WO2022255205A1 - Substrat muni d' un film - Google Patents

Substrat muni d' un film Download PDF

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Publication number
WO2022255205A1
WO2022255205A1 PCT/JP2022/021464 JP2022021464W WO2022255205A1 WO 2022255205 A1 WO2022255205 A1 WO 2022255205A1 JP 2022021464 W JP2022021464 W JP 2022021464W WO 2022255205 A1 WO2022255205 A1 WO 2022255205A1
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WIPO (PCT)
Prior art keywords
film
coated substrate
glass
layer
less
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PCT/JP2022/021464
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English (en)
Japanese (ja)
Inventor
卓 立川
淳志 関
Original Assignee
Ａｇｃ株式会社
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Publication date
Priority claimed from JP2021214755A external-priority patent/JP7283530B1/ja
Priority claimed from JP2021214754A external-priority patent/JP7283529B1/ja
Application filed by Ａｇｃ株式会社 filed Critical Ａｇｃ株式会社
Priority to CN202280010183.8A priority Critical patent/CN116724010A/zh
Publication of WO2022255205A1 publication Critical patent/WO2022255205A1/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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • 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
    • 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
    • B32B7/027—Thermal 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
    • 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
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/26—Reflecting filters

Definitions

  • the present invention relates to a film-coated substrate, and more particularly to a film-coated substrate suitable for laminated glass.
  • 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).
  • laminated glass is widely used for window glass of vehicles, aircraft, buildings, etc., because the amount of scattered glass fragments is small when broken due to external impact, and it is excellent in safety.
  • Laminated glass includes at least a pair of glass sheets which are integrated with an intermediate film interposed between them, and the desired effect is obtained by the function of each constituent member.
  • Patent Document 3 discloses a solar radiation shield that reduces the visible light transmittance of a solar radiation shield having a heat ray shielding function and satisfies a specific relationship between the solar radiation transmittance and the visible light transmittance. Laminated glass is described by interposing this as an intermediate film between two sheet glasses. Also, US Pat. No. 6,000,000 proposes a panoramic vehicle roof laminate comprising at least one plastic adhesive layer between the first and second glass layers, the visible light transmission of the plastic adhesive layer being less than 50%. It is
  • the panoramic roof of a vehicle is required to have heat shielding, heat insulating properties, and a high-class color.
  • By providing an intermediate film with a reduced visible light transmittance desired transmittance and emissivity are both achieved.
  • the requirements for transmittance and emissivity have diversified, requiring manufacturers to manufacture a wide variety of products. There was a problem that a plurality of types had to be prepared, making it difficult to improve productivity.
  • the transmittance suitable for panoramic roofs is said to be between 3% and 8%.
  • a glass substrate with a film to be combined with an intermediate film and one glass there has been no substrate that can provide a laminated glass suitable for a panoramic roof by combining the intermediate film and the glass.
  • the present invention has been made to solve the above problems, and an object of the present invention is to provide means for improving productivity when manufacturing laminated glass.
  • the inventors of the present invention have made earnest efforts to solve the above problems, and found that the above problems can be solved by providing both a heat insulating function and a light shielding function to the film-coated glass substrate, leading to the present invention. rice field.
  • the present invention consists of the following configurations.
  • a film-coated substrate comprising a glass substrate and a film disposed on the glass substrate, wherein the glass substrate has a plate thickness of 5 mm or less, and has first and first surfaces facing each other. the film is disposed on the first surface of the glass substrate, the transmittance of the film-coated substrate based on a standard A light source is less than 30%, and the emission of the film-side surface is A film-coated substrate having a modulus of less than 0.25.
  • a vehicle window glass comprising the film-coated substrate according to (1) above.
  • a laminated glass comprising the film-coated base material according to (1) above, an intermediate film, and an outer glass plate in this order.
  • a panoramic roof having the laminated glass according to (3) above.
  • the film-coated base material of the present invention has a heat insulating function and a light shielding function, it is not necessary to separately prepare both the glass base material and the interlayer film for each type when manufacturing laminated glass.
  • a common intermediate film can be used by fabricating a substrate with a film by changing the heat insulating properties and transmittance of the substrate. Since the intermediate film can be used in common, the productivity can be improved and the cost can be reduced even in the production of many types of laminated glass.
  • many panoramic roofs for automobiles generally have a transmittance based on standard A light source (hereinafter also referred to as A light source transmittance) between 3% and 8%.
  • a light source transmittance of the film-coated substrate of the present invention is adjusted from 3% to 13%, and a laminated glass is produced by laminating a film-coated substrate, a transparent intermediate film, and colored glass in this order, A The light source transmittance can be 3% to 8%.
  • FIG. 1 is a cross-sectional view of a film-coated substrate for explaining the configuration of one embodiment of the film-coated substrate of the present invention.
  • FIG. 2 is a cross-sectional view of a film-coated substrate for explaining the configuration of another embodiment of the film-coated substrate of the present invention.
  • FIG. 3 is a flow diagram schematically showing an example of the method for producing a film-coated substrate of the present invention.
  • the film-coated substrate of the present invention has a glass substrate and a film placed on the glass substrate.
  • the film imparts a desired function to the film-coated glass substrate.
  • the film-coated substrate of the present invention has a transmittance of less than 30% based on the standard A light source and an emissivity of the film-side surface of less than 0.25.
  • the membrane may consist of one layer, or may include two or more layers.
  • FIG. 1 shows an embodiment of the film-coated substrate of the present invention.
  • the film-coated substrate 10 shown in FIG. 1 includes a glass substrate 1 and a film 2 placed on the glass substrate 1 .
  • the glass substrate has a first surface 1a and a second surface 1b facing each other, and a film 2 is placed on the first surface 1a of the glass substrate 1.
  • the film 2 is a laminated film having a heat ray absorbing layer 3 and an infrared reflecting layer 5 in this order from the side closer to the glass substrate 1 .
  • Each layer will be described below.
  • the glass substrate 1 serves as a framework for the film-coated substrate 10 and has self-supporting properties.
  • Examples of glass constituting the glass substrate include soda lime silicate glass, aluminosilicate glass, borate glass, lithium aluminosilicate glass, quartz glass, borosilicate glass, alkali-free glass, and the like.
  • the glass substrate can be transparent, translucent, or opaque, depending on the application and purpose of the film-coated base material. Further, the glass substrate may be colorless or colored.
  • the shape of the glass substrate 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 plate thickness of the glass substrate is 5 mm or less. When the plate thickness of the glass substrate is 5 mm or less, the plate thickness is suitable for in-vehicle use.
  • the plate thickness of the glass substrate is preferably 4.5 mm or less, more preferably 4.3 mm or less, and even more preferably 4.1 mm or less.
  • the plate thickness of the glass substrate is preferably 1 mm or more, more preferably 1.3 mm or more, and even more preferably 1.6 mm or more.
  • the size (area) of the glass substrate is not particularly limited, and may be appropriately adjusted according to the application and purpose of use of the film-coated substrate.
  • the area of the main surface of the glass substrate is preferably 0.5 to 5 m 2
  • the main surface of the glass substrate is area is preferably 0.5 to 10 m 2 .
  • the film laminated on the glass substrate comprises a heat ray absorbing layer 3 and an infrared reflecting layer 5 from the side closer to the glass substrate 1 .
  • the heat-absorbing layer 3 is a layer that reflects solar heat and imparts heat shielding properties to the film-coated substrate, and has crystallinity.
  • Materials for forming the heat-absorbing layer include, for example, metal oxides such as tin oxide, indium oxide, zinc oxide, titanium oxide, niobium oxide, and tantalum oxide.
  • the metal oxide forming the heat absorbing layer may be a doped metal oxide doped with another element (impurity element). By forming the heat ray absorbing layer from a doped metal oxide, the heat ray absorbing layer can be given a desired function.
  • impurity elements with which the doped metal oxide is doped include antimony, fluorine, tin, potassium, aluminum, tantalum, niobium, nitrogen, boron, and indium.
  • the concentration of the impurity element to be doped is preferably 30 mol % or less.
  • the impurity element concentration is 30 mol % or less, the crystal structure before doping can be maintained.
  • the impurity element concentration is preferably 30 mol % or less, more preferably 25 mol % or less, and even more preferably 20 mol % or less.
  • the concentration of the impurity element is preferably 0.1 mol % or more.
  • the concentration of the impurity element is preferably 1 mol% or more, more preferably 2 mol% or more, particularly preferably 4 mol% or more, and 6 mol%. The above is most preferred.
  • the heat-absorbing layer preferably comprises a film made of antimony-doped tin oxide (ATO, a metal oxide obtained by adding Sb to SnO 2 ).
  • ATO antimony-doped tin oxide
  • the antimony-doped tin oxide film reduces the amount of heat transferred to the inside of the substrate, and gives the film-coated substrate excellent heat shielding properties.
  • the concentration of antimony contained in the heat absorbing layer is preferably 5-20 mol %. When the antimony concentration in the heat-absorbing layer is 5 mol % or more, heat shielding properties can be exhibited and the transmittance can be lowered, and when the antimony concentration is 20 mol % or less, the crystal structure before doping can be maintained.
  • the concentration of antimony contained in the heat-absorbing layer is more preferably 6 mol% or more, still more preferably 7 mol% or more, particularly preferably 8 mol% or more, more preferably 19 mol% or less, and 18 mol% or less. More preferably, 15 mol % or less is particularly preferable.
  • the composition of the heat-absorbing layer and the concentration of impurity elements to be doped can be identified by X-ray photoelectron spectroscopy (XPS) or secondary ion mass spectrometry (SIMS).
  • XPS X-ray photoelectron spectroscopy
  • SIMS secondary ion mass spectrometry
  • the antimony (Sb) concentration can be examined from the intensity ratio of Sb and Sn by analyzing the depth direction by X-ray photoelectron spectroscopy (XPS).
  • the fluorine (F) concentration is analyzed in the depth direction by secondary ion mass spectrometry (SIMS), and can be examined from the intensity ratio of F and Sn.
  • SIMS it is necessary to measure fluorine-added tin SnO 2 of known concentration and obtain a coefficient for converting the intensity ratio of F/Sn into concentration.
  • the heat ray absorbing layer may consist of a single layer film, or may consist of two or more layers of films with different materials, metal contents, and the like.
  • the thickness of the heat-absorbing layer is preferably 300-700 nm.
  • the film-coated base material has sufficient heat shielding properties, and the transmittance of the film-coated base material can be easily adjusted to a predetermined value.
  • crystal grains can be grown to a certain extent in the heat-absorbing layer, it becomes easier to grow the crystal grain size in the infrared reflective layer when forming the infrared reflective layer.
  • the thickness of the heat-absorbing layer is 1000 nm or less, it is easy to keep the film surface flat.
  • the thickness of the heat-absorbing layer is preferably 350 nm or more, more preferably 400 nm or more, particularly preferably 450 nm or more, more preferably 900 nm or less, further preferably 800 nm or less, and particularly preferably 700 nm or less. .
  • the thickness of the heat-absorbing layer can be measured by analysis in the depth direction by X-ray photoelectron spectroscopy. Since the heat-absorbing layer is formed of metal oxide crystal grains, the surface opposite to the glass substrate 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 average thickness of the heat ray absorbing layer in the measurement area.
  • the size of crystal grains in the heat absorbing layer is preferably 30 to 1500 nm.
  • the crystal grain size is 30 nm or more, the crystal grain shape of the infrared reflective layer formed on the heat-absorbing layer can be made sufficiently large, and the emissivity can be lowered.
  • the size of the crystal grains is preferably 30 nm or more, more preferably 50 nm or more, and even more preferably 80 nm or more. Since the larger the crystal grain shape, the better, there is no particular upper limit, but generally 1500 nm or less. is preferred, 1200 nm or less is more preferred, and 1000 nm or less is even more preferred.
  • the size of the crystal grains can be measured by observing a cross section of the film-coated substrate cut in the thickness direction with a scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • the infrared reflective layer 5 is a layer that reflects infrared rays, imparts heat insulation to the film-coated substrate, and has crystallinity.
  • Materials for forming 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 indium oxide
  • Ga gallium-doped zinc oxide
  • AZO aluminum-doped zinc 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
  • the infrared reflective layer preferably comprises a film made of a doped metal oxide in which at least one metal oxide selected from the group consisting of tin oxide, indium oxide and zinc oxide is doped with another element. is preferably at least one selected from the group consisting of fluorine, antimony, tin, gallium and aluminum.
  • the infrared reflective layer is a 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 is more preferable to have at least one doped metal oxide film selected from, and from the viewpoint of obtaining higher heat insulation, it is even more preferable to have a fluorine-doped tin oxide (FTO) film.
  • FTO fluorine-doped tin oxide
  • 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, the heat insulation effect can be exhibited, and the transmittance of the film-coated substrate can be easily adjusted to a predetermined value, and it is preferably 20 mol% or less. Crystallinity can be maintained.
  • concentration of the impurity element contained in the infrared reflective layer is preferably 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.
  • concentration of the impurity element is the total amount when the infrared reflective layer contains a plurality of impurity elements.
  • 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 spectrometry (SIMS), as described above.
  • XPS X-ray photoelectron spectroscopy
  • SIMS secondary ion mass spectrometry
  • the thickness of the infrared reflective layer is preferably 100 to 400 nm.
  • the thickness of the infrared reflective layer is 100 nm or more, the heat insulation performance of the film-coated substrate is improved, and the transmittance of the film-coated substrate can be easily adjusted to a predetermined value.
  • the thickness of the infrared reflective layer is 400 nm or less, the surface can be flattened.
  • the thickness of the infrared reflective layer is more preferably 120 nm or more, still more preferably 130 nm or more, particularly preferably 150 nm or more, and more preferably 380 nm or less, further preferably 350 nm or less.
  • the thickness of the infrared reflective layer can be measured by depth direction analysis by 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 on which the infrared reflective layer is laminated 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 average thickness of the infrared reflective layer in the measurement area.
  • the size of the crystal grains in the infrared reflective layer is preferably 30 nm or more.
  • the size of the crystal grain is preferably 30 nm or more, more preferably 50 nm or more, and even more preferably 80 nm or more. Since the larger the crystal grain shape, the better, there is no particular upper limit, but generally 1000 nm or less. is preferably 800 nm or less, and even more preferably 500 nm or less.
  • the size of crystal grains can be measured by cross-sectional observation with a scanning electron microscope (SEM) in the same manner as described above.
  • the arithmetic mean roughness Ra of the surface of the infrared reflective layer is preferably 30 nm or less, more preferably 25 nm or less.
  • the heat-absorbing layer and the infrared-reflecting layer are preferably formed containing the same kind of metal oxide.
  • the metal oxide contained in the heat-absorbing layer and the metal oxide contained in the infrared reflective layer are of the same type, the crystal grains in the infrared reflective layer grow without interruption when forming the infrared reflective layer. can grow significantly.
  • the infrared reflective layer is preferably a doped tin oxide film.
  • the heat-absorbing layer is made of an antimony-doped tin oxide (ATO) film
  • the infrared ray-reflecting layer is made of a fluorine-doped tin oxide (FTO) film.
  • the concentration of fluorine contained in the infrared reflective layer is preferably 0.01 to 10 mol %.
  • concentration of fluorine contained in the infrared reflective layer is 0.01 mol% or more, a sufficient heat insulation effect can be exhibited, and when it is 10 mol% or less, the concentration of inert fluorine is suppressed and impurity scattering is reduced, resulting in reduced mobility.
  • the concentration of fluorine contained in the infrared reflective layer is more preferably 0.05 mol % or more, more preferably 0.1 mol % or more, more preferably 5 mol % or less, and still more preferably 3 mol % or less.
  • the total thickness of the infrared reflecting layer and the heat absorbing layer is preferably 500-1500 nm.
  • the crystal grains in the infrared reflective layer can be sufficiently grown, so that the emissivity can be improved and the transmittance can be easily adjusted within a predetermined range.
  • the total thickness of each layer is 1500 nm or less, the film-coated substrate does not become too thick.
  • the total thickness of the infrared reflecting layer and the heat absorbing layer is more preferably 550 nm or more, more preferably 600 nm or more, particularly preferably 650 nm or more, more preferably 1100 nm or less, and even more preferably 900 nm or less. .
  • the film 2 may further have an optical adjustment layer 7 as shown in FIG.
  • the optical adjustment layer 7 is preferably arranged between the glass substrate 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 glass substrate side, and a TiO2 film and a SiO2 film in this order from the glass substrate 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 glass substrate 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 5-40 mol %, more preferably 10-33 mol %.
  • the thickness of the optical adjustment layer is preferably 10-100 nm. When the thickness of the optical adjustment layer is 10 nm or more, the surface of the glass substrate can be uniformly coated. A desired effect can be exhibited as a layer.
  • the thickness of the optical adjustment layer is preferably 20 nm or more, more preferably 25 nm or more, particularly preferably 30 nm or more, and is preferably 100 nm or less, more preferably 90 nm or less, and further preferably 80 nm or less. 70 nm or less is particularly preferred.
  • the "thickness" of the optical adjustment layer is represented by the total thickness of each layer.
  • the thickness of the film is preferably 500-1600 nm.
  • the thickness of the film is 500 nm or more, the crystal grains in the film grow sufficiently, so that the emissivity can be improved and the transmittance can be easily adjusted. Further, when the thickness of the film is 1600 nm or less, the film-coated substrate does not become too thick.
  • the film-coated substrate 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 film-coated substrate of the present invention has a transmittance based on standard A light source (Tva, A light source transmittance) of less than 30%.
  • a light source transmittance (Tva) is preferably 28% or less, more preferably 25% or less, still more preferably 20% or less, and particularly preferably 13% or less.
  • the A light source transmittance (Tva) is preferably 1% or more, more preferably 2% or more, and further preferably 3% or more. 4% or more is particularly preferred, and 5% or more is most preferred.
  • the A light source transmittance (Tva) can be measured using a commercially available spectrophotometer (eg, "Lambda 1050" manufactured by PerkinElmer).
  • the solar transmittance (Te) of the film-coated substrate is preferably less than 30%.
  • the solar transmittance (Te) is more preferably 28% or less, even more preferably 25% or less, and particularly preferably 20% or less.
  • the solar transmittance (Te) is preferably 1% or more, more preferably 2% or more, and even more preferably 4% or more. .
  • the solar transmittance (Te) can be measured using a commercially available spectrophotometer (eg, "Lambda 1050” manufactured by PerkinElmer).
  • a light source transmittance and the solar transmittance can be adjusted to desired transmittances by adjusting the impurity concentration in the film and the thickness of each layer constituting the film.
  • the film-coated substrate has an emissivity (En) of less than 0.25 on the film-side surface.
  • the emissivity (En) is more preferably 0.23 or less, still more preferably 0.20 or less, and particularly preferably 0.17 or less.
  • the lower limit of the emissivity is not particularly limited, but it is preferably 0.01 or more, more preferably 0.02 or more, and further preferably 0.04 or more.
  • Emissivity is the ratio of the light energy (radiance) emitted by an object as thermal radiation to the light energy emitted by a black body of the same temperature (black body radiation) as 1.
  • the emissivity of the film-coated substrate can be measured on the film-side surface by the method described in JIS R3106 (2019) using a commercially available emissometer (for example, "Emissometer model AE1" manufactured by Devices & Services).
  • the emissivity can be adjusted to a desired value by adjusting the film thickness, carrier density, mobility, sheet resistance, etc. of the infrared reflective layer.
  • the sheet resistance value of the film-coated substrate is preferably 30 ⁇ / ⁇ (ohm/square) or less.
  • the emissivity is low because electricity flows easily, and thus excellent heat insulation can be obtained.
  • the sheet resistance value is more preferably 25 ⁇ / ⁇ or less, and even more preferably 20 ⁇ / ⁇ or less.
  • the lower the sheet resistance value the easier it is for electricity to flow and the lower the emissivity is. Therefore, the lower limit of the sheet resistance value is not particularly limited, but it is preferably 1 ⁇ / ⁇ or more, more preferably 2 ⁇ / ⁇ or more. , 3 ⁇ / ⁇ or more is more preferable.
  • the sheet resistance value can be measured by Hall effect measurement.
  • the film-coated base material of the present invention preferably has a color coordinate a * of a reflected color in the L * a * b * color system when light from a D65 light source is incident at an incident angle of 10 degrees, preferably from -20 to 5.
  • b * is preferably from ⁇ 20 to 10.
  • color and saturation are represented by a * and b * , with large a * (+a * ) in the red direction, small a * (-a * ) in the green direction, and , a large b * (+b * ) indicates a yellow direction, and a small b * (-b * ) indicates a blue direction.
  • the a * value is more preferably ⁇ 15 or more, more preferably ⁇ 12 or more, more preferably 2 or less, and still more preferably 0 or less.
  • the b * value is more preferably ⁇ 15 or more, more preferably ⁇ 10 or more, more preferably 5 or less, and still more preferably 2 or less.
  • the color coordinate L * of the reflected color in the L * a * b * color system is 42 or less when light from a D65 light source is incident at an incident angle of 10 degrees. .
  • L * represents lightness, and when the L * value is 42 or less, the intensity of reflected light can be suppressed, and undesirable reflection can be suppressed.
  • the L * value is more preferably 40 or less, even more preferably 35 or less.
  • the L * value is preferably 20 or more, more preferably 25 or more, and particularly preferably 30 or more, considering the reflectance of a general infrared reflective layer.
  • the a * value, b * value, and L * value can be measured by a UV-visible spectrophotometer or a chromaticity meter, and the values are measured using these measuring instruments when the light from a D65 light source is irradiated at an incident angle of 10 degrees. .
  • the a * , b * and L * values can be adjusted to desired values by adjusting the impurity concentration in the film and the thickness of each layer constituting the film.
  • the mobility of the film of the film-coated substrate is preferably 20 cm 2 /Vs or more.
  • the mobility of the film is more preferably 25 cm 2 /Vs or higher, even more preferably 27 cm 2 /Vs or higher, particularly preferably 30 cm 2 /Vs or higher, and most preferably 35 cm 2 /Vs or higher.
  • the upper limit is not particularly limited because the higher the mobility, the better .
  • the mobility of the infrared reflective layer is preferably 20 cm 2 /Vs or more.
  • the mobility of the infrared reflective layer is more preferably 25 cm 2 /Vs or higher, still more preferably 27 cm 2 /Vs or higher, particularly preferably 30 cm 2 /Vs or higher, and most preferably 35 cm 2 /Vs or higher.
  • the upper limit is not particularly limited because the higher the mobility, the better .
  • the mobility of the film-coated substrate and the infrared reflective layer can be measured by Hall effect measurement.
  • the carrier density of the film-coated substrate is preferably 1 ⁇ 10 19 /cm 3 or more.
  • Carrier density refers to the number of free electrons or holes per unit volume in a substance.
  • the carrier density of the film-coated substrate is more preferably 2 ⁇ 10 19 /cm 3 or higher, still more preferably 5 ⁇ 10 19 /cm 3 or higher, and particularly preferably 1 ⁇ 10 20 /cm 3 or higher.
  • the upper limit is not particularly limited because the higher the carrier density , the better . 3 or less is more preferable.
  • the carrier density of the infrared reflective layer is preferably 1 ⁇ 10 19 /cm 3 or more.
  • the carrier density of the infrared reflective layer is more preferably 2 ⁇ 10 19 /cm 3 or higher, still more preferably 5 ⁇ 10 19 /cm 3 or higher, and particularly preferably 1 ⁇ 10 20 /cm 3 or higher.
  • the upper limit is not particularly limited because the higher the carrier density , the better . 3 or less is more preferable.
  • the carrier density of the film-coated substrate and the infrared reflective layer can be measured by Hall effect measurement.
  • the film-coated substrate preferably has a haze of 10% or less.
  • the haze is 10% or less, the appearance of white turbidity in the film-coated substrate is suppressed, and a film-coated substrate with excellent appearance can be obtained.
  • Haze is more preferably 9% or less, still more preferably 7% or less, and particularly preferably 5% or less.
  • the lower limit is not particularly limited.
  • Haze can be measured using a commercially available measuring instrument (eg, haze meter "HZ-V3" manufactured by Suga Test Instruments Co., Ltd.).
  • a commercially available measuring instrument eg, haze meter "HZ-V3" manufactured by Suga Test Instruments Co., Ltd.
  • FIG. 3 schematically shows an example of the flow of the method for manufacturing the film-coated substrate 10 .
  • the method for producing a film-coated substrate of the present invention comprises: (a) placing a heat absorbing layer on the first surface of the glass substrate (step S1); (b) placing an infrared reflective layer on the heat absorbing layer (step S2); have
  • a glass substrate is prepared.
  • the type of glass substrate is not particularly limited, and may be a soda lime silicate-based high-transmittance glass.
  • step S1 a heat ray absorbing layer is formed on the first surface of the glass substrate.
  • 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 spraying
  • the heat-absorbing layer is, for example, tin oxide, indium oxide, zinc oxide, antimony-doped tin oxide (ATO), fluorine-doped tin oxide (FTO), tin-doped indium oxide (ITO), gallium-doped zinc oxide (GZO ), and aluminum-doped zinc oxide (AZO).
  • ATO antimony-doped tin oxide
  • FTO fluorine-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 fluorine-doped tin oxide (FTO)
  • the heat ray absorbing layer is composed of antimony-doped tin oxide (ATO)
  • each layer is formed by thermal CVD.
  • a mixture of an inorganic or organic tin compound and an antimony compound is used as a raw material for the heat ray absorbing layer.
  • 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 raw material gases may be mixed in advance and then transported.
  • the raw material gases may be mixed on the surface of the glass substrate 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 per 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, and as a result, the heat absorption function of antimony tends to decrease. 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 mol, the volume of the source gas increases as the amount of water increases, and the flow rate of the source 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 source gas increases, and the flow rate of the source gas increases, which may reduce the deposition efficiency.
  • the temperature of the glass substrate when forming the heat absorbing layer is preferably 500 to 650.degree. 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.
  • Step S2 an infrared reflecting 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
  • electron beam deposition electron beam deposition
  • vacuum deposition vacuum deposition
  • sputtering sputtering
  • spraying spraying
  • 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, making it easy to adjust the color tone 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) and formed by a thermal CVD method
  • FTO fluorine-doped tin oxide layer
  • a mixture of an inorganic or organic tin compound and a fluorine compound is used as a 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 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 per 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, and as a result, the infrared reflecting function tends to decrease. 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 mol, the volume of the source gas increases as the amount of water increases, and the flow rate of the source 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 less than 4 mol, the resulting film may have an increased resistance value. On the other hand, if the amount of oxygen exceeds 40 mol, the volume of the source gas increases, and the flow rate of the source gas increases, which may reduce the 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 to 650°C. 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. On the other hand, if 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.
  • 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.
  • 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.
  • steps S1 and S2 may be performed by an online method in the process of manufacturing a glass substrate with a float facility.
  • film formation may be performed by reheating the glass substrate manufactured by the float method by an off-line method. From the viewpoint of manufacturing efficiency, it is preferable to perform steps S1 and S2 by a thermal CVD method to form a film on a glass substrate manufacturing line.
  • the optical adjustment layer when an optical adjustment layer is provided between the glass substrate and the heat absorption layer, the optical adjustment layer is arranged on the first surface of the glass substrate before step S1.
  • the optical adjustment layer can be formed by chemical vapor deposition (CVD), electron beam evaporation, vacuum deposition, sputtering, chemical plating, wet coating, spraying, etc. It can be formed using various film formation methods. Preferably, steps S1 and S2 are performed in the same manner.
  • CVD chemical vapor deposition
  • electron beam evaporation electron beam evaporation
  • vacuum deposition vacuum deposition
  • sputtering chemical plating
  • wet coating wet coating
  • spraying etc. It can be formed using various film formation methods.
  • steps S1 and S2 are performed in the same manner.
  • 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 a thermal CVD method.
  • a mixed gas containing monosilane (SiH 4 ), ethylene and carbon dioxide can be used as the raw material.
  • a carbon-containing gas When such a carbon-containing gas is used, a particulate silicon compound is easily formed together with a film-like silicon compound, and the haze ratio can be increased.
  • the raw material gases may be mixed in advance and then transported onto the first surface of the glass substrate. Alternatively, source gases may be mixed on the first surface of the glass substrate.
  • 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 glass substrate when forming the optical adjustment layer is preferably 500 to 900°C. If the temperature of the glass substrate is less than 500° C. or more than 900° C., the film formation rate tends to decrease.
  • a method of forming a layer made of SiO x Cy (hereinafter also referred to as a SiO x Cy layer) as an optical adjustment layer by a CVD method will be described.
  • the CVD method it is preferable to react a glass substrate heated to a temperature of, for example, 500 to 800° C. with a gas raw material to form a SiO x Cy layer on the glass substrate.
  • the temperature of the glass substrate is preferably 500° C. or higher, more preferably 600° C. or higher, and even more preferably 700° C. or higher, from the viewpoint of improving the reaction rate of the CVD method.
  • the temperature of the glass substrate is more preferably 800° C. or lower, more preferably 760° C. or lower, from the viewpoint of glass softening.
  • the gas source preferably contains a silicon-containing substance, an oxidizing agent and an unsaturated hydrocarbon.
  • Silicon-containing substances include silanes such as monosilane (SiH 4 ), disilane (Si 2 H 6 ), dichlorosilane (SiH 2 Cl 2 ), silane trioxide (SiHCl 3 ), tetramethylsilane ((CH 3 ) 4 Si), silicon tetrafluoride (SiF 4 ), silicon tetrachloride (SiCl 4 ), etc., with silanes being preferred, and monosilane being more preferred.
  • silanes such as monosilane (SiH 4 ), disilane (Si 2 H 6 ), dichlorosilane (SiH 2 Cl 2 ), silane trioxide (SiHCl 3 ), tetramethylsilane ((CH 3 ) 4 Si), silicon tetrafluoride (SiF 4 ), silicon tetrachloride (SiCl 4 ), etc., with silanes being preferred, and monosilane being more preferred.
  • oxidizing agent examples include compounds containing an oxygen element such as carbon dioxide (CO 2 ), carbon monoxide (CO), oxygen (O 2 ) and water vapor (H 2 O), with carbon dioxide being preferred.
  • CO 2 carbon dioxide
  • CO carbon monoxide
  • O 2 oxygen
  • H 2 O water vapor
  • unsaturated hydrocarbons examples include ethylenically unsaturated hydrocarbons (olefins), acetylenically unsaturated hydrocarbons, aromatic compounds, and the like, and compounds that are gaseous at normal temperature and normal pressure are preferred.
  • olefins are preferred, olefins having 2 to 4 carbon atoms are more preferred, and ethylene is even more preferred.
  • the composition of SiO x Cy in the SiO x Cy layer can be adjusted by adjusting the mixing ratio of the gas source.
  • the volume ratio of the oxidizing agent to the silicon-containing substance is preferably 8.5 or higher, more preferably 12 or higher, and even more preferably 20 or higher.
  • the volume ratio of the oxidizing agent to the silicon-containing substance is preferably 50 or less.
  • the volume ratio of the unsaturated hydrocarbon to the silicon-containing substance is preferably 0.5 or more, more preferably 1.0 or more. Also, the volume ratio of the unsaturated hydrocarbon to the silicon-containing substance is preferably 3.5 or less, more preferably 2.7 or less.
  • composition of SiO x Cy changes due to the interaction between the oxidizing agent and the unsaturated hydrocarbon. Therefore, in order to adjust the composition of SiO x Cy to the preferred range, the combination of both the volume ratio of the oxidizing agent and the volume ratio of the unsaturated hydrocarbon to the silicon-containing material is important, and both are set to the above-described preferred range. A range is preferred.
  • the thickness of the SiO x Cy layer is preferably 10 nm or more, more preferably 20 nm or more, and even more preferably 25 nm or more. From the viewpoint of suppressing light absorption by the SiO x Cy layer, the thickness is preferably 90 nm or less, more preferably 80 nm or less, and even more preferably 70 nm or less.
  • the thickness of the SiO x Cy layer can be controlled by the type of raw material, the raw material gas concentration, the flow rate of the raw material gas blown onto the glass ribbon or the glass substrate, the substrate temperature, the reaction gas residence time derived from the coating beam structure, and the like.
  • 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 then applied over the infrared reflective layer of the film-coated substrate.
  • the coating method is not particularly limited, and a common means such as spin coating may be used.
  • the film-coated substrate provided with the coating solution is heat-treated in the atmosphere.
  • the temperature of the heat treatment is, for example, in the range of 80-650.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 film-coated substrate of the present invention can be produced.
  • the method for producing a film-coated substrate of the present invention may further include a step of tempering or chemically tempering the glass substrate (strengthening step).
  • This strengthening step may be performed in any order, for example, before step S1 or after manufacturing the film-coated substrate. By carrying out the strengthening step, the strength of the glass substrate and the resulting film-coated substrate can be increased.
  • the resulting film-coated base material may be subjected to bending.
  • a laminated glass can also be obtained by laminating the film-coated substrate of the present invention, an intermediate film, and an outer glass plate in this order.
  • the intermediate layer can be used in common, thereby improving productivity and reducing costs.
  • the film-coated base material 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.
  • a laminated glass having the film-coated substrate of the present invention, an intermediate film and an outer glass plate in this order is suitable for a panoramic roof.
  • a film-coated base material comprising a glass substrate and a film disposed on the glass substrate, wherein the glass substrate has a thickness of 5 mm or less, and the first surface and the first surface facing each other the film is disposed on the first surface of the glass substrate, the transmittance of the film-coated substrate based on a standard A light source is less than 30%, and the emission of the film-side surface is A film-coated substrate having a modulus of less than 0.25.
  • ⁇ 3> The film-coated substrate according to ⁇ 1> or ⁇ 2>, wherein the film has a carrier density of 1 ⁇ 10 19 /cm 3 or more.
  • ⁇ 4> The film-coated substrate according to any one of ⁇ 1> to ⁇ 3>, wherein the mobility of the film is 20 cm 2 /Vs or more.
  • ⁇ 5> The film-coated substrate according to any one of ⁇ 1> to ⁇ 4>, wherein the film-coated substrate has a solar transmittance of less than 30%.
  • ⁇ 6> The film-coated substrate according to any one of ⁇ 1> to ⁇ 5>, wherein the transmittance based on the standard A light source is 3 to 13%.
  • ⁇ 7> The film-coated substrate according to any one of ⁇ 1> to ⁇ 6>, wherein the transmittance based on the standard A light source is 5 to 13%.
  • the film includes a heat ray absorbing layer and an infrared reflecting layer in order from the glass substrate side.
  • the infrared reflective layer comprises at least one doped 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.
  • ⁇ 10> The film-coated substrate according to ⁇ 8> or ⁇ 9>, wherein the infrared reflective layer comprises a fluorine-doped tin oxide film.
  • the infrared reflective layer has a thickness of 100 to 400 nm.
  • the heat-absorbing layer includes an antimony-doped tin oxide film.
  • ⁇ 13> The base material with a film according to ⁇ 12>, wherein the antimony concentration contained in the heat ray absorbing layer is 5 to 20 mol %.
  • ⁇ 14> The film-coated substrate according to any one of ⁇ 8> to ⁇ 13>, wherein the heat-absorbing layer has a thickness of 300 to 700 nm.
  • the film further has an optical adjustment layer, and the optical adjustment layer is disposed between the glass substrate and the heat ray absorbing layer.
  • the optical adjustment layer comprises at least one film selected from the group consisting of a SiOC film, a SiOC/ SiO2 laminated film, a TiO2 / SiO2 laminated film, and a SnO2 / SiO2 laminated film; 15> The base material with a film according to above.
  • ⁇ 20> A vehicle window glass comprising the film-coated substrate according to any one of ⁇ 1> to ⁇ 19>.
  • ⁇ 21> A laminated glass comprising the film-coated substrate according to any one of ⁇ 1> to ⁇ 19>, an intermediate film, and an outer glass plate in this order.
  • the laminated glass according to ⁇ 21> which is used for a roof of a vehicle.
  • ⁇ 23> A panoramic roof comprising the laminated glass according to ⁇ 21>.
  • the film-coated base material was cut in the thickness direction, and the cross section was observed with a scanning electron microscope (SEM, "SU 70" manufactured by Hitachi, Ltd.).
  • SEM scanning electron microscope
  • the film thickness of each layer was examined directly from the SEM image.
  • the thickness of each layer was derived using the intermediate 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 were adopted as standard observation conditions. 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 was 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 was 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 was set as the interface between the heat ray absorption layer and the optical adjustment layer.
  • the film thickness of each layer can be derived 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 was calculated from the X-ray peak intensity using software PHI MULTIPAC manufactured by ULVAC.
  • the antimony concentration was analyzed in the depth direction by X-ray photoelectron spectroscopy (XPS) and examined from the intensity ratio of Sb and Sn.
  • XPS X-ray photoelectron spectroscopy
  • PHI 5000 Versa Probe manufactured by ULVAC-PHI was used.
  • the XPS analysis method is the same as when evaluating each layer thickness.
  • the haze of the film-coated substrate was measured using a haze meter "HZ-V3" manufactured by Suga Test Instruments Co., Ltd.
  • the film-coated substrate was cut into 1 cm squares, and the mobility of the layers (heat ray absorption layer and infrared reflective layer) through which electricity flows in the film-coated substrate was measured using a Hall measuring instrument ("HL 5500 PC” manufactured by Nanometrics) (Van der Pauw method).
  • the film-coated substrate was cut into 1 cm squares, and the sheet carrier density (1/cm 2 ) is measured (Van der Pauw method) and divided by the sum of the film thicknesses of the heat ray absorbing layer and the infrared reflective layer to obtain the carrier density ( 1/cm 3 ) was derived.
  • Example 1 A substrate with a film was produced by the following method. First, a glass substrate (soda lime silicate glass: manufactured by AGC Corporation) having a thickness of 2.1 mm was prepared.
  • the heat absorbing layer is made of antimony-doped tin oxide (SnO 2 :Sb, ATO) and deposited by thermal CVD.
  • 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 of the heat-absorbing layer was set to 500 nm.
  • the infrared reflective layer was a fluorine-doped tin oxide layer (SnO 2 :F, FTO) and was deposited by thermal CVD.
  • 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 of the infrared reflective layer was 300 nm. Thus, a film-coated substrate was obtained.
  • Example 23 By the same method as in Example 1, a film-coated substrate having the layer structure shown in Table 1 was produced.
  • the antimony concentration was adjusted by adjusting the ratio of monobutyl tin trichloride (MBTC) and antimony trichloride (SbCl 3 ).
  • Examples 1 to 19 had low emissivity, excellent heat resistance, and low transmittance. From this, it was found that both heat insulation performance and light shielding performance were achieved.

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  • Laminated Bodies (AREA)

Abstract

La présente invention fournit un moyen d'amélioration de productivité lors de la fabrication de verre feuilleté. Ce substrat muni d'un film comprend un substrat de verre et un film qui est disposé sur le substrat de verre. Le substrat de verre présente une épaisseur de 5 mm ou moins, et comprend une première surface et une seconde surface se faisant face. Le film est disposé sur la première surface du substrat de verre. La transmittance du substrat muni d'un film est inférieure à 30 % sur la base d'une source de lumière A standard, et l'émissivité de la surface côté film est inférieure à 0,25.
PCT/JP2022/021464 2021-05-31 2022-05-25 Substrat muni d' un film WO2022255205A1 (fr)

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JP2021214755A JP7283530B1 (ja) 2021-12-28 2021-12-28 積層膜付き基材
JP2021-214754 2021-12-28
JP2021214754A JP7283529B1 (ja) 2021-12-28 2021-12-28 積層膜付き基材
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6858306B1 (en) * 1999-08-10 2005-02-22 Pilkington North America Inc. Glass article having a solar control coating
US20060141265A1 (en) * 2004-12-28 2006-06-29 Russo David A Solar control coated glass composition with reduced haze

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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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