WO2022255200A1 - Substrat muni d'un film stratifié - Google Patents

Substrat muni d'un film stratifié Download PDF

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Publication number
WO2022255200A1
WO2022255200A1 PCT/JP2022/021449 JP2022021449W WO2022255200A1 WO 2022255200 A1 WO2022255200 A1 WO 2022255200A1 JP 2022021449 W JP2022021449 W JP 2022021449W WO 2022255200 A1 WO2022255200 A1 WO 2022255200A1
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Prior art keywords
laminated film
layer
film
substrate
antimony
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PCT/JP2022/021449
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English (en)
Japanese (ja)
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淳志 関
卓 立川
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Ａｇｃ株式会社
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Priority to CN202280038933.2A priority Critical patent/CN117396446A/zh
Priority to JP2023525762A priority patent/JPWO2022255200A1/ja
Publication of WO2022255200A1 publication Critical patent/WO2022255200A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions

Definitions

  • the present invention relates to a laminated film-coated base material, and more particularly to a laminated film-coated base material suitable for use in heat shielding and heat insulation of vehicles, buildings, and other structures.
  • Glass substrates with thin films and substrates with films, such as films with thin films, are widely used in various fields as materials that satisfy various required properties by laminating a functional film on the glass or film that is the main material.
  • Low-emissivity glass With heat insulation and heat shielding properties is used due to the recent heightened awareness of energy conservation.
  • Low-emissivity glass is constructed by laminating one or more functional layers made of metal oxide or the like on a glass substrate. It has a light absorption layer, an optical adjustment layer, and the like.
  • Patent Document 1 describes antimony-containing/tin oxide-based thin films containing at least antimony and fluorine-containing/fluorine-containing thin films as metal oxide-based thin films on the surface of a glass substrate.
  • Low emissivity glasses including tin oxide based thin films are described.
  • Patent Document 2 discloses (a) a glass substrate, (b) an antimony-doped tin oxide coating applied to the glass substrate, and (c) a fluorine-doped oxide applied to the antimony-doped tin oxide coating. Visible light transmission (reference illuminant C) and total It is stated to be selected to have a difference between the solar energy transmission (for an air mass of 1.5).
  • the present invention has been made to solve the above problems, and is a substrate with a laminated film having a plurality of functional layers on a main material, which has robustness against color tone and when enlarged
  • An object of the present invention is to provide a laminated film-attached base material capable of suppressing color spots.
  • the present inventors have worked diligently to solve the above problems with respect to a base material that has both heat shielding and heat insulating properties.
  • the present inventors have found that the above problems can be solved by adopting an antimony-doped tin oxide film and setting the concentration of antimony contained in the heat-absorbing layer and the thickness of the heat-absorbing layer within specific ranges, thereby completing the present invention.
  • the present invention consists of the following configurations.
  • a laminated film-attached base material comprising a main material and a laminated film disposed on the main material,
  • the main member has a first surface and a second surface facing each other, and the laminated film is provided on the first surface of the main member,
  • the laminated film has a heat ray absorbing layer and an infrared reflective layer from the side closer to the main material,
  • the heat ray absorbing layer is formed of an antimony-doped tin oxide film, the concentration of antimony contained in the heat ray absorbing layer is 3 to 14 mol%, and the thickness of the heat ray absorbing layer is 100 to 300 nm or 425 to 1000 nm.
  • a substrate with a laminated film comprising a main material and a laminated film disposed on the main material,
  • the main member has a first surface and a second surface facing each other, and the laminated film is provided on the first surface of the main member,
  • the laminated film has
  • the base material with a laminated film of the present invention includes a heat ray absorbing layer and an infrared reflective layer, it has heat shielding and heat insulating properties, and the heat ray absorbing layer contains antimony at a concentration of 3 to 14 mol% and has a thickness of is 100 to 300 nm or 425 to 1000 nm, it is possible to significantly suppress the reflection color tone unevenness in the visible light region in the surface of the substrate with the laminated film on the infrared reflective layer side, and to have excellent color tone robustness. As a result, even when the laminated film-coated base material has a large area of 0.5 m 2 or more, it is possible to suppress variations in reflection color within the surface, and thus color spots can be reduced.
  • FIG. 1 is a cross-sectional view of a substrate with a laminated film for explaining the configuration of one embodiment of the substrate with a laminated film of the present invention.
  • FIG. 2 is a cross-sectional view of a laminated film-attached substrate for explaining the configuration of another embodiment of the laminated film-attached substrate of the present invention.
  • FIG. 3 is a schematic diagram for explaining the mechanism of occurrence of color spots.
  • FIG. 4 is a flow diagram schematically showing an example of the method for producing a substrate with a laminated film of the present invention.
  • FIG. 5 is a diagram showing the results of the reflection spectrum comparison performed in Experimental Example 2.
  • FIG. 5(a) is Example 19
  • FIG. 5(b) is Example 20
  • FIG. , FIG. 5(d) is Example 22, and
  • FIG. 5(e) is Example 23.
  • FIG. 1 is a cross-sectional view for explaining the configuration of the laminated film-attached base material of the present invention.
  • the laminated film-attached substrate 10 of the present invention comprises a main member 1 and a laminated film 2 disposed on the main member 1 .
  • the main member 1 has a first surface 1a and a second surface 1b facing each other, and a laminated film 2 is provided on the first surface 1a of the main member 1 .
  • the laminated film 2 has a heat ray absorbing layer 3 and an infrared reflecting layer 5 in order from the side closer to the main material 1 .
  • the heat ray absorbing layer 3 is formed of an antimony-doped tin oxide film, the concentration of antimony contained in the heat ray absorbing layer 3 is 3 to 14 mol %, and the thickness of the heat ray absorbing layer 3 is 100 to 300 nm or 425 to 1000 nm. be.
  • the main material 1 serves as a skeleton of the base material 10 with a laminated film and has self-supporting properties.
  • Materials constituting the main material include, for example, glass and resin.
  • glass examples include soda lime silicate glass, aluminosilicate glass, borate glass, lithium aluminosilicate glass, quartz glass, borosilicate glass, alkali-free glass, and the like.
  • resins include polyolefin resins, polyester resins, polyamide resins, polystyrene resins, polyethylene terephthalate resins, polyvinyl chloride resins, and polycarbonate resins.
  • Polyolefin resins include, for example, polyethylene (low density, medium density, high density), polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer and the like.
  • glass can be suitably used as the main material for the base material with the laminated film of the present invention.
  • the main material can be selected from transparent, translucent, or opaque depending on the application and purpose of use of the base material with a laminated film. is preferred.
  • the main material may be colorless or colored.
  • the shape of the main material is not particularly limited, and may be plate-like, film-like, sheet-like, etc., and any shape is possible depending on the intended use.
  • it is preferably plate-shaped for use in vehicle members and construction members.
  • the size of the main material is not particularly limited, and may be appropriately adjusted according to the application and purpose of use of the base material with a laminated film.
  • a glass plate is used as the main material, the thickness of the glass plate is 1 mm to 5 mm, and the area of the main surface of the glass plate is 0.5 to 5 m 2 .
  • the base material with laminated film is used in a building, a glass plate is used as the main material, the thickness of the glass plate is 4 mm to 8 mm, and the area of the main surface of the glass plate is 0.5 to 10 m 2 . is preferred.
  • the heat absorbing layer 3 is composed of an antimony-doped tin oxide (ATO, a metal oxide obtained by adding Sb to SnO 2 ) film.
  • ATO antimony-doped tin oxide
  • Sb antimony
  • the heat absorbing layer may be composed of one layer of antimony-doped tin oxide film, or may be composed of two or more layers of antimony-doped tin oxide films having different antimony concentrations.
  • the concentration of antimony contained in the heat-absorbing layer is 3-14 mol %.
  • the concentration of antimony contained in the heat ray absorbing layer is 3 mol% or more, the heat shielding effect can be exhibited, and the base material with the laminated film can have color tone robustness. Since the refractive index difference of the reflective layer is small and the reflection at the interface does not increase, robustness can be ensured.
  • the concentration of antimony contained in the heat-absorbing layer is preferably 4 mol% or more, more preferably 5 mol% or more, still more preferably 6 mol%, preferably 13 mol% or less, more preferably 12 mol% or less, 11 mol % or less is more preferable.
  • the concentration of antimony contained in the heat absorption layer can be identified by X-ray photoelectron spectroscopy (XPS) or secondary ion mass spectroscopy (SIMS).
  • XPS X-ray photoelectron spectroscopy
  • SIMS secondary ion mass spectroscopy
  • analysis in the depth direction is performed by X-ray photoelectron spectroscopy (XPS), and the intensity ratio between Sb and Sn can be examined.
  • the thickness of the heat absorption layer is 100-300 nm or 425-1000 nm.
  • Tin oxide to which antimony has been added has a high absorption of visible light, and when the thickness of the heat ray absorbing layer is within the above range, interference of visible light in the heat ray absorbing layer can be suppressed, so color tone robustness can be obtained.
  • the thickness of the heat absorption layer is more than 300 nm and less than 425 nm, the effect of the present invention cannot be obtained when the antimony concentration is 3 to 14 mol %. It is assumed that this is because interference of visible light occurs within the heat ray absorbing layer.
  • the thickness of the heat-absorbing layer is preferably 120 nm or more, more preferably 150 nm or more, still more preferably 200 nm or more, further preferably 290 nm or less, and 280 nm or less when the thickness is in the range of 100 to 300 nm. more preferred.
  • the thickness in the range of 425 to 1000 nm is preferably 450 nm or more, more preferably 470 nm or more, and preferably 900 nm or less, more preferably 800 nm or less.
  • the thickness of the heat-absorbing layer can be measured by analysis in the depth direction using X-ray photoelectron spectroscopy (XPS). Since the heat absorbing layer is formed of crystal grains of antimony and tin oxide, the surface opposite to the main material side has an uneven shape. Therefore, although the "thickness" of the heat ray absorbing layer varies depending on the location, in the present invention, it represents the maximum thickness of the heat ray absorbing layer in the measurement area.
  • XPS X-ray photoelectron spectroscopy
  • the infrared reflective layer 5 is a layer that reflects infrared rays and imparts heat insulation to the base material with the laminated film, and is laminated on the heat ray absorbing layer 3 .
  • the material constituting the infrared reflective layer is not particularly limited as long as it has a function of reflecting infrared rays.
  • Materials constituting the infrared reflective layer include, for example, at least one metal oxide selected from the group consisting of tin oxide, indium oxide, zinc oxide, titanium oxide, tantalum oxide, and niobium oxide, and other elements (impurity elements). doped metal oxides. Impurity elements to be doped include, for example, fluorine, antimony, tin, potassium, aluminum, tantalum, niobium, nitrogen, boron, and indium.
  • Specific doped metal oxides include, for example, fluorine-doped tin oxide (FTO, a metal oxide in which F is added to SnO2 ), antimony-doped tin oxide (ATO, a metal oxide in which Sb is added to SnO2 ).
  • FTO fluorine-doped tin oxide
  • ATO antimony-doped tin oxide
  • ITO metal oxide in which Sn is added to In 2 O 3
  • gallium-doped zinc oxide GZO, metal oxide in which Ga is added to ZnO
  • aluminum-doped zinc oxide AZO, ZnO to which Al is added doped metal oxide
  • tantalum-doped tin oxide metal oxide with Ta added to SnO2
  • niobium-doped tin oxide metal oxide with Nb added to SnO2
  • tantalum-doped titanium oxide Ti with Ta added niobium-doped titanium oxide (metal oxide in which Nb is added to Ti
  • aluminum-doped tin oxide metal oxide in which Al is added to SnO2
  • fluorine-doped titanium oxide metal oxide in which F is added to Ti
  • nitrogen-doped titanium oxide a metal oxide in which N is added to Ti
  • At least selected from the group consisting of fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), tin-doped indium oxide (ITO), gallium-doped zinc oxide (GZO) and aluminum-doped zinc oxide (AZO) It preferably comprises a single metal oxide film. Among them, it is preferable to include a fluorine-doped tin oxide (FTO) film from the viewpoint of obtaining higher heat insulation.
  • the infrared reflective layer may consist of a single layer film, or may consist of two or more layers of films with different materials, element contents, and the like.
  • the content of impurity elements contained in the infrared reflective layer is preferably 0.01 to 20 mol % in concentration.
  • concentration of the impurity element contained in the infrared reflective layer is 0.01 mol % or more, more preferably 0.1 mol % or more, still more preferably 0.5 mol % or more, and more preferably 10 mol % or less. It is preferably 8 mol % or less, more preferably 5 mol % or less.
  • the concentration of the impurity element is the total amount when the infrared reflective layer contains a plurality of impurity elements.
  • the composition of the infrared reflective layer and the concentration of impurity elements can be identified by X-ray photoelectron spectroscopy (XPS) or secondary ion mass spectroscopy (SIMS).
  • XPS X-ray photoelectron spectroscopy
  • SIMS secondary ion mass spectrometry
  • the infrared reflective layer contains a fluorine-doped tin oxide film, and the concentration of fluorine contained in the infrared reflective layer is 0.01. ⁇ 10 mol% is particularly preferred.
  • the thickness of the infrared reflective layer is preferably 50-400 nm.
  • the thickness of the infrared reflective layer is more preferably 75 nm or more, still more preferably 100 nm or more, particularly preferably 110 nm or more, more preferably 380 nm or less, even more preferably 350 nm or less, and particularly 325 nm or less. preferable.
  • the thickness of the infrared reflective layer can be measured by analysis in the depth direction by X-ray photoelectron spectroscopy (XPS) measurement, or the like.
  • XPS X-ray photoelectron spectroscopy
  • the "thickness" of the infrared reflective layer is represented by the total thickness of each layer.
  • the infrared reflective layer is formed of metal oxide crystal grains, and the surface of the heat ray absorbing layer laminated as described above has an uneven shape. The surface opposite to the heat-absorbing layer) has an uneven shape. Therefore, although the "thickness" of the infrared reflective layer varies depending on the location, in the present invention it represents the maximum thickness of the infrared reflective layer in the measurement area.
  • the arithmetic mean roughness Ra of the surface of the infrared reflective layer is preferably in the range of 3 nm to 50 nm, more preferably in the range of 5 nm to 30 nm.
  • the laminated film 2 may further have an optical adjustment layer 7 as shown in FIG.
  • the optical adjustment layer 7 is arranged between the main material 1 and the heat absorption layer 3 .
  • optical adjustment layer Materials constituting the optical adjustment layer include, for example, silicon carbide oxide (SiOC), silicon oxide (SiO 2 ), titanium oxide (TiO 2 ), tin oxide (SnO 2 ), silicon nitride oxide (SiON), and the like. .
  • the optical adjustment layer may consist of one layer, or may consist of two or more layers. It may also be a mixture of any two or more of the above materials.
  • the optical adjustment layer includes a SiOC film, a SiOC/ SiO2 laminated film in which the SiOC film and the SiO2 film are laminated in this order from the main material side, and a TiO2 film and a SiO2 film in this order from the main material side. and a SnO 2 /SiO 2 laminated film in which the SnO 2 film and the SiO 2 film are laminated in this order from the main material side.
  • the optical adjustment layer preferably contains silicon, and is a group consisting of a SiOC film, a SiOC/SiO 2 laminated film, a TiO 2 /SiO 2 laminated film, and a SnO 2 /SiO 2 laminated film. and more preferably comprising a SiOC film.
  • the amount of silicon contained in the entire optical adjustment layer is preferably in the range of 5 to 40 mol%, more preferably 10 to 33 mol%.
  • the thickness of the optical adjustment layer is preferably 20-100 nm. When the thickness of the optical adjustment layer is 20 nm or more, the surface of the main material can be uniformly coated. A desired effect can be exhibited as an adjustment layer.
  • the thickness of the optical adjustment layer is preferably 20 nm or more, more preferably 25 nm or more, still more preferably 30 nm or more, and preferably 100 nm or less, more preferably 90 nm or less, and even more preferably 80 nm or less.
  • the "thickness" of the optical adjustment layer is represented by the total thickness of each layer.
  • the laminated film-coated base material of the present invention may have other layers as long as the effects of the present invention are not impaired.
  • Other layers include an overcoat layer and the like.
  • the laminated film-coated substrate of the present invention preferably has an in-plane reflection color variation ⁇ C (ie, reflection color variation) measured at an incident angle of 30 degrees using a D65 light source within 2.25. It is considered that the main cause of color spots in the base material with the laminated film is the film thickness distribution of the infrared reflective layer.
  • FIG. 3 shows the mechanism of color spots in a laminated structure of an infrared reflective layer (eg, FTO film) and a heat ray absorbing layer (eg, ATO film).
  • an infrared reflective layer eg, FTO film
  • a heat ray absorbing layer eg, ATO film
  • reflected light paths There are three reflected light paths: a reflected light path B and a reflected light path C that passes through the infrared reflecting layer 5 and the heat absorbing layer 3 and is reflected at the interface with the optical adjustment layer 7 . These reflected lights interfere with each other to determine the reflected color.
  • a reflected light path B and a reflected light path C that passes through the infrared reflecting layer 5 and the heat absorbing layer 3 and is reflected at the interface with the optical adjustment layer 7 .
  • These reflected lights interfere with each other to determine the reflected color.
  • the thickness of the infrared reflective layer 5 fluctuates in the plane of the base material 20 with a laminated film
  • color spots occur because the interference wavelength between the reflected light path A and the reflected light path B changes, and the thickness of the heat ray absorbing layer 3 fluctuates.
  • the interference wavelengths of the reflected light path B and the reflected light path C change, so color spots occur.
  • antimony-doped tin oxide film ATO film
  • antimony easily absorbs visible light.
  • the intensity is weak, the effect of interference between the reflected light path B and the reflected light path C is weak, and the effect on color spots is small.
  • the variation ⁇ C of the reflected color by the measurement is within 2.25, even when the substrate with the laminated film has a large area of 0.5 m 2 or more, the variation of the reflected color in the plane can be suppressed, and the color spotting. It can suppress the occurrence.
  • the variation ⁇ C of the reflected color by the measurement is more preferably within 2.1, still more preferably within 2.0, and particularly preferably within 1.8.
  • the lower limit is not particularly limited, but it is preferably 0.1 or more, more preferably 0.2 or more, and even more preferably 0.3 or more.
  • ⁇ C can be obtained by measuring the distribution of reflected colors (a * , b * ) viewed from the infrared reflective layer side of the base material with the laminated film.
  • the light source is a D65 light source, both the incident angle and the reflection angle are set to 30 degrees with respect to the base material with the laminated film, and the light is irradiated from the main material side of the base material with the laminated film.
  • the spot size of the light source is adjusted to about 1 to 4 cm 2 on the surface of the main material, and the reflection spectrum is measured at intervals of 3 cm in the plane of the main material.
  • the reflected color (a * , b * ) at each measurement point is calculated from the obtained spectrum.
  • the Euclidean distance ⁇ C 12 ((a 1 * -a 2 * ) 2 +(b 1 * -b 2 * ) 2 ) 0.5 on the color coordinates is the maximum ( A combination of a 1 * , b 1 * ) and (a 2 * , b 2 * ) is selected, and its ⁇ C 12 is defined as the reflection color variation ⁇ C of the base material with the laminated film.
  • the base material with the laminated film has a reflectance of 20% or less on the infrared reflective layer side surface.
  • the reflectance is more preferably 18% or less, even more preferably 16% or less, and particularly preferably 14% or less.
  • the lower limit of reflectance is not specified, it is more preferably 0.5% or more, still more preferably 1.0% or more, and particularly preferably 1.5% or more.
  • the reflectance of the laminated film-coated substrate can be measured by the method described in ISO9050:2003.
  • the laminated film-attached substrate preferably has a visible light transmittance of 70% or less.
  • the transmittance is more preferably 60% or less, more preferably 55% or less, particularly preferably 45% or less, even more preferably 35% or less, and most preferably 30% or less.
  • the lower limit of the transmittance is not specified, it is more preferably 0.5% or more, still more preferably 1% or more, and particularly preferably 1.5% or more.
  • the transmittance of the base material with laminated film can be measured by the method described in ISO9050:2003.
  • FIG. 4 schematically shows an example of the flow of the method for manufacturing the substrate 10 with a laminated film.
  • the method for producing a laminated film-attached base material of the present invention comprises: (a) placing a heat-absorbing layer on the first surface of the main material (step S1); (b) placing an infrared reflective layer on the heat absorbing layer (step S2); have
  • Step S1 the main material is prepared.
  • the type of main material is not particularly limited.
  • soda lime silicate-based high-transmittance glass may be used.
  • step S1 a heat ray absorbing layer is arranged on the first surface of the main material.
  • the heat ray absorbing layer can be formed using various film forming methods such as chemical vapor deposition (CVD), electron beam deposition, vacuum deposition, sputtering, and spraying.
  • CVD chemical vapor deposition
  • electron beam deposition electron beam deposition
  • vacuum deposition vacuum deposition
  • sputtering sputtering
  • spraying a thermal CVD method is preferable because a high-temperature process is required to increase the crystal grain size.
  • a large-scale vacuum apparatus becomes unnecessary, and the productivity can be further improved.
  • the heat ray absorbing layer is formed by thermal CVD, a mixture of an inorganic or organic tin compound and an antimony compound is used as the raw material.
  • Tin compounds include monobutyltin trichloride ( C4H9SnCl3 ) and tin tetrachloride ( SnCl4 ).
  • tin compound an organic tin compound is particularly preferable.
  • an inorganic tin compound is used as the tin compound, the growth rate of crystal grains is high, and the surface tends to become uneven.
  • Antimony compounds include antimony trichloride (SbCl 3 ) and antimony pentachloride (SbCl 5 ).
  • Antimony trichloride is particularly preferred as the antimony compound.
  • antimony trichloride reacts violently with water in the source gas to produce particle clusters of antimony trioxide (Sb 2 O 3 ) and antimony pentoxide (Sb 2 O 5 ) in the gas phase. Therefore, by including those particle clusters in the film, the degree of unevenness of the surface can be controlled.
  • the ratio of the antimony compound and the tin compound is adjusted, the film formation temperature, etc. are adjusted.
  • the raw material gases may be mixed in advance and then transported.
  • the raw material gases may be mixed on the surface of the main material to be deposited.
  • the raw material may be vaporized into a gas by using a bubbling method, a vaporizer, or the like.
  • the amount of water to 1 mol of the tin compound in the source gas is preferably 5 to 50 mol. If the amount of water is less than 5 mol, the resistance value of the film to be formed tends to increase, resulting in a decrease in the heat ray absorbing function. In addition, the number of starting points for nucleation is reduced, and as a result, crystal grains tend to grow larger, and the surface tends to become rougher. On the other hand, if the amount of water exceeds 50 moles, the volume of the raw material gas increases as the amount of water increases, and the flow rate of the raw material gas increases, which may reduce the film deposition efficiency. In addition, the number of starting points for nucleation increases, and as a result, crystal grains tend to grow smaller and the surface tends to become flat.
  • the amount of oxygen per 1 mol of the tin compound in the source gas is preferably more than 0 mol and 40 mol or less, more preferably 4 to 40 mol. If the amount of oxygen is too small, the resulting film may have an increased resistance value, so it is more preferably 4 mol or more. On the other hand, if the amount of oxygen exceeds 40 mol, the volume of the raw material gas increases and the flow rate of the raw material gas increases, which may reduce the film deposition efficiency.
  • the molar ratio of the antimony compound to the tin compound in the range of 1:100 to 3:1.
  • the temperature of the main material when forming the heat-absorbing layer is preferably 500°C to 650°C. If the temperature of the glass is less than 500°C, the formation speed of the heat-absorbing layer may decrease. In addition, the precursor generated by the decomposition of the raw material gas diffuses faster on the surface of the glass and the heat-absorbing layer than reacts on the surface of the glass and the heat-absorbing layer. As a result, more of the precursor flows into the irregularities on the surface of the glass and the heat-absorbing layer, which tends to flatten the surface. On the other hand, if the temperature of the glass exceeds 650° C., film formation is performed in a state in which the viscosity of the glass is low.
  • reaction rate of the precursor on the surface of the glass and the heat-absorbing layer is higher than the diffusion rate of the precursor on the surface of the glass and the heat-absorbing layer.
  • the precursor tends to flow less into the irregularities on the surface of the glass and the heat-absorbing layer, and the irregularities on the surface tend to increase.
  • the temperature of the main material when forming the heat-absorbing layer is preferably 30 to 400°C.
  • the thickness of the heat absorption layer is 100-300 nm or 425-1000 nm.
  • the film thickness of the heat ray absorbing layer can be adjusted by adjusting the supply amount of the raw material, the substrate transport speed, the film forming temperature, the spraying flow rate, the distance between the film forming apparatus and the substrate, and the like.
  • Step S2 an infrared reflective layer is formed on the heat absorbing layer.
  • the infrared reflective layer can be formed using various film-forming methods such as chemical vapor deposition (CVD), electron beam deposition, vacuum deposition, sputtering, and spraying. .
  • CVD chemical vapor deposition
  • the thermal CVD method is preferable because a high-temperature process is necessary to increase the infrared reflectivity by increasing the crystal grain size and increasing the electron mobility.
  • a large-scale vacuum apparatus becomes unnecessary, and the productivity can be further improved.
  • the infrared reflective layer is, for example, fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), tin-doped indium oxide (ITO), gallium-doped zinc oxide (GZO), aluminum-doped zinc oxide (AZO), as described above. etc., can be configured using various thin film materials.
  • FTO fluorine-doped tin oxide
  • ATO antimony-doped tin oxide
  • ITO tin-doped indium oxide
  • GZO gallium-doped zinc oxide
  • AZO aluminum-doped zinc oxide
  • the infrared reflective layer is composed of, for example, fluorine-doped tin oxide (FTO) or antimony-doped tin oxide (ATO), the unevenness of the surface of the infrared reflective layer can be increased, and the color tone can be adjusted within a predetermined range.
  • FTO fluorine-doped tin oxide
  • ATO antimony-doped tin oxide
  • the infrared reflective layer is composed of, for example, aluminum-doped zinc oxide (AZO) or gallium-doped zinc oxide (GZO), the crystal orientation tends to be uniform and the surface tends to be flat.
  • AZO aluminum-doped zinc oxide
  • GZO gallium-doped zinc oxide
  • tin-doped indium oxide has a strong function of reflecting infrared rays, and is often used in a film thickness range of around 100 nm. Therefore, when the infrared reflective layer is made of tin-doped indium oxide (ITO), it may be difficult to adjust the color tone of the reflected color within a predetermined range, resulting in insufficient crystal grain growth and surface roughness. It tends to be flat.
  • the infrared reflective layer is composed of a fluorine-doped tin oxide layer (FTO)
  • the infrared reflective layer may be deposited by atmospheric pressure CVD.
  • a mixture of an inorganic or organic tin compound and a fluorine compound is used as the raw material.
  • Tin compounds include monobutyltin trichloride (C 4 H 9 SnCl 3 ) and tin tetrachloride (SnCl 4 ), as described above.
  • tin compound an organic tin compound is particularly preferable.
  • an inorganic tin compound is used as the tin compound, the growth rate of crystal grains is high, and the surface tends to be rough.
  • Fluorine compounds include hydrogen fluoride and trifluoroacetic acid.
  • the infrared reflective layer is composed of an antimony-doped tin oxide layer (ATO)
  • the infrared reflective layer may be deposited by atmospheric pressure CVD.
  • a mixture of an inorganic or organic tin compound and an antimony compound is used as the raw material.
  • an organic tin compound is particularly preferable.
  • an inorganic tin compound is used as the tin compound, the growth rate of crystal grains is high, and the surface tends to be rough.
  • Antimony compounds include antimony trichloride (SbCl 3 ) and antimony pentachloride (SbCl 5 ).
  • Antimony trichloride is particularly preferred as the antimony compound.
  • antimony trichloride reacts violently with water in the source gas to produce particle clusters of antimony trioxide (Sb 2 O 3 ) and antimony pentoxide (Sb 2 O 5 ) in the gas phase. Therefore, by including those particle clusters in the film, the degree of unevenness of the surface can be controlled.
  • the concentration of antimony in the infrared reflective layer is preferably in the range of more than 0 mol % and 3 mol % or less in order to obtain a heat insulating effect.
  • the infrared reflective layer is composed of gallium-doped zinc oxide (GZO), trimethylgallium (Ga(CH 3 ) 3 ) and trimethylaluminum (Al(CH 3 ) 3 ) are used as raw materials.
  • the infrared reflective layer is composed of aluminum-doped zinc oxide (AZO), trimethylaluminum and diethylzinc Zn( C2H5 ) 2 are used as raw materials.
  • the infrared reflective layer is composed of tin-doped indium oxide (ITO), indium acetylacetonate (In(C 5 H 7 O 2 ) 3 ), tin acetylacetonate (Sn(C 5 H 7 O 2 ) 2 ) is used.
  • ITO tin-doped indium oxide
  • In(C 5 H 7 O 2 ) 3 indium acetylacetonate
  • Sn(C 5 H 7 O 2 ) 2 tin acetylacetonate
  • the raw material gases may be mixed in advance and then transported.
  • the raw material gases may be mixed on the surface of the film-forming object (specifically, the heat-absorbing layer).
  • the raw material may be vaporized into a gas by using a bubbling method, a vaporizer, or the like.
  • the amount of water to 1 mol of the tin compound or zinc compound in the source gas is preferably 5 to 50 mol. If the amount of water is less than 5 mol, the resistance value of the film to be formed tends to increase, resulting in a decrease in the infrared reflecting function. In addition, the number of starting points for nucleation is reduced, and as a result, crystal grains tend to grow larger, and the surface tends to become rougher. On the other hand, if the amount of water exceeds 50 moles, the volume of the raw material gas increases as the amount of water increases, and the flow rate of the raw material gas increases, which may reduce the film deposition efficiency. In addition, the number of starting points for nucleation increases, and as a result, crystal grains tend to grow smaller and the surface tends to become flat.
  • the amount of oxygen per 1 mol of the tin compound or zinc compound in the source gas is preferably more than 0 mol and 40 mol or less, more preferably 4 to 40 mol. If the amount of oxygen is less than 4 moles, the resistance of the resulting film may increase. On the other hand, if the amount of oxygen exceeds 40 mol, the volume of the raw material gas increases and the flow rate of the raw material gas increases, which may reduce the film deposition efficiency.
  • the amount of the fluorine compound relative to 1 mol of the tin compound in the source gas is preferably 0.1 to 1.2 mol.
  • the resistance value of the formed film tends to increase.
  • the temperature for forming the infrared reflective layer is preferably 500° C. to 650° C. when a glass plate is used as the main material. If the treatment temperature is lower than 500°C, the formation speed of the infrared reflective layer may decrease. In addition, the precursor generated by the decomposition of the raw material gas diffuses faster on the surface of the glass and the infrared reflective layer than it reacts on the surface of the glass and the infrared reflective layer. As a result, more of the precursor flows into the surface irregularities of the glass and the infrared reflective layer, tending to flatten the surface.
  • the processing temperature is higher than 650° C.
  • film formation is performed while the viscosity of the glass is low, and warping may occur in the process of cooling the glass to room temperature.
  • the reaction speed of the precursor on the surface of the glass and the infrared reflective layer is higher than the speed of diffusion on the surface of the glass and the infrared reflective layer. As a result, the precursor tends to flow less into the irregularities on the surface of the glass and the infrared reflective layer, and the irregularities on the surface tend to increase.
  • the processing temperature for forming the infrared reflective layer is preferably 30 to 400°C.
  • steps S1 and S2 may be performed by an online method during the process of producing glass using a float facility.
  • film formation may be performed by reheating the glass plate manufactured by the float method by an off-line method.
  • the optical adjustment layer when an optical adjustment layer is provided between the main material and the heat absorbing layer, the optical adjustment layer is arranged on the first surface of the main material before step S1.
  • the optical adjustment layer is formed using various film formation methods such as chemical vapor deposition (CVD), electron beam evaporation, vacuum deposition, sputtering, and spraying. can be formed.
  • CVD chemical vapor deposition
  • electron beam evaporation electron beam evaporation
  • vacuum deposition vacuum deposition
  • sputtering sputtering
  • spraying spraying
  • the optical adjustment layer can be configured using various thin film materials such as SiOC, SiO2 , TiO2 , SnO2 , etc., as described above. Also, the optical adjustment layer may consist of one layer, or may be a laminate of two or more layers.
  • the optical adjustment layer when the optical adjustment layer includes a silicon carbide oxide (SiOC) layer, the optical adjustment layer may be deposited by atmospheric pressure CVD.
  • a mixed gas containing monosilane (SiH 4 ), ethylene and carbon dioxide can be used as the raw material.
  • SiH 4 monosilane
  • ethylene and carbon dioxide when such a carbon-containing gas is used, it becomes easy to form a particulate silicon compound together with a film-like silicon compound, thereby increasing the haze ratio.
  • the raw material gases may be mixed in advance and then conveyed onto the first surface of the main member. Alternatively, the raw material gases may be mixed on the first surface of the main material.
  • the optical adjustment layer includes a silicon oxide (SiO 2 ) layer
  • mixed gases such as monosilane (SiH 4 ), tetraethoxysilane, and oxygen can be used as raw materials.
  • examples of raw materials include tetraisopropyl orthotitanate (TTIP) and titanium tetrachloride. Among them, tetraisopropyl orthotitanate (TTIP) is more preferable.
  • the temperature of the main material when forming the optical adjustment layer is preferably 500°C to 900°C. If the temperature of the main material is less than 500°C or more than 900°C, the film formation rate tends to decrease.
  • the overcoat layer is arranged on the surface of the infrared reflective layer after step S2.
  • the overcoat layer is formed, for example, by a wet method.
  • a coating solution for the overcoat layer is prepared.
  • the coating solution contains a metal oxide precursor, an organic solvent, and water. Particles and/or solids may also be added to the coating solution.
  • the composition of the particles may be the same as or different from the metal oxide precursor.
  • a coating solution is applied onto the infrared reflective layer of the laminated film-coated substrate.
  • the coating method is not particularly limited, and a common means such as spin coating may be used.
  • the laminated film-coated substrate on which the coating solution is applied is heat-treated in the air.
  • the temperature of the heat treatment is, for example, in the range of 80.degree. C. to 650.degree.
  • the heating time is, for example, in the range of 5 minutes to 360 minutes.
  • the heat treatment may be performed using a common device such as a hot air circulation furnace or an IR heater furnace.
  • An overcoat layer may also be formed from the coating solution by UV curing treatment, microwave treatment, or the like.
  • an overcoat layer can be formed on the infrared reflective layer.
  • the above heat treatment does not necessarily have to be performed at this stage. That is, the coating solution may be heated using a heating step that is performed in separate stages.
  • the substrate with a laminated film of the present invention can be produced.
  • the method for producing a base material with a laminated film of the present invention may further include a step (strengthening step) of air-cooling strengthening or chemical strengthening of the main material.
  • This strengthening step may be performed in any order, for example, before step S1 or after manufacturing the base material with the laminated film.
  • the obtained base material with the laminated film may be subjected to bending.
  • a step of bonding another glass plate on the glass plate side surface may be carried out.
  • the substrate with a laminated film of the present invention has color tone robustness, even when the substrate has a large area of 0.5 m 2 or more, the in-plane reflection color variation is suppressed and color spots are reduced. can. Therefore, it can be used for applications that use a base material that is relatively large.
  • the laminated film-coated substrate of the present invention can be used, for example, for vehicle window glass (front glass, rear glass, side glass, roof glass, etc.), building window glass, and the like.
  • vehicle window glass front glass, rear glass, side glass, roof glass, etc.
  • building window glass and the like.
  • a base material with a laminated film comprising a main material and a laminated film disposed on the main material, the main material having a first surface and a second surface facing each other,
  • the laminated film is provided on the first surface of the main material, the laminated film has a heat absorption layer and an infrared reflective layer in this order from the side close to the main material, and the heat absorption layer is antimony-doped tin oxide.
  • a base material with a laminated film formed of a film wherein the concentration of antimony contained in the heat ray absorption layer is 3 to 14 mol %, and the thickness of the heat ray absorption layer is 100 to 300 nm or 425 to 1000 nm.
  • the infrared reflective layer comprises at least one metal oxide film selected from the group consisting of fluorine-doped tin oxide, antimony-doped tin oxide, tin-doped indium oxide, gallium-doped zinc oxide, and aluminum-doped zinc oxide.
  • ⁇ 5> The substrate with a laminated film according to any one of ⁇ 1> to ⁇ 4>, wherein the main material is glass.
  • the laminated film further includes an optical adjustment layer, and the optical adjustment layer is disposed between the main material and the heat ray absorbing layer.
  • the optical adjustment layer has at least one film selected from the group consisting of a SiOC film, a SiOC/SiO 2 laminated film, a TiO 2 /SiO 2 laminated film, and a SnO 2 /SiO 2 laminated film. 6>, the laminated film-attached substrate.
  • Example 1 When a thin film is formed on a glass plate using the CVD method, the film thickness varies within the surface, resulting in color spots.
  • the infrared reflective layer is composed of a fluorine-doped tin oxide film (SnO 2 :F, FTO), and the heat ray absorbing layer is composed of an antimony-doped tin oxide film (SnO 2 :Sb, ATO).
  • SnO 2 :F, FTO fluorine-doped tin oxide film
  • SnO 2 :Sb, ATO antimony-doped tin oxide film
  • the reflection spectrum was calculated using Fresnel's formula from the experimentally derived optical constants (refractive index and extinction coefficient) of the ATO film and the FTO film.
  • the a * value was calculated from the obtained reflectance spectrum based on the definition of JIS (JIS Z 8781-4:2013).
  • the optical constants of the ATO film and the FTO film were measured by forming the ATO film and the FTO film on a glass substrate and measuring them with a spectroscopic ellipsometer J.M.
  • Spectroscopic ellipsometry was measured using Woollam's "M-2000 DI" (apparatus name), and analysis software J.M. A. Derived using WVASE 32 manufactured by Woollam.
  • the size of color mottling was defined as the size of change in film surface reflection color (reflection color change ⁇ C) on Lab coordinates when the film thickness of the FTO film fluctuated by 5 nm.
  • the heat ray absorbing layer contains antimony, the reflected light path B passing through the infrared reflecting layer 5 and reflected at the interface with the heat ray absorbing layer 3, the infrared reflecting layer 5, and the heat absorbing layer 3 shown in FIG.
  • the interference with the reflected light path C that passes through and is reflected at the interface with the optical adjustment layer 7 is weak, and the effect on color spots is small.
  • the optical simulation was performed using a D65 light source as the light source, with both the incident angle and the reflection angle of 30 degrees.
  • Examples 1-18 The method for producing the laminated film-attached substrates of Examples 1 to 18 having the configurations shown in Table 1 is as follows. First, a glass substrate (soda lime silicate glass: manufactured by AGC Co., Ltd.) having a thickness of 2.1 mm and an area of 1 m 2 was prepared. form a film. Monosilane, ethylene, and carbon dioxide are used as raw material gases, and nitrogen is used as a carrier gas. Next, an antimony-doped tin oxide film (SnO 2 :Sb, ATO) is formed as a heat absorption layer on the SiOC layer by CVD.
  • SnO 2 :Sb, ATO antimony-doped tin oxide film
  • Monobutyltin trichloride (C 4 H 9 SnCl 3 , MBTC), antimony trichloride (SbCl 3 ), water, air, and hydrogen chloride are used as source gases, and nitrogen is used as carrier gas.
  • the thickness (maximum thickness) of the heat ray absorbing layer is a predetermined thickness of 200 to 700 nm.
  • a fluorine-doped tin oxide film (SnO 2 :F, FTO) is formed as an infrared reflective layer on the heat absorbing layer by CVD.
  • Monobutyltin trichloride (C 4 H 9 SnCl 3 , MBTC), water, air, trifluoroacetic acid (FTO), and nitric acid are used as source gases, and nitrogen is used as carrier gas.
  • the thickness (maximum thickness) of the infrared reflective layer is a predetermined thickness of 120 to 300 nm. Thereby, a base material with a laminated film is obtained.
  • each layer of the laminated film-coated base material is a value measured by the following measurement methods.
  • ⁇ Measurement of thickness of each layer> The film-coated substrate is cut in the thickness direction, and the cross section is observed with a scanning electron microscope (SEM, "SU 70" manufactured by Hitachi, Ltd.).
  • SEM scanning electron microscope
  • the film thickness of each layer is checked directly from the SEM image.
  • the film thickness of each layer is derived using the middle line between the horizontal lines of the lowest valley and the highest peak as a guideline. If the observation magnification is too low, the accuracy of film thickness measurement will be insufficient. exists.
  • an electron gun of 1.5 kV, a working distance of 2.4 mm, and a magnification of 50,000 are adopted. If the interface between the heat absorption layer and the infrared reflection layer cannot be confirmed by SEM observation, after examining the sum of the thickness of the heat absorption layer and the infrared reflection layer from the SEM image, the depth direction by X-ray photoelectron spectroscopy (XPS) was used to examine the thickness ratio of the heat-absorbing layer and the infrared-reflecting layer. The depth direction analysis is performed by XPS measurement while etching the film using Ar sputtering in an XPS chamber with a degree of vacuum of 10 ⁇ 6 Pa.
  • XPS X-ray photoelectron spectroscopy
  • the X-ray irradiation area was 100 ⁇ m ⁇ , and the X-ray irradiation angle was 45 deg. fixed to Since the heat-absorbing layer in this example is an ATO (antimony-doped tin oxide) film, the point (time) at which the Sb molar ratio obtained by XPS depth profile analysis begins to increase with respect to the etching time and the point at which the increase ends The middle point (time) at which the slope becomes approximately zero is set as the interface between the heat ray absorbing layer and the infrared reflective layer.
  • ATO antimony-doped tin oxide
  • the optical adjustment layer in this example is a SiOC film
  • the cross point at which the molar ratio of Sn and Si exhibits the same value is set as the interface between the heat ray absorption layer and the optical adjustment layer. According to this method, it is possible to derive the film thickness of each layer with high reproducibility while referring to the etching rates of the heat ray absorbing layer and the infrared reflecting layer, which have been measured in advance for single-layer film products.
  • the composition is calculated from the X-ray peak intensity using software PHI MULTIPAC manufactured by ULVAC.
  • the electronic information of the O1s, Si2p, Sn3d5, and Sb3d3 orbitals was referred to. is calibrated by subtracting 1.5 times from the peak intensity of O1s.
  • "PHI 5000 Versa Probe" manufactured by ULVAC-PHI was used.
  • the antimony concentration is analyzed in the depth direction by X-ray photoelectron spectrometry (XPS) and examined from the intensity ratio of Sb and Sn.
  • XPS X-ray photoelectron spectrometry
  • PHI 5000 Versa Probe manufactured by ULVAC-PHI is used.
  • the antimony concentration may be distributed in the film thickness direction of the heat ray absorbing layer. In that case, the average value in the depth direction is used as the antimony concentration.
  • ⁇ Measurement of reflected color variation ( ⁇ C)> In order to calculate the size of color spots, the distribution of reflected colors (a * , b * ) viewed from the glass substrate side of the laminated film-coated substrate is measured. A D65 light source was used as the light source, and both the incident angle and the reflection angle were set at 30 degrees with respect to the laminated film-coated substrate, and the light was irradiated from the glass surface side of the laminated film-coated substrate. The spot size of the light source was adjusted to about 1 cm 2 on the glass surface, and the reflection spectrum was measured at intervals of 3 cm in the plane of the glass substrate. The reflected color (a * , b * ) at each measurement point is calculated from the obtained spectrum.
  • the Euclidean distance ⁇ C 12 ((a 1 * -a 2 * ) 2 +(b 1 * -b 2 * ) 2 ) 0.5 on the color coordinates is the maximum ( A combination of a 1 * , b 1 * ) and (a 2 * , b 2 * ) is selected, and its ⁇ C 12 is defined as the reflection color variation ⁇ C of the base material with the laminated film.
  • the chromaticity of the film-coated substrate is measured using a spectrophotometer (“CM-2500d” manufactured by Konica Minolta, Inc.).
  • the reflectance of the substrate with the laminated film on the side of the infrared reflective layer is measured by the method described in ISO9050:2003.
  • the transmittance of the laminated film-attached substrate is measured by the method described in ISO9050:2003.
  • Table 1 shows the results of the optical simulation.
  • Examples 19-23 Base materials with laminated films of Examples 19 to 23 having the configurations shown in Table 2 were produced.
  • a glass substrate sida lime silicate glass: manufactured by AGC Co., Ltd.
  • a SiOC layer was formed as an optical adjustment layer on the glass substrate by a CVD method.
  • Monosilane, ethylene, and carbon dioxide were used as raw material gases, and nitrogen was used as a carrier gas.
  • the target thickness of the SiOC layer was set to 70 nm.
  • an antimony-doped tin oxide film SnO 2 :Sb, ATO
  • Monobutyltin trichloride C 4 H 9 SnCl 3 , MBTC
  • antimony trichloride SbCl 3
  • water, air, and hydrogen chloride were used as source gases, and nitrogen was used as carrier gas.
  • the target thickness (maximum thickness) of the heat ray absorbing layer was 350 to 630 nm.
  • a fluorine-doped tin oxide film SnO 2 :F, FTO was formed as an infrared reflective layer on the heat ray absorbing layer by the CVD method.
  • Monobutyltin trichloride C 4 H 9 SnCl 3 , MBTC
  • water, air, trifluoroacetic acid (FTO), and nitric acid were used as source gases, and nitrogen was used as carrier gas.
  • the target thickness (maximum thickness) of the infrared reflective layer was 175 to 300 nm. Thus, a laminated film-attached base material was obtained.
  • the concentration of antimony and the film thickness were measured by the measurement method described in Experimental Example 1, and the reflection spectra of the optical simulation and the actually measured reflection spectra were compared.
  • Reflectance spectra for optical simulation were obtained by the method described in Experimental Example 1.
  • the actually measured reflection spectrum was measured using Lambda950 manufactured by PerkinElmer.
  • the reflection spectrum of the optical simulation and the measured reflection spectrum are similar, and the peak wavelength is also similar, so the reflectance of the substrates with laminated films of Examples 1 to 18 evaluated in Experimental Example 1, It can be judged that the measured values of the transmittance and the reflected color variation ⁇ C are equivalent to the simulation results.

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Abstract

La présente invention concerne un substrat muni d'un film stratifié, ledit substrat étant robuste en termes de tonalité de couleur et pouvant supprimer les taches de couleur lorsqu'il est utilisé sur une grande surface. Le substrat muni d'un film stratifié selon l'invention comprend un matériau primaire et un film stratifié disposé sur le matériau primaire. Le matériau primaire possède une première surface et une seconde surface se faisant face. Le film stratifié est disposé sur la première surface du matériau primaire et, du côté proche du matériau primaire, le film stratifié comporte une couche absorbant la chaleur et une couche réfléchissant les infrarouges. La couche absorbant la chaleur est formée à partir d'un film d'oxyde d'étain dopé à l'antimoine, la concentration d'antimoine incluse dans la couche absorbant la chaleur est de 3 à 14 % en moles, et l'épaisseur de la couche absorbant la chaleur est de 100 à 300 nm ou de 425 à 1000 nm.
PCT/JP2022/021449 2021-05-31 2022-05-25 Substrat muni d'un film stratifié WO2022255200A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04154647A (ja) * 1990-10-16 1992-05-27 Asahi Glass Co Ltd 透明導電性積層体
JP2000103648A (ja) * 1998-08-21 2000-04-11 Elf Atochem North America Inc 太陽光線制御被覆ガラス
JP2001007363A (ja) * 1999-06-18 2001-01-12 Nippon Sheet Glass Co Ltd 太陽電池用透明電極付きガラス
JP2001199744A (ja) * 1999-03-19 2001-07-24 Nippon Sheet Glass Co Ltd 低放射ガラスと該低放射ガラスを使用したガラス物品
JP2003535004A (ja) * 1999-08-10 2003-11-25 リビー−オーウェンズ−フォード・カンパニー ソーラーコントロールコーティングを有するガラス製品
US20060141265A1 (en) * 2004-12-28 2006-06-29 Russo David A Solar control coated glass composition with reduced haze
CN103539365A (zh) * 2013-10-09 2014-01-29 河源旗滨硅业有限公司 一种反射性阳光控制低辐射镀膜玻璃及其制备方法
WO2017212214A1 (fr) * 2016-06-09 2017-12-14 Pilkington Group Limited Article en verre enduit et vitre pour véhicule comprenant celui-ci

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04154647A (ja) * 1990-10-16 1992-05-27 Asahi Glass Co Ltd 透明導電性積層体
JP2000103648A (ja) * 1998-08-21 2000-04-11 Elf Atochem North America Inc 太陽光線制御被覆ガラス
JP2001199744A (ja) * 1999-03-19 2001-07-24 Nippon Sheet Glass Co Ltd 低放射ガラスと該低放射ガラスを使用したガラス物品
JP2001007363A (ja) * 1999-06-18 2001-01-12 Nippon Sheet Glass Co Ltd 太陽電池用透明電極付きガラス
JP2003535004A (ja) * 1999-08-10 2003-11-25 リビー−オーウェンズ−フォード・カンパニー ソーラーコントロールコーティングを有するガラス製品
US20060141265A1 (en) * 2004-12-28 2006-06-29 Russo David A Solar control coated glass composition with reduced haze
CN103539365A (zh) * 2013-10-09 2014-01-29 河源旗滨硅业有限公司 一种反射性阳光控制低辐射镀膜玻璃及其制备方法
WO2017212214A1 (fr) * 2016-06-09 2017-12-14 Pilkington Group Limited Article en verre enduit et vitre pour véhicule comprenant celui-ci

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