WO2022255199A1 - 積層膜付き基材 - Google Patents

積層膜付き基材 Download PDF

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Publication number
WO2022255199A1
WO2022255199A1 PCT/JP2022/021448 JP2022021448W WO2022255199A1 WO 2022255199 A1 WO2022255199 A1 WO 2022255199A1 JP 2022021448 W JP2022021448 W JP 2022021448W WO 2022255199 A1 WO2022255199 A1 WO 2022255199A1
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Prior art keywords
laminated film
substrate
layer
film
infrared reflective
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PCT/JP2022/021448
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English (en)
French (fr)
Japanese (ja)
Inventor
淳志 関
卓 立川
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Ａｇｃ株式会社
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Priority to CN202280038979.4A priority Critical patent/CN117412935A/zh
Priority to JP2023525761A priority patent/JPWO2022255199A1/ja
Publication of WO2022255199A1 publication Critical patent/WO2022255199A1/ja

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

Definitions

  • the present invention relates to a 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 It is stated to be selected to have a difference between the solar energy transmission (for an air mass of 1.5).
  • Low-emissivity glasses such as those described in Patent Documents 1 and 2 have heat insulation due to the fluorine-doped tin oxide layer on the surface.
  • a heat insulating effect suitable for the usage environment can be obtained.
  • physical properties such as surface roughness change, and a laminated film having desired properties may not be obtained.
  • an object of the present invention is to provide a substrate with a laminated film having heat insulation properties, which exhibits excellent heat insulation properties and has a thinned layer that exhibits heat insulation properties.
  • the present inventors have worked diligently to solve the above problem, and have found that the above problem is achieved by forming a crystalline infrared reflective layer on the main material via a crystalline crystal growth base layer having a specific film thickness. can be solved, and the present invention has been achieved.
  • the present invention consists of the following configurations.
  • a laminated film-attached base material comprising a main material and a laminated film disposed on the main material, The main member has a first surface and a second surface facing each other, and the laminated film is provided on the first surface of the main member,
  • the laminated film has a crystalline crystal growth base layer and a crystalline infrared reflective layer from the side closer to the main material,
  • the crystal growth base layer has a thickness of 200 nm or more
  • a base material with a laminated film wherein the emissivity of the surface of the base material with the laminated film on the infrared reflective layer side is 0.40 or less.
  • 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.
  • the laminated film-coated base material of the present invention has excellent heat insulation properties, and the infrared reflective layer can be made thin, so it is possible to reduce manufacturing costs.
  • the base material is imparted with heat shielding properties, and a base material with a laminated film having heat insulation and heat shielding properties can be obtained.
  • 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 1 has a first surface 1a and a second surface 1b facing each other, and a laminated film 2 is provided on the first surface 1a of the main member 1 .
  • the laminated film 2 has a crystalline crystal growth base layer 3 and a crystalline infrared reflecting layer 5 in order from the side closer to the main material 1, and the thickness of the crystal growth base layer 3 is 200 nm or more.
  • the emissivity of the infrared reflective layer 5 side surface of the substrate 10 with the laminated film is 0.40 or less.
  • the emissivity is the reflectance for visible light measured according to ISO9050:2003.
  • the main material 1 serves as a skeleton of the base material 10 with a laminated film and has self-supporting properties.
  • Materials constituting the main material include, for example, glass and resin.
  • glass examples include soda lime silicate glass, aluminosilicate glass, borate glass, lithium aluminosilicate glass, quartz glass, borosilicate glass, alkali-free glass, and the like.
  • resins include polyolefin resins, polyester resins, polyamide resins, polystyrene resins, polyethylene terephthalate resins, polyvinyl chloride resins, and polycarbonate resins.
  • Polyolefin resins include, for example, polyethylene (low density, medium density, high density), polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer and the like.
  • glass can be suitably used as the main material for the base material with the laminated film of the present invention.
  • the main material can be selected from transparent, translucent, and opaque depending on the application and purpose of use of the laminated film-coated base material. 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.
  • a glass plate is used as the main material, the thickness of the glass plate is 1 mm to 5 mm, and the area of the main surface of the glass plate is 0.5 to 5 m 2 .
  • the base material with laminated film is used in a building, a glass plate is used as the main material, the thickness of the glass plate is 4 mm to 8 mm, and the area of the main surface of the glass plate is 0.5 to 10 m 2 . is preferred.
  • the 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 doped metal oxide obtained by doping at least one metal oxide of tin oxide and titanium oxide with another element, and the other element is fluorine, tantalum, niobium and At least one selected from the group consisting of aluminum is preferred.
  • the infrared reflective layer contains at least one dope selected from the group consisting of fluorine-doped tin oxide (FTO), tantalum-doped tin oxide, niobium-doped tin oxide, tantalum-doped titanium oxide, niobium-doped titanium oxide, and aluminum-doped tin oxide. It is more preferably made of a type metal oxide, and more preferably a fluorine-doped tin oxide (FTO) film from the viewpoint of obtaining higher heat insulation.
  • 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.
  • the composition of the infrared reflective layer and the concentration of impurity elements can be identified by X-ray photoelectron spectroscopy (XPS) or secondary ion mass spectroscopy (SIMS).
  • XPS X-ray photoelectron spectroscopy
  • SIMS secondary ion mass spectrometry
  • the thickness of the infrared reflective layer is preferably 50-1000 nm.
  • the thickness of the infrared reflective layer is preferably 50 nm or more, more preferably 80 nm or more, still more preferably 130 nm or more, more preferably 500 nm or less, even more preferably 450 nm or less, and particularly preferably 400 nm or less.
  • the thickness of the infrared reflective layer can be measured by depth direction analysis by X-ray photoelectron spectroscopy, cross-sectional observation by a scanning electron microscope, depth direction analysis by SIMS, or the like.
  • 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 crystal growth base layer on which the infrared reflective layer is laminated as described later has an uneven shape.
  • the base layer side surface and the surface opposite to the crystal growth base layer) have an uneven shape. Therefore, although the "thickness" of the infrared reflective layer varies depending on the location, in the present invention it represents the maximum thickness of the infrared reflective layer in the measurement area.
  • the size of the crystal grains in the infrared reflective layer is preferably 30 nm or more.
  • the size of the crystal grain is more preferably 30 nm or more, more preferably 50 nm or more, and particularly preferably 80 nm or more. Since the larger the crystal grain shape, the better, there is no particular upper limit, but it is generally 1000 nm. It is more preferably 800 nm or less, particularly preferably 500 nm or less.
  • 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 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 crystal growth base layer 3 is a layer that accelerates the crystal growth in the infrared reflective layer 5 laminated on the crystal growth base layer 3 to grow large crystal grains, and has crystallinity.
  • the infrared reflective layer 5 is formed of metal oxide crystal grains. Since the crystal grains grown in the infrared reflective layer 5 are grown based on the crystal grains 3, the crystal grains in the infrared reflective layer 5 can be grown large. Thereby, the emissivity of the infrared reflective layer 5 can be reduced to 0.40 or less.
  • Materials forming the crystal growth base layer include, for example, at least one metal oxide selected from the group consisting of tin oxide, indium oxide, zinc oxide, titanium oxide, niobium oxide, and tantalum oxide.
  • the crystal growth underlayer is preferably formed from the same type of metal oxide as the metal oxide contained in the infrared reflective layer.
  • the infrared reflective layer is a fluorine-doped tin oxide (FTO) film
  • FTO fluorine-doped tin oxide
  • the crystal growth base layer is preferably a tin oxide film. If the metal oxide is of the same kind as the metal oxide contained in the infrared reflective layer, the growth of crystal grains does not stop when forming the infrared reflective layer, and the crystal grains in the infrared reflective layer can grow large. can.
  • the metal oxide forming the crystal growth base layer may be a doped metal oxide doped with another element (impurity element).
  • the crystal growth base layer can be given a desired function.
  • the crystal growth substrate has heat absorption properties.
  • the impurity metal with which the doped metal oxide is doped is the same as described above, and examples thereof include fluorine, antimony, tin, potassium, aluminum, tantalum, niobium, nitrogen, boron, and indium.
  • antimony-doped tin oxide (ATO, a metal oxide in which Sb is added to SnO2 ) forms the base layer for crystal growth, which absorbs sunlight and reduces the amount of heat transmitted to the inside of the base material, thereby forming a laminated film.
  • Excellent heat shielding properties can be given to the attached base material.
  • the concentration of the impurity element to be doped is preferably 30 mol % or less.
  • the concentration of the metal to be doped is 30 mol % or less, the crystal structure before doping can be maintained.
  • the concentration of the doped metal 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 in order to impart heat shielding properties to the crystal growth base layer.
  • the concentration of the impurity element is more preferably 1 mol % or more, more preferably 2 mol % or more, particularly preferably 4 mol % or more, and 6 mol %. % or more is most preferable.
  • the concentration of antimony contained in the heat-absorbing layer is preferably 5 to 20 mol %.
  • 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 crystal growth base 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.
  • composition of the crystal growth base layer and the concentration of the impurity element to be doped 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 crystal growth base 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 crystal growth base layer is 200 nm or more.
  • the thickness of the crystal growth base layer is 200 m or more, the crystal grain size of the infrared reflective layer can be easily grown, and the crystal grains of the infrared reflective layer can be grown to a desired size. Crystal growth of the metal oxide is ensured during film formation, and the crystal grains of the infrared reflective layer become large.
  • the thickness of the crystal growth base layer is more preferably 250 nm or more, more preferably 300 nm or more. From the viewpoint of surface flatness, the thickness of the crystal growth base layer is preferably 1000 nm or less, more preferably 900 nm or less, and even more preferably 700 nm or less.
  • the thickness of the crystal growth base layer can be measured by analysis in the depth direction by X-ray photoelectron spectroscopy. Since the crystal growth base 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 crystal growth base layer varies depending on the location, in the present invention, it represents the maximum thickness of the crystal growth base layer in the measurement area.
  • the crystal grain size in the crystal growth base layer is preferably 30 to 1500 nm.
  • the crystal grain shape of the infrared reflective layer formed on the crystal growth base layer can be made sufficiently large.
  • the size of the crystal grains is more preferably 30 nm or more, more preferably 50 nm or more, and particularly preferably 80 nm or more. Since the larger the crystal grain shape, the better, there is no particular upper limit, but generally 1500 nm. It is more preferably 1200 nm or less, particularly preferably 1000 nm or less.
  • the size of the crystal grains is the same as above, and can be measured by cross-sectional observation with a scanning electron microscope.
  • the total thickness of the infrared reflecting layer and the crystal growth base layer is preferably 250-1500 nm.
  • the crystal grains in the infrared reflective layer can be sufficiently grown, and when it is 1500 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 crystal growth base layer is preferably 300 nm or more, more preferably 400 nm or more, particularly preferably 500 nm or more, and preferably 1500 nm or less, more preferably 1100 nm or less. , 900 nm or less.
  • the laminated film 2 may further have an optical adjustment layer 7 as shown in FIG.
  • the optical adjustment layer 7 is arranged between the main material 1 and the crystal growth base layer 3 .
  • optical adjustment layer Materials constituting the optical adjustment layer include, for example, silicon carbide oxide (SiOC), silicon oxide (SiO 2 ), titanium oxide (TiO 2 ), tin oxide (SnO 2 ), silicon nitride oxide (SiON), and the like. .
  • the optical adjustment layer may consist of one layer, or may consist of two or more layers. It may also be a mixture of any two or more of the above materials.
  • the optical adjustment layer includes a SiOC film, a SiOC/ SiO2 laminated film in which the SiOC film and the SiO2 film are laminated in this order from the main material side, and a TiO2 film and a SiO2 film in this order from the main material side. and a SnO 2 /SiO 2 laminated film in which the SnO 2 film and the SiO 2 film are laminated in this order from the main material side.
  • the optical adjustment layer preferably contains silicon, and is a group consisting of a SiOC film, a SiOC/SiO 2 laminated film, a TiO 2 /SiO 2 laminated film, and a SnO 2 /SiO 2 laminated film. and more preferably comprising a SiOC film.
  • the amount of silicon contained in the entire optical adjustment layer is preferably in the range of 5 to 40 mol%, more preferably 10 to 33 mol%.
  • the thickness of the optical adjustment layer is preferably 20-100 nm. When the thickness of the optical adjustment layer is 20 nm or more, the surface of the main material can be uniformly coated. A desired effect can be exhibited as an adjustment layer.
  • the thickness of the optical adjustment layer is preferably 20 nm or more, more preferably 25 nm or more, still more preferably 30 nm or more, and preferably 100 nm or less, more preferably 90 nm or less, and even more preferably 80 nm or less.
  • the "thickness" of the optical adjustment layer is represented by the total thickness of each layer.
  • the laminated film-coated base material of the present invention may have other layers as long as the effects of the present invention are not impaired.
  • Other layers include an overcoat layer and the like.
  • the emissivity of the surface on the infrared reflective layer side is 0.40 or less.
  • the emissivity is preferably 0.35 or less, more preferably 0.30 or less, and even more preferably 0.27 or less.
  • the lower limit of the emissivity is not particularly limited, but it is preferably 0.01 or more, more preferably 0.03 or more, and further preferably 0.10 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 laminated film-coated substrate can be measured using a commercially available emissometer (for example, "Emissometer model AE1" manufactured by Devices & Services) by the method described in JIS R3106 (2019) on the laminated film side surface.
  • the value of the sheet resistance of the laminated film-coated substrate is preferably 30 ohm/square (ohm/sq.: ⁇ / ⁇ ) or less.
  • the sheet resistance is 30 ohm/sq. When it is less than that, electricity flows easily, so the emissivity is low, and therefore excellent heat insulation can be obtained.
  • the value of sheet resistance is 30 ohm/sq. below, preferably 25 ohm/sq. The following is more preferable, and 20 ohm/sq. More preferred are:
  • the lower the sheet resistance the easier the flow of electricity and the lower the emissivity. Therefore, the lower limit of the sheet resistance is not particularly limited. 2 ohm/sq. 3 ohm/sq. The above is more preferable.
  • the sheet resistance value can be measured by Hall measurement.
  • the laminated film-coated substrate preferably has a transmittance (Tva, hereinafter also referred to as "A light source transmittance") based on standard A light source 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 2% or more, more preferably 3% or more, and further preferably 4% or more. Preferably, 5% or more is particularly 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 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 laminated film and the thickness of each layer constituting the laminated film.
  • the film-coated base material of the present invention preferably has a reflected color coordinate L * of 42 or less in the L * a * b * color system 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 is suppressed, and undesirable glare 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 film-coated substrate 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, which is -20 to 12.
  • 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 7 or less, more preferably 5 or less, even more preferably 3.5 or less, even more preferably 3 or less, particularly preferably 2.5 or less, most preferably 2 or less, Moreover, it is more preferably -15 or more, and even more preferably -12 or more.
  • the b * value is more preferably 5 or less, more preferably 2.5 or less, particularly preferably 2 or less, more preferably -15 or more, and even more preferably -10 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 a * , b * and L * values can be adjusted to desired values by adjusting the impurity concentration in the laminated film and the thickness of each layer constituting the film.
  • the mobility of the laminated film of the substrate with the laminated film is preferably 20 cm 2 /Vs or more.
  • the mobility of the laminated film is 20 cm 2 /Vs or more, excellent heat insulating properties can be obtained.
  • the mobility of the laminated film 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 substrate with a laminated film has a mobility of the infrared reflective layer of 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 laminated film and the infrared reflective layer of the film-coated substrate 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 laminated film-attached substrate 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 crystal growth base layer on the first surface of the main material (step S1); (b) placing an infrared reflective layer on the crystal growth substrate (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 crystal growth base layer is formed on the first surface of the main material.
  • the crystal growth base layer can be formed using various film formation methods such as chemical vapor deposition (CVD), electron beam deposition, vacuum deposition, sputtering, and spraying. Among them, a thermal CVD method is preferable because a high-temperature process is required to increase the crystal grain size. Furthermore, if it can be formed by the atmospheric pressure CVD method, a large-scale vacuum apparatus becomes unnecessary, and the productivity can be further improved.
  • CVD chemical vapor deposition
  • electron beam deposition electron beam deposition
  • vacuum deposition vacuum deposition
  • sputtering sputtering
  • spraying a thermal CVD method is preferable because a high-temperature process is required to increase the crystal grain size. Furthermore, if it can be formed by the atmospheric pressure CVD method, a large-scale vacuum apparatus becomes unnecessary, and the productivity can be further improved.
  • the crystal growth substrate is, for example, tin oxide, indium oxide, zinc oxide, 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).
  • the material forming the crystal growth base layer is preferably the same metal oxide used when forming the infrared reflective layer.
  • the infrared reflective layer is composed of fluorine-doped tin oxide (FTO)
  • the crystal growth base layer is composed of antimony-doped tin oxide (ATO) containing tin oxide, which is the same material as the metal oxide forming the infrared reflective layer, A case where each layer is formed by a thermal CVD method will be described.
  • a mixture of an inorganic or organic tin compound and an antimony compound is used as a raw material for the crystal growth base 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. Alternatively, the raw material gases may be mixed on the surface of the main material to be deposited. When the raw material is liquid, the raw material may be vaporized into a gas by using a bubbling method, a vaporizer, or the like.
  • the amount of water to 1 mol of the tin compound in the source gas is preferably 5 to 50 mol. If the amount of water is less than 5 mol, the resistance value of the film to be formed tends to increase, 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 moles, the volume of the raw material gas increases as the amount of water increases, and the flow rate of the raw material gas increases, which may reduce the film deposition efficiency. In addition, the number of starting points for nucleation increases, and as a result, crystal grains tend to grow smaller and the surface tends to become flat.
  • the amount of oxygen per 1 mol of the tin compound in the source gas is preferably more than 0 mol and 40 mol or less, more preferably 4 to 40 mol. If the amount of oxygen is too small, the resulting film may have an increased resistance value, so it is more preferably 4 mol or more. On the other hand, if the amount of oxygen exceeds 40 mol, the volume of the raw material gas increases and the flow rate of the raw material gas increases, which may reduce the film deposition efficiency.
  • the temperature of the main material for forming the crystal growth substrate is preferably 500° C. to 650° C. when the main material is a glass plate. If the temperature of the glass is less than 500°C, the rate of formation of the crystal growth base 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 crystal growth substrate than it reacts on the surface of the glass and the crystal growth substrate. As a result, more precursor flows into the surface irregularities of the glass and the crystal growth substrate, tending 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.
  • the speed at which the precursor reacts on the surface of the glass and the crystal growth substrate is faster than the speed at which the precursor diffuses on the surface of the glass and the crystal growth substrate.
  • the precursor tends to flow into the irregularities on the surface of the glass and the crystal growth base layer less, and the irregularities on the surface tend to increase.
  • the temperature of the main material when forming the crystal growth base layer is preferably 30 to 400°C.
  • the thickness of the crystal growth base layer is set to 200 nm or more.
  • the thickness of the crystal growth base layer is more preferably 250 nm or more, more preferably 300 nm or more.
  • the thickness of the crystal growth base layer is preferably 1000 nm or less, more preferably 900 nm or less, and even more preferably 700 nm or less.
  • the film thickness of the crystal growth base layer can be adjusted by adjusting the supply amount of the raw material, the substrate transport speed, the film forming temperature, the spraying flow rate, the distance between the film forming apparatus and the substrate, and the like.
  • Step S2 Next, an infrared reflective layer is formed on the crystal growth base layer.
  • the infrared reflective layer can also be formed using various film forming methods such as chemical vapor deposition (CVD), electron beam deposition, vacuum deposition, sputtering, and spraying. .
  • CVD chemical vapor deposition
  • the thermal CVD method is preferable because a high-temperature process is necessary to increase the infrared reflectivity by increasing the crystal grain size and increasing the electron mobility.
  • a large-scale vacuum apparatus becomes unnecessary, and the productivity can be further improved.
  • the infrared reflective layer is, for example, fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), tin-doped indium oxide (ITO), gallium-doped zinc oxide (GZO), aluminum-doped zinc oxide (AZO), as described above. etc., can be configured using various thin film materials.
  • FTO fluorine-doped tin oxide
  • ATO antimony-doped tin oxide
  • ITO tin-doped indium oxide
  • GZO gallium-doped zinc oxide
  • AZO aluminum-doped zinc oxide
  • the infrared reflective layer is composed of, for example, fluorine-doped tin oxide (FTO) or antimony-doped tin oxide (ATO), the unevenness of the surface of the infrared reflective layer can be increased, and the color tone can be adjusted within a predetermined range.
  • FTO fluorine-doped tin oxide
  • ATO antimony-doped tin oxide
  • the infrared reflective layer is composed of, for example, aluminum-doped zinc oxide (AZO) or gallium-doped zinc oxide (GZO), the crystal orientation tends to be uniform and the surface tends to be flat.
  • AZO aluminum-doped zinc oxide
  • GZO gallium-doped zinc oxide
  • tin-doped indium oxide has a strong function of reflecting infrared rays, and is often used in a film thickness range of around 100 nm. Therefore, when the infrared reflective layer is made of tin-doped indium oxide (ITO), it may be difficult to adjust the color tone of the reflected color within a predetermined range, resulting in insufficient crystal grain growth and surface roughness. It tends to be flat.
  • the infrared reflective layer is composed of a fluorine-doped tin oxide layer (FTO) 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 crystal growth base layer).
  • the raw material may be vaporized into a gas by using a bubbling method, a vaporizer, or the like.
  • the amount of water to 1 mol of the tin compound in the source gas is preferably 5 to 50 mol. If the amount of water is less than 5 mol, the resistance value of the film to be formed tends to increase, resulting in a decrease in the infrared reflecting function. In addition, the number of starting points for nucleation is reduced, and as a result, crystal grains tend to grow larger, and the surface tends to become rougher. On the other hand, if the amount of water exceeds 50 moles, the volume of the raw material gas increases as the amount of water increases, and the flow rate of the raw material gas increases, which may reduce the film deposition efficiency. In addition, the number of starting points for nucleation increases, and as a result, crystal grains tend to grow smaller and the surface tends to become flat.
  • the amount of oxygen per 1 mol of the tin compound in the source gas is preferably more than 0 mol and 40 mol or less, more preferably 4 to 40 mol. If the amount of oxygen is less than 4 moles, the resistance of the resulting film may increase. On the other hand, if the amount of oxygen exceeds 40 mol, the volume of the raw material gas increases and the flow rate of the raw material gas increases, which may reduce the film deposition efficiency.
  • the amount of the fluorine compound relative to 1 mol of the tin compound in the source gas is preferably 0.1 to 1.2 mol.
  • the resistance value of the formed film tends to increase.
  • the temperature for forming the infrared reflective layer is preferably 500° C. to 650° C. when a glass plate is used as the main material. If the treatment temperature is lower than 500°C, the formation speed of the infrared reflective layer may decrease. In addition, the precursor generated by the decomposition of the raw material gas diffuses faster on the surface of the glass and the infrared reflective layer than it reacts on the surface of the glass and the infrared reflective layer. As a result, more of the precursor flows into the surface irregularities of the glass and the infrared reflective layer, tending to flatten the surface.
  • the processing temperature is higher than 650° C.
  • film formation is performed while the viscosity of the glass is low, and warping may occur in the process of cooling the glass to room temperature.
  • the reaction speed of the precursor on the surface of the glass and the infrared reflective layer is higher than the speed of diffusion on the surface of the glass and the infrared reflective layer. As a result, the precursor tends to flow less into the irregularities on the surface of the glass and the infrared reflective layer, and the irregularities on the surface tend to increase.
  • the processing temperature for forming the infrared reflective layer is preferably 30 to 400°C.
  • steps S1 and S2 may be performed by an online method during the process of producing glass using a float facility.
  • film formation may be performed by reheating the glass plate manufactured by the float method by an off-line method.
  • the optical adjustment layer when an optical adjustment layer is provided between the main material and the crystal growth base layer, the optical adjustment layer is arranged on the first surface of the main material before step S1.
  • the optical adjustment layer is formed using various film formation methods such as chemical vapor deposition (CVD), electron beam evaporation, vacuum deposition, sputtering, and spraying. can be formed.
  • CVD chemical vapor deposition
  • electron beam evaporation electron beam evaporation
  • vacuum deposition vacuum deposition
  • sputtering sputtering
  • spraying spraying
  • the optical adjustment layer can be configured using various thin film materials such as SiOC, SiO2 , TiO2 , SnO2 , etc., as described above. Also, the optical adjustment layer may consist of one layer, or may be a laminate of two or more layers.
  • the optical adjustment layer when the optical adjustment layer includes a silicon carbide oxide (SiOC) layer, the optical adjustment layer may be deposited by a thermal CVD method.
  • a mixed gas containing monosilane (SiH 4 ), ethylene and carbon dioxide can be used as the raw material.
  • SiH 4 monosilane
  • ethylene and carbon dioxide when such a carbon-containing gas is used, it becomes easy to form a particulate silicon compound together with a film-like silicon compound, thereby increasing the haze ratio.
  • the raw material gases may be mixed in advance and then conveyed onto the first surface of the main member. Alternatively, the raw material gases may be mixed on the first surface of the main material.
  • the optical adjustment layer includes a silicon oxide (SiO 2 ) layer
  • mixed gases such as monosilane (SiH 4 ), tetraethoxysilane, and oxygen can be used as raw materials.
  • examples of raw materials include tetraisopropyl orthotitanate (TTIP) and titanium tetrachloride. Among them, tetraisopropyl orthotitanate (TTIP) is more preferable.
  • the temperature of the main material when forming the optical adjustment layer is preferably 500°C to 900°C. If the temperature of the main material is less than 500°C or more than 900°C, the film formation rate tends to decrease.
  • the overcoat layer is arranged on the surface of the infrared reflective layer after step S2.
  • the overcoat layer is formed, for example, by a wet method.
  • a coating solution for the overcoat layer is prepared.
  • the coating solution contains a metal oxide precursor, an organic solvent, and water. Particles and/or solids may also be added to the coating solution.
  • the composition of the particles may be the same as or different from the metal oxide precursor.
  • a coating solution is applied onto the infrared reflective layer of the laminated film-coated substrate.
  • the coating method is not particularly limited, and a common means such as spin coating may be used.
  • the laminated film-coated substrate on which the coating solution is applied is heat-treated in the atmosphere.
  • the temperature of the heat treatment is, for example, in the range of 80.degree. C. to 650.degree.
  • the heating time is, for example, in the range of 5 minutes to 360 minutes.
  • the heat treatment may be performed using a common device such as a hot air circulation furnace or an IR heater furnace.
  • An overcoat layer may also be formed from the coating solution by UV curing treatment, microwave treatment, or the like.
  • an overcoat layer can be formed on the infrared reflective layer.
  • the above heat treatment does not necessarily have to be performed at this stage. That is, the coating solution may be heated using a heating step that is performed in separate stages.
  • the substrate with a laminated film of the present invention can be produced.
  • the method for producing a base material with a laminated film of the present invention may further include a step (strengthening step) of air-cooling strengthening or chemical strengthening of the main material.
  • This strengthening step may be performed in any order, for example, before step S1 or after manufacturing the base material with the laminated film.
  • the obtained base material with the laminated film may be subjected to bending.
  • a step of bonding another glass plate to the surface on the glass plate side may be carried out.
  • the laminated film-coated base material of the present invention is also suitable for use as a base material for laminated glass, and laminated glass is obtained by laminating the laminated film-coated base material of the present invention, an intermediate film, and an outer glass plate in this order. be able to.
  • the laminated film-coated substrate of the present invention can be used, for example, for vehicle window glass (front glass, rear glass, side glass, roof glass, etc.), building window glass, and the like.
  • laminated glass provided with the film-coated substrate of the present invention is suitable for panoramic roofs.
  • 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, and the laminated film has a crystalline crystal growth base layer and a crystalline infrared reflective layer from the side closer to the main material, and the crystal growth A substrate with a laminated film, wherein the thickness of the base layer is 200 nm or more, and the emissivity of the surface of the substrate with the laminated film on the infrared reflective layer side is 0.40 or less.
  • ⁇ 2> The base material with a laminated film according to ⁇ 1>, wherein the infrared reflective layer has a thickness of 50 to 1000 nm.
  • ⁇ 3> The laminate according to ⁇ 1> or ⁇ 2>, wherein the infrared reflective layer is made of a doped metal oxide obtained by doping at least one metal oxide of tin oxide and titanium oxide with another element.
  • ⁇ 4> The laminated film-coated substrate according to ⁇ 3>, wherein the other element is at least one selected from the group consisting of fluorine, tantalum, niobium, and aluminum.
  • ⁇ 5> The laminated film according to ⁇ 3> or ⁇ 4>, wherein the concentration of the other element doped in the doped metal oxide forming the infrared reflective layer is 0.01 to 20 mol%.
  • Base material with. ⁇ 6> The substrate with a laminated film according to any one of ⁇ 3> to ⁇ 5>, wherein the crystal growth base layer is made of the same metal oxide as the metal oxide contained in the infrared reflective layer. . ⁇ 7> Any one of ⁇ 3> to ⁇ 5> above, wherein the crystal growth base layer is made of a doped metal oxide obtained by doping antimony to the same metal oxide as the metal oxide contained in the infrared reflective layer. 1. The base material with a laminated film according to one.
  • ⁇ 8> The substrate with a laminated film according to ⁇ 7>, wherein the concentration of the element doped in the doped metal oxide forming the crystal growth base layer is 30 mol % or less.
  • ⁇ 9> The laminated film-attached substrate according to any one of ⁇ 1> to ⁇ 8>, wherein the infrared reflective layer is formed from fluorine-doped tin oxide, and the crystal growth base layer is formed from antimony-doped tin oxide. material.
  • ⁇ 10> The substrate with a laminated film according to any one of ⁇ 1> to ⁇ 9>, wherein the crystal growth base layer has heat absorption properties.
  • ⁇ 11> The laminated film-coated substrate according to any one of ⁇ 1> to ⁇ 10>, wherein the laminated film-coated substrate has a solar transmittance of less than 30%.
  • ⁇ 12> The laminated film-coated substrate according to any one of ⁇ 1> to ⁇ 11>, wherein the laminated film-coated substrate has a transmittance of less than 30% based on a standard A light source.
  • ⁇ 13> The film-coated substrate according to ⁇ 12>, wherein the transmittance based on the standard A light source is 3 to 13%.
  • the laminated film-coated substrate has a sheet resistance value of 30 ohm/
  • ⁇ 17> The laminated film-attached substrate according to any one of ⁇ 1> to ⁇ 16>, wherein the laminated film has a mobility of 20 cm 2 /Vs or more.
  • ⁇ 18> The above ⁇ 1> to ⁇ 17>, wherein the color coordinate a * 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.
  • the base material with a laminated film according to any one of the above.
  • ⁇ 19> Any of the above ⁇ 1> to ⁇ 18>, wherein the color coordinate b * of the reflected color in the L * a * b * color system is 5 or less when light from a D65 light source is incident at an incident angle of 10 degrees. or a substrate with a laminated film according to any one of the above.
  • ⁇ 20> The substrate with a laminated film according to any one of ⁇ 1> to ⁇ 19>, wherein the main material is glass.
  • the laminated film further includes an optical adjustment layer, and the optical adjustment layer is disposed between the main material and the crystal growth base layer. 3.
  • the optical adjustment layer has at least one film selected from the group consisting of a SiOC film, a SiOC/SiO 2 laminated film, a TiO 2 /SiO 2 laminated film, and a SnO 2 /SiO 2 laminated film. 21>, the laminated film-attached substrate. ⁇ 23> The substrate with a laminated film according to ⁇ 22>, wherein the optical adjustment layer includes a SiOC film. ⁇ 24> The film-coated substrate according to any one of ⁇ 1> to ⁇ 23>, wherein the laminated film is formed by a thermal CVD method. ⁇ 25> The film-coated substrate according to ⁇ 24>, wherein the main material is glass, and the laminated film is formed by the thermal CVD method on a production line for the glass.
  • ⁇ 26> A vehicle window glass comprising the film-coated substrate according to any one of ⁇ 1> to ⁇ 25>.
  • ⁇ 27) A laminated glass comprising the film-coated substrate according to any one of ⁇ 1> to ⁇ 25>, an intermediate film and an outer glass plate in this order.
  • ⁇ 28> The laminated glass according to ⁇ 27>, which is used for a roof of a vehicle.
  • ⁇ 29> A panoramic roof comprising the laminated glass according to ⁇ 27>.
  • 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 directly examined 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 crystal growth base layer and the infrared reflective layer cannot be confirmed by SEM observation, after examining the sum of the thicknesses of the crystal growth base layer and the infrared reflective layer from the SEM image, the depth direction by X-ray photoelectron spectroscopy (XPS). was used to investigate the thickness ratio of the crystal growth base layer and the infrared reflective 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 crystal growth base layer in this example is an ATO (antimony-doped tin oxide) film, the point (time) at which the molar ratio of Sb obtained by depth profile analysis by XPS begins to increase with respect to the etching time and the point at which the increase ends The midpoint between the points (time) at which the slope becomes approximately zero was set as the interface between the crystal growth base 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 showing the same molar ratio of Sn and Si was set as the interface between the crystal growth base 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 crystal growth base layer and the infrared reflective 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 electronic information of the O1s, Si2p, Sn3d5, and Sb3d3 orbitals was referred to. was corrected by subtracting 1.5 times from the O1s peak intensity.
  • "PHI 5000 Versa Probe" manufactured by ULVAC-PHI was used.
  • 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 emissivity of the substrate with the laminated film on the infrared reflective layer side was measured by the method described in JIS R3106 (2019) using "Emissometer model AE1" manufactured by Devices & Services. Then, in order to confirm the degree of improvement in heat insulation by the crystal growth base layer, the rate of decrease in emissivity was calculated as follows.
  • the emissivity of the laminated film-coated substrate prepared in each example is Te1, and an infrared reflective layer having the same film thickness as the infrared reflective layer of the laminated film-coated substrate is formed directly on the optical adjustment layer without providing a crystal growth base layer.
  • the laminated film-attached base material 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 laminated film-coated substrate is cut into 1 cm squares, and the mobility of the layers (the crystal growth base layer and the infrared reflective layer) in which electricity flows in the laminated film-coated substrate is measured using a Hall measuring instrument ("HL 5500 PC” manufactured by Nanometrics). Van der Pauw method).
  • the laminated film-coated substrate is cut into 1 cm squares, and a sheet carrier density (1 /cm 2 ) was measured (Van der Pauw method) and divided by the sum of the film thicknesses of the crystal growth base layer and the infrared reflective layer to obtain the portion (the crystal growth base layer and the infrared reflective layer) where electricity flows in the substrate with the laminated film.
  • a carrier density (1/cm 3 ) was derived.
  • the haze of the laminated film-coated substrate was measured using a haze meter "HZ-V3" manufactured by Suga Test Instruments Co., Ltd.
  • 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.
  • a crystal growth base layer was formed on the SiOC layer.
  • Antimony-doped tin oxide SnO 2 :Sb, ATO
  • SnO 2 :Sb, ATO Antimony-doped tin oxide
  • MBTC Monobutyltin trichloride
  • SbCl 3 antimony trichloride
  • water, air, and hydrogen chloride were used as source gases, and nitrogen was used as carrier gas.
  • the target thickness (maximum thickness) of the crystal growth base layer was set to 450 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 (maximum thickness) of the infrared reflective layer was 250 nm. As a result, a base material with a laminated film was obtained.
  • Examples 2-22 By the same method as in Example 1, a substrate with a laminated film having the layer structure shown in Table 1 was produced. In Examples 16 to 22, the FTO film (infrared reflective layer) was directly formed on the SiOC layer (optical adjustment layer) without the crystal growth base layer.
  • Examples 1 to 15 all showed lower emissivity than Examples 16 to 22, and the decrease rate was also low. From these results, it was found that by laminating an infrared reflective layer on the crystal growth base layer, the emissivity of the base material can be reduced and excellent heat insulation can be obtained.

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
JP2002193640A (ja) * 2000-10-30 2002-07-10 Atofina Chemicals Inc ソーラーコントール被覆ガラス
JP2003535004A (ja) * 1999-08-10 2003-11-25 リビー−オーウェンズ−フォード・カンパニー ソーラーコントロールコーティングを有するガラス製品
WO2012176467A1 (ja) * 2011-06-24 2012-12-27 日本板硝子株式会社 透明導電膜付きガラス板およびその製造方法
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

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
JP2002193640A (ja) * 2000-10-30 2002-07-10 Atofina Chemicals Inc ソーラーコントール被覆ガラス
WO2012176467A1 (ja) * 2011-06-24 2012-12-27 日本板硝子株式会社 透明導電膜付きガラス板およびその製造方法
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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