The film structure, material, and thickness of the laminated films formed in each sample are shown in Table 1. Examples 1 to 5, 8, and 11 to 16 are working examples, and Examples 6 to 7 and 9 to 10 are comparative examples. The samples prepared in this manner were evaluated.

[0075]

[0076] <Durability Evaluation> Assuming glass sheet bending processing, the samples of Examples 1 to 8 were baked at 660°C for 4 minutes and evaluated for the presence or absence of cracks. The results are shown in Table 2. As shown in Table 2, Examples 1 to 5 and 8 showed good results with no cracks. On the other hand, Examples 6 and 7 showed cracks.

[0077]

[0078] <Color Tone Evaluation> For each sample in Examples 1 to 8, the color coordinates a on the glass surface and the film surface were ＊ and b ＊ Specifically, the spectral transmittance spectrum of each sample was measured using a spectrophotometer (U-4100, manufactured by Hitachi). The obtained spectral transmittance was measured according to CIE 1976 L ＊ a ＊ b ＊ The results were expressed in color space (D65 light source, 2° field of view). The glass surface refers to the main surface of the laminated film-coated glass plate on which the laminated film is not formed. The film surface refers to the main surface of the laminated film-coated glass plate on which the laminated film is formed. The actual measurement results are shown in Table 2. As shown in Table 2, the color coordinate a of the reflected light from the glass surface side ＊ In all of Examples 1 to 8, the color coordinate b of the reflected light from the glass surface side was in the range of −10 to 10. ＊ was in the range of −10 to 10 in Examples 1, 7 and 8.

[0079] <Visible Light Transmittance> The visible light transmittance was measured for each of the samples of Examples 1 to 8. Specifically, the spectral transmission spectrum of each of the samples of Examples 1 to 8 was measured using a spectrophotometer (U-4100, manufactured by Hitachi, Ltd.). The obtained spectral spectrum was used to calculate the visible light transmittance in accordance with JIS R3106. The measurement results are shown in Table 2. As shown in Table 2, the visible light transmittance was 8% or less in Examples 1 to 5 and 8, which was good. On the other hand, the visible light transmittance was more than 8% in Examples 6 to 7.

[0080] <Visible Light Reflectance> For each of the samples in Examples 1 to 8, the visible light reflectance was measured on the glass surface side and the film surface side. Specifically, for each of the samples in Examples 1 to 8, the spectral reflectance spectrum was measured in the range of 300 nm to 2500 nm using a spectrophotometer (U-4100: manufactured by Hitachi). Using the obtained spectral spectrum, the visible light reflectance was calculated in accordance with JIS R3106. The measurement results are shown in Table 2. As shown in Table 2, the visible light reflectance was 35% or less in all of Examples 1 to 8.

[0081] <Energy Reflectance> For each of the samples in Examples 1 to 8, the energy reflectance on the glass surface side was measured. Specifically, for each of the samples in Examples 1 to 8, the spectral reflectance spectrum was measured in the range of 300 nm to 2500 nm using a spectrophotometer (U-4100: manufactured by Hitachi Ltd.). Using the obtained spectral spectrum, the energy reflectance was calculated in accordance with JIS R3106. The measurement results are shown in Table 2. As shown in Table 2, the energy reflectance was 30% or more in all of Examples 1 to 8.

[0082] <Evaluation of Tensile Stress> A tensile stress simulation was performed for each sample according to Examples 1 to 13. The maximum tensile stress value for each sample is shown in Table 3. As shown in Table 3, the maximum tensile stress value was 1158.50 or less in Examples 1 to 5 and 8, and exceeded 1158.50 in Examples 6 and 7.

[0083]

[0084] <Examples 14 to 16> For each sample in Examples 14 to 16, the color coordinates a on the glass surface and the film surface were ＊ and b ＊ The visible light transmittance, visible light reflectance on the film surface side, and energy reflectance on the glass surface side were calculated by optical simulation. The optical simulation was carried out in accordance with Fresnel's law based on the refractive index and wavelength spectrum of the extinction coefficient of each material and the film thickness of each layer. The calculation results are shown in Table 4. As shown in Table 4, the color coordinate a of the reflected light from the glass surface side ＊ In all of Examples 14 to 16, the color coordinate b of the reflected light from the glass surface side was in the range of −10 to 10. ＊In Examples 14 to 16, the visible light transmittance was in the range of -10 to 10. In all of Examples 14 to 16, the visible light reflectance on the film surface side was 8% or less. In all of Examples 14 to 16, the visible light reflectance on the film surface side was 35% or less. In all of Examples 14 to 16, the energy reflectance was 20% or more.

[0085]

[0086] The present invention has been described above in accordance with the above-mentioned embodiment, but the present invention is not limited to the configuration of the above-mentioned embodiment, and naturally includes various modifications, alterations, and combinations that a person skilled in the art can make within the scope of the invention as defined in the claims of this application.

[0087] This application claims priority based on Japanese Patent Application No. 2024-108916, filed on July 5, 2024, the disclosure of which is incorporated herein in its entirety by reference.

[0088] 100, 200, 300 Glass sheet with laminated film 400 Laminated glass 10 Glass sheet 11 First main surface 12 Second main surface 20 Laminated film 21 First dielectric layer 22 First functional layer 23 Second dielectric layer 24 Second functional layer 25 Third dielectric layer 30 Laminated film 31 Base layer 40 Laminated film 41 First base layer 42 Second base layer 60 Interlayer 70 Second glass sheet

Claims

1. A laminated film-coated glass plate comprising: a glass plate having a first principal surface and a second principal surface; and a laminated film on the first principal surface, wherein the laminated film comprises, in order from the first principal surface side, a first dielectric layer, a first functional layer, a second dielectric layer, a second functional layer, and a third dielectric layer, wherein the first functional layer and the second functional layer contain at least one of titanium nitride, chromium nitride, zirconium nitride, and tantalum nitride, and the first dielectric layer, the second dielectric layer, and the third dielectric layer contain silicon nitride or aluminum nitride, the film thickness of the first dielectric layer is 60 nm or more and 150 nm or less, the visible light transmittance is 8% or less, and the visible light reflectance on the second principal surface side is 35% or less.

2. The glass plate with a laminate film according to claim 1, wherein the laminate film has an underlayer containing zirconium nitride between the second dielectric layer and the second functional layer.

3. The glass plate with a laminate film according to claim 1, wherein the laminate film comprises: a first base layer containing zirconium nitride between the first dielectric layer and the first functional layer; and a second base layer containing zirconium nitride between the second dielectric layer and the second functional layer.

4. A laminated film-coated glass plate according to any one of claims 1 to 3, wherein the total thickness of the first functional layer and the second functional layer is in a ratio of 0.4 to 3.3 relative to the thickness of the first dielectric layer, the total thickness of the first functional layer and the second functional layer is in a ratio of 0.1 to 2.1 relative to the thickness of the second dielectric layer, and the total thickness of the first functional layer and the second functional layer is in a ratio of 0.5 to 12.5 relative to the thickness of the third dielectric layer.

5. The laminated film-coated glass plate according to claim 2, wherein the thickness of the underlayer relative to the thickness of the second dielectric layer is 0.1 or less in terms of thickness ratio.

6. A glass plate with a laminated film according to claim 3, wherein the ratio of the thickness of the first base layer to the thickness of the first dielectric layer is 0.1 or less, and the ratio of the thickness of the second base layer to the thickness of the second dielectric layer is 0.1 or less.

7. The thickness of the first dielectric layer is 80 nm or more and 100 nm or less, the thickness of the first functional layer is 50 nm or more and 65 nm or less, the thickness of the second dielectric layer is 35 nm or more and 60 nm or less, the thickness of the underlayer is 2 nm or more and 10 nm or less, the thickness of the second functional layer is 45 nm or more and 65 nm or less, the thickness of the third dielectric layer is 25 nm or more and 50 nm or less, the energy reflectance on the second main surface side is 30% or more and 50% or less, the visible light transmittance on the second main surface side is 6% or less, and the color tone of the reflected light on the second main surface side is L as standardized by CIE. ＊ a ＊ b ＊ Color coordinates a defined by the display system ＊ and b ＊ The laminated film-coated glass sheet according to claim 2, wherein the value of the σ is −5 or more and 5 or less.

8. The thickness of the first dielectric layer is 80 nm or more and 100 nm or less, the thickness of the first functional layer is 70 nm or more and 90 nm or less, the thickness of the second dielectric layer is 10 nm or more and 30 nm or less, the thickness of the underlayer is 3 nm or more and 10 nm or less, the thickness of the second functional layer is 75 nm or more and 95 nm or less, the thickness of the third dielectric layer is 20 nm or more and 30 nm or less, the energy reflectance on the second main surface side is 32% or more and 50% or less, the visible light transmittance on the second main surface side is 2% or less, and the color tone of the reflected light on the second main surface side is L as standardized by CIE. ＊ a ＊ b ＊ Color coordinates a defined by the display system ＊ The laminated film-coated glass sheet according to claim 2, wherein the value of the σ is −5 or more and 10 or less.

9. The film thickness of the first dielectric layer is 90 nm or more and 110 nm or less, the film thickness of the first underlayer is 1 nm or more and 5 nm or less, the film thickness of the first functional layer is 50 nm or more and 70 nm or less, the film thickness of the second dielectric layer is 50 nm or more and 70 nm or less, the film thickness of the second underlayer is 3 nm or more and 10 nm or less, the film thickness of the second functional layer is 25 nm or more and 45 nm or less, the film thickness of the third dielectric layer is 10 nm or more and 30 nm or less, the energy reflectance on the second main surface side is 30% or more and 50% or less, the visible light transmittance on the second main surface side is 7% or less, and the color tone of the reflected light on the second main surface side is L as standardized by CIE. ＊ a ＊ b ＊ Color coordinates a defined by the display system ＊ is between -5 and 5, and the color coordinate b ＊ The laminated film-coated glass sheet according to claim 3, wherein the value of the σ is -10 or more and 10 or less.

10. The thickness of the first dielectric layer is 95 nm or more and 115 nm or less, the thickness of the first underlayer is 1 nm or more and 5 nm or less, the thickness of the first functional layer is 80 nm or more and 100 nm or less, the thickness of the second dielectric layer is 50 nm or more and 70 nm or less, the thickness of the second underlayer is 3 nm or more and 10 nm or less, the thickness of the second functional layer is 25 nm or more and 45 nm or less, the thickness of the third dielectric layer is 10 nm or more and 30 nm or less, the energy reflectance on the second main surface side is 30% or more and 50% or less, the visible light transmittance on the second main surface side is 3% or less, and the color tone of the reflected light on the second main surface side is L as standardized by CIE. ＊ a ＊ b ＊ Color coordinates a defined by the display system ＊ The laminated film-coated glass sheet according to claim 3, wherein the value of the σ is −5 or more and 5 or less.

11. The film thickness of the first dielectric layer is 80 nm or more and 100 nm or less, the film thickness of the first functional layer is 80 nm or more and 100 nm or less, the film thickness of the second dielectric layer is 10 nm or more and 30 nm or less, the film thickness of the second functional layer is 5 nm or more and 15 nm or less, the film thickness of the third dielectric layer is 70 nm or more and 90 nm or less, the energy reflectance on the second main surface side is 35% or more and 70% or less, the visible light transmittance on the second main surface side is 7% or less, and the color tone of the reflected light on the second main surface side is L as standardized by CIE. ＊ a ＊ b ＊ Color coordinates a defined by the display system ＊ The laminated film-coated glass sheet according to claim 1, wherein the value of the σ is -5 or more and 10 or less.

12. The laminated film-coated glass plate according to any one of claims 1 to 3, wherein the total film thickness of the first functional layer and the second functional layer is 10 nm or more and 185 nm or less.

13. The laminated film-coated glass plate according to any one of claims 1 to 3, wherein the first functional layer and the second functional layer have an extinction coefficient k of 1 or more at 550 nm.

14. The glass plate with a laminate film according to any one of claims 1 to 3, wherein the laminate film has an outermost layer on the third dielectric layer, and the outermost layer has a film thickness of 1 nm or more and 10 nm or less.

15. The outermost layer contains a metal oxide, and the metal oxide is SnO Ｘ , TiO Ｘ , SiO Ｘ 15. The laminated film-coated glass sheet according to claim 14, wherein at least one selected from the group consisting of X, Xb, Xc, Xd, Xe, Xf, Xf, Xg, Xh, Xh, Xm, Xm is a number of 0.9 or more and 2.1 or less.

16. The visible light transmittance on the second main surface side is 8% or less, and the color tone of the reflected light on the second main surface side is L standardized by CIE. ＊ a ＊ b ＊ Color coordinates a defined by the display system ＊ is between -5 and 5, and the color coordinate b ＊ A vehicle window glass using the laminated film-coated glass sheet according to any one of claims 1 to 3, wherein the value of the laminated film is -10 or more and 10 or less.

17. The visible light transmittance on the second main surface side is 3% or less, and the color tone of the reflected light on the second main surface side is L standardized by CIE. ＊ a ＊ b ＊ Color coordinates a defined by the display system ＊ is between -5 and 5, and the color coordinate b ＊ A vehicle window glass using the laminated film-coated glass sheet according to any one of claims 1 to 3, wherein the value of the laminated film is -10 or more and 10 or less.

18. A laminated glass for vehicles comprising a first glass plate, an interlayer film, and a second glass plate in this order, wherein the first glass plate is a glass plate with a laminated film according to any one of claims 1 to 3, and the interlayer film is disposed on the first main surface side of the first glass plate.

19. A laminated glass for a vehicle roof, comprising a first glass sheet, an interlayer film, and a second glass sheet in this order, wherein the first glass sheet is a glass sheet with a laminated film according to any one of claims 1 to 3, and the interlayer film is disposed on the first main surface side of the first glass sheet.

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