WO2022255201A1 - Substrat avec film stratifié - Google Patents

Substrat avec film stratifié Download PDF

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Publication number
WO2022255201A1
WO2022255201A1 PCT/JP2022/021454 JP2022021454W WO2022255201A1 WO 2022255201 A1 WO2022255201 A1 WO 2022255201A1 JP 2022021454 W JP2022021454 W JP 2022021454W WO 2022255201 A1 WO2022255201 A1 WO 2022255201A1
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Prior art keywords
laminated film
layer
substrate
heat
less
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PCT/JP2022/021454
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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 CN202280010187.6A priority Critical patent/CN116724011A/zh
Publication of WO2022255201A1 publication Critical patent/WO2022255201A1/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 base material with a laminated film, and more particularly to a base material with a laminated film suitable for 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 solar energy transmission (air mass 1.5) are described.
  • Low emissivity glasses such as those described in Patent Literatures 1 and 2 have a heat insulating property due to a fluorine-doped tin oxide layer on the surface. By adjusting the thickness of the fluorine-doped tin oxide layer, it is possible to obtain a heat insulating effect suitable for the usage environment.
  • glass laminates such as low-emissivity glass, change color due to the light interference effect of the functional film.
  • the color tone of window glass for vehicles since red, orange, yellow, etc. are warning colors, there is a tendency to prefer bluish hues, which are protective colors, and there has been a demand for low-emissivity glass with excellent external color tone.
  • an object of the present invention is to provide a base material with a laminated film having heat insulation and heat shielding properties and an appearance color suitable for vehicle use.
  • the present inventors have made earnest efforts to solve the above problems, and found that in a base material with a laminated film having a heat ray absorbing layer and an infrared reflective layer on a main material, the heat ray absorbing layer contains antimony at a predetermined concentration.
  • the present inventors have found that the above problems can be solved by providing a doped tin oxide film and setting the thickness of the infrared reflective layer to a predetermined value, and have completed the present invention.
  • the present invention consists of the following configurations.
  • 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.
  • the laminated film-attached base material of the present invention can provide a base material that has excellent heat insulating properties and heat shielding properties and has a bluish tint. Therefore, when the laminated film-coated base material of the present invention is used for the roof glass of a vehicle, the appearance is excellent and the vehicle body can be given a high-class feeling.
  • 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 flow diagram schematically showing an example of the method for producing a substrate with a laminated film of the present invention.
  • 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 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 . Each layer will be described below.
  • 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 transparent, translucent, or opaque, depending on the application and purpose of the base material with laminated film. Also, 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.
  • the main material is a glass plate, the thickness of the glass plate is 1 to 5 mm, and the area of the main surface of the glass plate is 0.5 to 5 m 2 .
  • the main material is a glass plate, the thickness of the glass plate is 4 to 8 mm, and the area of the main surface of the glass plate is 0.5 to 10 m 2 . preferable.
  • the heat-absorbing layer 3 is a layer that reflects solar heat and imparts heat-shielding properties to the substrate with a laminated film, 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 heat absorbing layer 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 transmitted to the inside of the base material, and gives the base material with the laminated film excellent heat shielding properties.
  • the concentration of antimony contained in the heat absorbing layer is 11.5 mol % or less. When the antimony concentration in the heat ray absorbing layer is 11.5 mol % or less, heat shielding properties can be exhibited while maintaining the color tone of the base material with the laminated film tending toward blue.
  • the concentration of antimony contained in the heat-absorbing layer is preferably 11 mol % or less, more preferably 10.5 mol % or less, even more preferably 10 mol % or less. From the viewpoint of heat absorption, the antimony concentration in the heat absorption layer is preferably 3 mol % or more, more preferably 4 mol % or more, and even more preferably 5 mol % or more.
  • 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. Among them, it is preferable that the heat-absorbing layer is made of an antimony-doped tin oxide film.
  • the thickness of the heat-absorbing layer is preferably 300 nm or more.
  • the thickness of the heat ray absorbing layer is 300 nm or more, sufficient heat shielding properties can be imparted to the substrate with the laminated film.
  • 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 more preferably 350 nm or more, even more preferably 400 nm or more. From the viewpoint of surface flatness, the thickness of the heat-absorbing layer is preferably 1000 nm or less, more preferably 900 nm or less, and even more preferably 800 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 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 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, resulting in excellent heat insulation.
  • 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 laminated film-attached 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 laminated 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, 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.
  • 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 shall be 200 nm or more.
  • the thickness of the infrared reflective layer is preferably 205 nm or more, more preferably 210 nm or more, even more preferably 215 nm or more.
  • the upper limit of the thickness of the infrared reflective layer is not particularly limited as long as the effect of the present invention is exhibited, but from the viewpoint of ensuring the transparency of the main material in the visible light region, it is preferably 1000 nm or less, and more preferably 750 nm or less. It is preferably 400 nm or less, more preferably 400 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 insulating effect can be exhibited, and when it is 10 mol % or less, the mobility of the infrared reflective layer increases and excellent heat insulating properties can be exhibited.
  • the concentration of fluorine contained in the infrared reflective layer is preferably 0.01 mol % or more, more preferably 0.2 mol % or more, still more preferably 0.5 mol % or more, and 8.5 mol % or less. More preferably, 7 mol % or less is even more preferable, and 6 mol % or less is particularly preferable.
  • 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, and when it is 2000 nm or less, the thickness of the laminated 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 2000 nm or less, and even more preferably 1500 nm or less. , 1100 nm or less are particularly preferred.
  • the laminated film 2 may further have an optical adjustment layer 7 as shown in FIG.
  • the optical adjustment layer 7 is preferably arranged between the main material 1 and the heat ray absorbing 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 5-40 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 main material 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, still more preferably 25 nm or more, particularly 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 color coordinate a* of the 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 is 2.5 or less.
  • 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. That is, the smaller a * and b * are, the more bluish the color becomes. Since blue is a protective color against warning colors such as red, orange, and yellow, it is suitable for application to vehicle window glass and the like.
  • the laminated film-coated substrate becomes bluish.
  • the a * value is more preferably 2.4 or less, even more preferably 2.3 or less, and particularly preferably 2.0 or less, from the viewpoint of making the color of the laminated film-attached substrate closer to blue.
  • the a * value is preferably ⁇ 20 or more, more preferably ⁇ 10 or more.
  • the color coordinate b * of the reflected color in the L * a * b * color system is 2.5 or less when light from a D65 light source is incident at an incident angle of 10 degrees. is preferred.
  • the laminated film-coated substrate becomes bluish.
  • the b * value is more preferably 2.4 or less, still more preferably 2.0 or less, particularly preferably 1.2 or less, from the viewpoint of making the color of the substrate with the laminated film closer to blue. 0 or less is most preferred.
  • the b * value is preferably ⁇ 20 or more, more preferably ⁇ 10 or more.
  • the laminated film-coated base material of the present invention has a color coordinate L * 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 is 30.0 to 40.0. 0 is preferred.
  • L * represents lightness, and there is a tendency that low lightness is preferred for substrates with laminated films that require deep color.
  • the L * value is more preferably 39.0 or less, even more preferably 38.5 or less, and particularly preferably 38.0 or less.
  • the lower limit is preferably 30.0 or more, more preferably 32.0 or more, and even more preferably 34.0 or more.
  • 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 base material with a laminated film has a transmittance (Tva, hereinafter also referred to as “A light source transmittance”) based on standard A light source of less than 30%. Sufficient heat ray absorptivity is obtained as A light source transmittance (Tva) is less than 30%.
  • a light source transmittance (Tva) is preferably 25% or less, more preferably 20% or less, and further preferably 16% or less, and the lower limit is not particularly limited, but is preferably 1% or more. 2% or more is more preferable, and 5% or more is even more preferable.
  • 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 laminated film-coated substrate is preferably 25% or less.
  • the solar transmittance (Te) is preferably 25% or less, more preferably 20% or less, still more preferably 15% or less, and although there is no lower limit, it is preferably 1% or more. % or more is more preferable, and 5% or more is even more preferable.
  • the solar transmittance (Te) can be measured using a commercially available spectrophotometer (eg, "Lambda 1050” manufactured by PerkinElmer).
  • the base material with a laminated film has an emissivity (En) of less than 0.25 on the infrared reflective layer side surface.
  • the emissivity (En) of the infrared reflective layer side surface is less than 0.25, excellent heat insulation can be obtained.
  • the emissivity (En) is more preferably 0.22 or less, still more preferably 0.20 or less, and particularly preferably 0.15 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 0.05 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 infrared reflective layer side of the laminated film-coated substrate can be measured by the method described in JIS R3106 (2019) using a commercially available emissometer (for example, "Emissometer model AE1" manufactured by Devices & Services).
  • the value of the sheet resistance of the substrate with the laminated film is preferably 30 ⁇ / ⁇ (ohm/square) or less.
  • the sheet resistance value is preferably 30 ⁇ / ⁇ or less, 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 mobility of the laminated film-attached substrate is preferably 25 cm 2 /Vs or more.
  • the mobility is more preferably 27 cm 2 /Vs or higher, still more preferably 30 cm 2 /Vs or higher, and particularly preferably 35 cm 2 /Vs or higher.
  • the upper limit is not particularly limited because the higher the mobility, the better .
  • Mobility can be measured by Hall effect measurement.
  • the carrier density of the laminated film-attached 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 laminated film-attached substrate is more preferably 2 ⁇ 10 19 /cm 3 or higher, even 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 infrared reflective layer preferably has a carrier density of 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 substrate with laminated film and the infrared reflective layer can be measured by Hall effect measurement.
  • the base material with a laminated film has a haze of 10% or less.
  • the haze is 10% or less, it is possible to suppress the appearance of white turbidity in the laminated film-coated substrate and to obtain a laminated film-coated substrate with excellent aesthetic appearance.
  • 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 substrate 10 with 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 formed 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 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
  • at least an antimony-doped tin oxide (ATO) film is provided as a heat absorption layer.
  • 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 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 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 main material when forming the heat ray absorbing layer is preferably 500 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 concentration of antimony contained in the heat-absorbing layer is set to 11.5 mol% or less.
  • the concentration of antimony contained in the heat-absorbing layer can be adjusted by adjusting the amount of antimony compound used relative to the tin compound used, changing the temperature during film formation, changing the ratio of water or oxygen to the tin compound, and the like.
  • 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
  • ITO tin-doped indium oxide
  • ITO tin-doped indium oxide
  • ITO uses In, which is a rare metal, it tends to be expensive.
  • ITO is generally produced by sputtering at a lower temperature than thermal CVD, FTO is more desirable from the viewpoint of durability.
  • 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. 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 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 atmospheric pressure CVD.
  • 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 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 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.
  • 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 plate heated to a temperature of 500 to 800° C. with a gas raw material to form a SiO x Cy layer on the glass plate.
  • the temperature of the glass plate 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 plate 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 plate, 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 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 80-650.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 to the surface on the glass plate side may be carried out.
  • the laminated 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, etc., and is particularly suitable for vehicle roof glass.
  • 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.
  • 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.
  • ⁇ 4> The base material with a laminated film according to any one of ⁇ 1> to ⁇ 3>, wherein the thickness of the heat ray absorbing layer is 300 nm or more.
  • ⁇ 5> The substrate with a laminated film according to any one of ⁇ 1> to ⁇ 4>, wherein the substrate with a laminated film has a transmittance of less than 30% based on a standard A light source.
  • ⁇ 6> The substrate with a laminated film according to any one of ⁇ 1> to ⁇ 5>, wherein the infrared reflective layer-side surface has an emissivity of less than 0.25.
  • ⁇ 9> The laminated film-coated substrate according to any one of ⁇ 1> to ⁇ 8>, wherein the laminated film-coated substrate has a mobility of 25 cm 2 /Vs or more.
  • ⁇ 10> The laminated film-coated substrate according to any one of ⁇ 1> to ⁇ 9>, wherein the laminated film-coated substrate has a carrier density of 1 ⁇ 10 19 /cm 3 or more.
  • ⁇ 11> The substrate with a laminated film according to any one of ⁇ 1> to ⁇ 10>, wherein the main material is glass.
  • ⁇ 12> The substrate with a laminated film according to any one of ⁇ 1> to ⁇ 11>, wherein the heat absorption layer and the infrared reflection layer are formed by a thermal CVD method.
  • the laminated film further includes an optical adjustment layer, and the optical adjustment layer is disposed between the main material and the heat-absorbing layer. 3.
  • 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; 13>, the laminated film-attached substrate.
  • the optical adjustment layer includes a SiOC film.
  • Test Example 1 substrates with laminated films of Examples 1 to 15 were produced.
  • the measurements performed in Test Example 1 are as follows.
  • the laminated film-attached 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 laminated film-attached substrate was cut into 1 cm squares, and the sheet resistance value was measured with a Hall measuring device ("HL 5500 PC” manufactured by Nanometrics).
  • the haze of the laminated film-coated substrate was measured using a haze meter "HZ-V3" manufactured by Suga Test Instruments Co., Ltd.
  • the substrate with the laminated film 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, so that the portion where electricity flows in the substrate with the laminated film (heat ray absorbing layer and infrared reflective layer) A carrier density (1/cm 3 ) was derived.
  • Example 1 A base material with a laminated 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. Next, a SiOC layer was formed as an optical adjustment layer on this glass substrate by a thermal 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.
  • 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 ray absorbing layer was 520 m.
  • 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 200 nm. As a result, a base material with a laminated film was obtained.
  • Examples 2-15) By the same method as in Example 1, a substrate with a laminated film having the layer structure shown in Table 1 was produced.
  • the antimony concentration was adjusted by adjusting the ratio of monobutyl tin trichloride (MBTC).
  • Table 1 shows the measurement results of the base material with the laminated film of each example.
  • Test Example 2 the color coordinates of the reflected colors of the substrates with laminated films of Examples 16 to 28 having FTO films of different thicknesses were evaluated using optical simulation. The evaluation was performed with respect to the color coordinate L * value and a * value of the reflected color that can be accurately simulated.
  • 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.

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Abstract

La présente invention concerne un substrat avec un film stratifié, ledit substrat ayant des propriétés d'isolation thermique et des propriétés de protection thermique et ayant un ton de couleur externe approprié pour des applications de véhicule. Le substrat avec un film stratifié selon l'invention comprend un matériau primaire et un film stratifié disposé sur le matériau primaire. Le matériau primaire présente une première surface et une seconde surface se faisant face. Le film stratifié est disposé sur la première surface du matériau primaire et, à partir du côté proche du matériau primaire, le film stratifié comporte une couche d'absorption de chaleur et une couche réfléchissant les infrarouges. La couche d'absorption de chaleur est pourvue d'un film d'oxyde d'étain dopé à l'antimoine et la concentration en antimoine incluse dans la couche d'absorption de chaleur n'est pas supérieure à 11,5 % en moles et l'épaisseur de la couche réfléchissant les infrarouges est d'au moins 200 nm.
PCT/JP2022/021454 2021-05-31 2022-05-25 Substrat avec film stratifié WO2022255201A1 (fr)

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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
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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

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WO2024181270A1 (fr) * 2023-02-27 2024-09-06 王子ホールディングス株式会社 Verre avec film, et film avec couche de revêtement dur

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