WO2014109369A1 - Corps stratifié et verre multicouche - Google Patents

Corps stratifié et verre multicouche Download PDF

Info

Publication number
WO2014109369A1
WO2014109369A1 PCT/JP2014/050248 JP2014050248W WO2014109369A1 WO 2014109369 A1 WO2014109369 A1 WO 2014109369A1 JP 2014050248 W JP2014050248 W JP 2014050248W WO 2014109369 A1 WO2014109369 A1 WO 2014109369A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
film
metal
dielectric
silver
Prior art date
Application number
PCT/JP2014/050248
Other languages
English (en)
Japanese (ja)
Inventor
すすむ 鈴木
史栄 坂本
秀文 小高
Original Assignee
旭硝子株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 旭硝子株式会社 filed Critical 旭硝子株式会社
Publication of WO2014109369A1 publication Critical patent/WO2014109369A1/fr

Links

Images

Classifications

    • E—FIXED CONSTRUCTIONS
    • E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
    • E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
    • E06B9/00—Screening or protective devices for wall or similar openings, with or without operating or securing mechanisms; Closures of similar construction
    • E06B9/24—Screens or other constructions affording protection against light, especially against sunshine; Similar screens for privacy or appearance; Slat blinds
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal 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
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • 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
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3618—Coatings of type glass/inorganic compound/other inorganic layers, at least one layer being metallic
    • 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
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3626—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer one layer at least containing a nitride, oxynitride, boronitride or carbonitride
    • 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
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3644—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the metal being silver
    • 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
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3657—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having optical properties
    • C03C17/366—Low-emissivity or solar control coatings
    • 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
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3681—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating being used in glazing, e.g. windows or windscreens
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/204—Di-electric
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/304—Insulating
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/418—Refractive
    • 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
    • B32B2551/00—Optical elements

Definitions

  • the present invention relates to a laminate and a multi-layer glass, and more particularly, to a multi-layer glass having one silver layer, good thermal insulation and obtaining specific optical characteristics, and a multi-layer glass using the same.
  • the silver layer has a neutral color (neutral color) in the visible and transmitted colors and a low resistivity.
  • neutral color neutral color
  • the thickness is about 10 nm, there is little absorption in the visible range, and the reflectance is several tens of percent. The reflectance increases as the wavelength becomes longer, and shows a high reflectance in the infrared region.
  • a silver multilayer film with a silver layer sandwiched between dielectric layers with low reflectivity in the visible range and high reflectivity in the infrared range shows the same appearance as general glass, and has low emissivity and high heat ray reflectivity. Show. Therefore, the silver-based multilayer film is used for highly heat-insulating Low-E glass and heat ray reflective glass having high transmittance in the visible light region. In recent years, with the growing awareness of energy saving, the demand for these glasses has increased.
  • a silver-based multilayer film having two silver layers is known (for example, see Patent Document 1). Moreover, what has two silver layers and a light absorption layer is known as a silver type multilayer film (for example, refer patent document 2, 3).
  • a silver multilayer film having two silver layers is known. Those having two silver layers have good heat shielding properties because the thickness of the silver layer is increased as a whole, but the productivity is not necessarily good because of the increased number of layers. On the other hand, those having one silver layer have good productivity because the number of laminated layers is small, but the heat shielding property is not necessarily good only with a thin silver layer.
  • window glass not only has good heat shielding properties, but also has specific visible light transmittance and visible light reflectance from the viewpoint of use place, usage, design, etc., and transmitted light It is also required that the reflected light has a specific color tone.
  • the present invention has been made in order to solve the above-mentioned problems, and has one silver layer, has good heat shielding properties, and has a good appearance by obtaining specific optical characteristics.
  • the purpose is to provide the body.
  • Another object of the present invention is to provide a multi-layer glass using such a laminate.
  • the laminate of the present invention has a transparent substrate and a laminated film provided on the transparent substrate.
  • the laminated film has a first dielectric layer, a silver layer, a light absorption layer, and a second dielectric layer in order from the transparent substrate side.
  • the first dielectric layer has a refractive index of 1.9 to 2.1 and a geometric thickness of 20 to 30 nm.
  • the silver layer is mainly composed of silver and has a geometric thickness of 11 to 18 nm.
  • the light absorbing layer has a geometric thickness of 1 to 6 nm.
  • the second dielectric layer has a refractive index of 1.9 to 2.1 and a geometric thickness of 35 to 48 nm.
  • the multilayer glass of the present invention has the above-described laminate of the present invention and a counter substrate disposed on the laminate film side of the laminate.
  • the laminated body of the present invention comprises, as a laminated film, a first dielectric layer having a refractive index of 1.9 to 2.1 and a geometric thickness of 20 to 30 nm in order from the transparent substrate side, and silver as a main component.
  • a second dielectric layer having a thickness.
  • Sectional drawing which shows one Embodiment of a laminated body Sectional drawing which shows the 1st structural example of a laminated body. Sectional drawing which shows the 2nd structural example of a laminated body. Sectional drawing which shows the 3rd structural example of a laminated body. Sectional drawing which shows one Embodiment of multilayer glass.
  • FIG. The figure which shows a * b * of the reflected light (board
  • FIG. The figure which shows a * b * of the reflected light (film
  • FIG. The figure which shows a * b * of the reflected light (film
  • FIG. 1 is a cross-sectional view showing an embodiment of a laminate.
  • the laminate 10 has a transparent substrate 11 and a laminate film 12 provided on the transparent substrate 11.
  • the laminated film 12 includes a first dielectric layer 13, a silver layer 14, a light absorbing layer 15, and a second dielectric layer 16 in order from the transparent substrate 11 side.
  • the first dielectric layer 13 has a refractive index of 1.9 to 2.1 and a geometric thickness of 20 to 30 nm.
  • the silver layer 14 is mainly composed of silver and has a geometric thickness of 11 to 18 nm.
  • the light absorption layer 15 has a geometric thickness of 1 to 6 nm.
  • the second dielectric layer 16 has a refractive index of 1.9 to 2.1 and a geometric thickness of 35 to 48 nm.
  • the refractive index in this invention means the refractive index in wavelength 550nm.
  • the laminate 10 is roughly divided into a non-heat treated product and a heat treated product.
  • the non-heat-treated product is simply a laminated film 12 formed into a final product in the final form, and no heat treatment for strengthening or bending is performed after the film formation.
  • the heat-treated product is subjected to a heat treatment for strengthening or bending after the formation of the laminated film 12 to be a final product in a final form.
  • the laminate 10 may be either a non-heat treated product or a heat treated product.
  • the above geometric thicknesses are all in the finished product.
  • the geometric thickness is after the formation of the laminated film 12, and in the case of a heat-treated product, after the formation of the laminated film 12. After heat treatment for strengthening or bending performed.
  • the thickness is assumed to be a geometric thickness unless otherwise specified.
  • the transparent substrate 11 is not particularly limited.
  • a glass plate having an inorganic transparency such as a window glass for buildings, a commonly used float glass, or a soda-lime glass manufactured by a roll-out method is used. Can be used.
  • colorless ones such as clear glass and high transmission glass and green ones such as heat ray absorbing glass can be used. In consideration of visible light transmittance, colorless glass such as clear glass and high transmittance glass is preferable among them.
  • Various tempered glasses such as air-cooled tempered glass and chemically tempered glass can also be used.
  • various glasses such as borosilicate glass, low expansion glass, zero expansion glass, low expansion crystallized glass, and zero expansion crystallized glass can be used.
  • the thickness of the transparent substrate 11 is not necessarily limited, but is preferably 0.5 to 20 mm, for example.
  • the first dielectric layer 13 is provided in order to adjust the reflectance in the visible range and the like by the optical interference effect so that the optical characteristics of the laminate 10 become desired characteristics.
  • the first dielectric layer 13 has a refractive index of 1.9 to 2.1. By setting it as such a refractive index, the reflectance etc. in a visible region are adjusted with a light interference effect, and the optical characteristic of the laminated body 10 can be made into a desired characteristic.
  • the first dielectric layer 13 has a thickness of 20 to 30 nm. By setting the thickness of the first dielectric layer 13 within the above range, the optical characteristics of the stacked body 10 can be adjusted to desired characteristics by adjusting the reflectance in the visible range by the optical interference effect.
  • the thickness of the first dielectric layer 13 is preferably 21 nm or more, more preferably 22 nm or more, and further preferably 23 nm or more.
  • the thickness of the first dielectric layer 13 is preferably 29 nm or less, more preferably 28 nm or less, and even more preferably 27 nm or less.
  • the constituent material of the first dielectric layer 13 is not particularly limited as long as it is a dielectric having the above refractive index, and includes various oxides and nitrides.
  • the oxide include an oxide mainly composed of an oxide of at least one element selected from zinc, tin, niobium, and titanium.
  • the nitride include those containing as a main component a nitride of at least one element selected from silicon and aluminum.
  • the oxide aluminum zinc oxide and tin zinc oxide are particularly preferable.
  • the aluminum zinc oxide preferably has an aluminum ratio of 1 to 10 atomic%, more preferably 3 to 7 atomic%, based on the total amount of zinc and aluminum.
  • the tin zinc oxide is preferably one in which the ratio of tin to the total amount of zinc and tin is 10 to 80% by mass, and more preferably 20 to 80% by mass.
  • the first dielectric layer 13 is not necessarily limited to a single-layer structure composed of one kind of dielectric layer, but may be a laminated structure in which two or more kinds of dielectric layers are laminated, although not shown.
  • the refractive indexes of the individual dielectric layers are not necessarily the same, and may be different as long as they are within the refractive index range of 1.9 to 2.1.
  • aluminum zinc oxide is preferred.
  • the aluminum zinc oxide preferably has an aluminum ratio of 1 to 10 atomic%, more preferably 3 to 7 atomic%, based on the total amount of zinc and aluminum.
  • the layer disposed at the position closest to the silver layer 14 is preferably aluminum zinc oxide.
  • the aluminum zinc oxide preferably has an aluminum ratio of 1 to 10 atomic%, more preferably 3 to 7 atomic%, based on the total amount of zinc and aluminum.
  • the thickness of the aluminum zinc oxide is preferably 1 nm or more, and more preferably 3 nm or more.
  • the layers other than the layer disposed at the position closest to the silver layer 14 are not necessarily limited, but tin zinc oxide is preferable.
  • the tin zinc oxide preferably has a tin ratio of 10 to 90% by mass and more preferably 20 to 80% by mass with respect to the total amount of zinc and tin.
  • the silver layer 14 only needs to be composed mainly of silver, and is made of, for example, silver alone or a silver alloy containing a metal such as palladium.
  • the ratio of the metal other than silver to the total amount of silver and a metal element other than silver is preferably 10% by mass or less, more preferably 5% by mass or less, more preferably 3% by mass in terms of heat shielding properties and cost. The following is more preferable.
  • the silver layer 14 consists essentially of silver.
  • the silver layer 14 has a thickness of 11 to 18 nm. By making the thickness of the silver layer 14 relatively large, 11 nm or more, the transmittance in the infrared region is lowered, and the heat shielding property can be improved. Moreover, the optical characteristic of the laminated body 10 can be made into a desired characteristic by the thickness of the silver layer 14 being 18 nm or less.
  • the thickness of the silver layer 14 is preferably 12 nm or more, more preferably 13 nm or more, and further preferably 14 nm or more.
  • the light absorption layer 15 has absorption in the visible light region, reduces visible light transmittance by absorption of visible light, improves thermal insulation, and makes the optical characteristics of the laminate 10 desired characteristics. .
  • the thickness of the light absorption layer 15 is 1 to 6 nm. By setting the thickness of the light absorption layer 15 to 1 nm or more, the visible light transmittance can be effectively reduced by absorbing visible light. Further, by setting the thickness of the light absorption layer 15 to 6 nm or less, excessive absorption of visible light can be suppressed, and the optical characteristics of the laminate 10 can be set to desired characteristics.
  • the thickness of the light absorption layer 15 is preferably 5 nm or less.
  • the constituent material of the light absorption layer 15 is not particularly limited as long as it has absorption in the visible light region.
  • Examples of the constituent material of the light absorption layer 15 include metals or nitrides having absorption in the visible light region.
  • the metal examples include metals such as titanium, zirconium, hafnium, niobium, nickel, and chromium, and alloys containing at least one of these metals.
  • the alloy examples include a titanium zirconium alloy, a titanium hafnium alloy, a nickel chromium alloy, a nickel aluminum alloy, and a nickel iron alloy. Among these, an alloy mainly containing titanium is preferable, an alloy containing 90% by mass or more of titanium is preferable, and only titanium is more preferable.
  • nitride examples include a nitride of at least one element selected from silicon, aluminum, and chromium.
  • the light absorption layer 15 preferably has a metal layer made of the above metal, and more preferably only a metal layer.
  • the light absorption layer 15 preferably has a nitride layer made of the nitride.
  • the light absorption layer 15 may have both a nitride layer and a metal layer.
  • the second dielectric layer 16 is provided in order to adjust the reflectance in the visible range by the optical interference effect and to make the optical characteristics of the laminate 10 desired characteristics.
  • the second dielectric layer 16 has a refractive index of 1.9 to 2.1. By setting it as such a refractive index, the reflectance etc. in a visible region are adjusted with a light interference effect, and the optical characteristic of the laminated body 10 can be made into a desired characteristic.
  • the second dielectric layer 16 is mainly composed of a dielectric film formed from the beginning (dielectric layer from the beginning).
  • the second dielectric layer 16 is not necessarily limited to the original dielectric layer. That is, the second dielectric layer 16 is a dielectric when it is finished, in addition to the original dielectric layer, and is continuous with the original dielectric layer. Is included.
  • Such a dielectric is, for example, a metal film functioning as a barrier film provided as a base layer positioned under the dielectric layer before the initial formation of the dielectric layer.
  • a metal film functioning as a barrier film provided as a base layer positioned under the dielectric layer before the initial formation of the dielectric layer. Examples are those that are oxidized when the dielectric layer is formed into a dielectric, and have a refractive index of 1.9 to 2.1.
  • an adhesive film provided as a base layer located under the protective film, and when the protective film is subsequently formed An oxide that has been oxidized into a dielectric and has a refractive index of 1.9 to 2.1 can be used.
  • the film formed as a barrier film or an adhesive film as described above is also a dielectric having a refractive index of 1.9 to 2.1 when it is a finished product, If it is continuously disposed as a dielectric relative to the layer, it is included in the second dielectric layer 16. That is, it is included in the thickness of the second dielectric layer 16.
  • the second dielectric layer 16 has a thickness of 35 to 48 nm. By setting the thickness of the second dielectric layer 16 within the above range, it is possible to adjust the reflectance in the visible range by the optical interference effect, and to make the optical characteristics of the stacked body 10 desired characteristics.
  • the thickness of the second dielectric layer 16 is preferably 37 nm or more, more preferably 38 nm or more, and further preferably 39 nm or more.
  • the thickness of the second dielectric layer 16 is preferably 47 nm or less.
  • the constituent material of the second dielectric layer 16 is not particularly limited as long as it is a dielectric having the above-described refractive index, and various oxides and nitrides can be used.
  • the oxide include an oxide mainly composed of an oxide of at least one element selected from zinc, tin, niobium, and titanium.
  • the nitride include those containing as a main component a nitride of at least one element selected from silicon and aluminum.
  • the constituent material of the second dielectric layer 16 that is a dielectric from the beginning is preferably an oxide, and particularly preferably aluminum zinc oxide or tin zinc oxide.
  • the aluminum zinc oxide preferably has an aluminum ratio of 1 to 10 atomic%, more preferably 3 to 7 atomic%, based on the total amount of zinc and aluminum.
  • the tin zinc oxide preferably has a tin ratio of 10 to 90% by mass, more preferably 20 to 80% by mass with respect to the total amount of zinc and tin.
  • the portion that has been a dielectric material from the beginning is not necessarily limited to a single-layer structure composed of one kind of dielectric layer, but may be a laminated structure in which two or more kinds of dielectric layers are laminated, although not shown. .
  • the refractive indexes of the individual dielectric layers are not necessarily the same, and may be different as long as they are within the refractive index range of 1.9 to 2.1.
  • aluminum zinc oxide or tin zinc oxide is preferable.
  • the aluminum zinc oxide preferably has an aluminum ratio of 1 to 10 atomic%, more preferably 3 to 7 atomic%, based on the total amount of zinc and aluminum.
  • the stacking order is not necessarily limited, and may be the order of aluminum zinc oxide and tin zinc oxide in order from the transparent substrate 11 side, or the order of tin zinc oxide and aluminum zinc oxide. Among these, the order of aluminum zinc oxide and tin zinc oxide is more preferable.
  • a metal oxide layer formed by oxidation of a metal film functioning as a barrier film is disposed on the light absorption layer 15 side of the second dielectric layer 16.
  • the metal oxide include metals such as titanium, zirconium, hafnium, niobium, nickel, and chromium, and alloys containing at least one of these metals.
  • the alloy include a titanium zirconium alloy, a titanium hafnium alloy, a nickel chromium alloy, a nickel aluminum alloy, and a nickel iron alloy.
  • the thickness of the metal oxide layer is usually about 1 to 3 nm.
  • FIG. 2 shows a first configuration example of the laminate 10.
  • the first configuration example is a preferable configuration example of the non-heat treated product.
  • the light absorption layer 15 preferably has a metal layer 151.
  • the metal oxide layer 17 is formed by oxidation of a metal film that functions as a barrier film. If the refractive index is in the range of 1.9 to 2.1, the metal oxide layer 17 is included in the second dielectric layer 16. If the refractive index is outside the range of 1.9 to 2.1, it is not included in the second dielectric layer 16.
  • the metal oxide layer 17 is preferably made of an oxide of the same metal as that contained in the metal layer 151.
  • the light absorbing layer 15 (metal layer 151), the metal oxide layer 17, and the second dielectric layer 16 are formed on the metal layer after a relatively thick metal film is formed on the silver layer 14.
  • the second dielectric layer 16 can be formed. That is, when the second dielectric layer 16 is formed, a part of the metal film on the second dielectric layer 16 side can be oxidized to form the metal oxide layer 17, and the silver layer 14 of the metal film can be formed.
  • the metal layer 151 can be formed by leaving the remaining portion on the side without being oxidized. In this case, the metal film is used for forming the metal layer 151 and also used as a barrier film for suppressing oxidation of the silver layer 14 when the second dielectric layer 16 is formed. With such a configuration, the light absorption layer 15 (metal layer 151) can be formed while suppressing the oxidation of the silver layer 14, and the productivity can be improved.
  • the thickness of the metal layer 151 is 1 to 6 nm.
  • the thickness of the metal layer 151 is more preferably 5 nm or less, further preferably 4 nm or less, and particularly preferably 3 nm or less.
  • the constituent material of the metal layer 151 include metals such as titanium, zirconium, hafnium, niobium, nickel, and chromium, and alloys containing at least one of these metals.
  • the alloy include a titanium zirconium alloy, a titanium hafnium alloy, a nickel chromium alloy, a nickel aluminum alloy, and a nickel iron alloy. Among these, an alloy mainly containing titanium is preferable, an alloy containing 90% by mass or more of titanium is more preferable, and only titanium is more preferable.
  • the metal oxide layer 17 is preferably made of the same metal oxide as the metal contained in the metal layer 151.
  • the metal oxide layer 17 is formed, for example, by oxidizing a part of the metal film that becomes the metal layer 151 when the second dielectric layer 16 is formed.
  • the thickness of the metal oxide layer 17 is usually about 1 to 3 nm.
  • an adhesive layer 18 and a protective layer 19 are provided in this order from the second dielectric layer 16 side as necessary.
  • the adhesive layer 18 is provided as necessary to improve the adhesiveness between the second dielectric layer 16 and the protective layer 19.
  • the constituent material of the adhesive layer 18 is not particularly limited as long as the adhesion between the second dielectric layer 16 and the protective layer 19 can be improved, but a nitride or a dielectric having a refractive index of 1.9 to 2.5 is preferable.
  • an oxide of titanium is preferable.
  • the adhesive layer 18 may be formed as a nitride film and then oxidized into an oxide film when the protective layer 19 is formed.
  • a thickness of 0.5 nm or more is preferable. By setting the thickness to 0.5 nm or more, the adhesion between the second dielectric layer 16 and the protective layer 19 can be effectively improved.
  • the thickness of the adhesive layer 18 is usually sufficient if it is 5 nm.
  • the protective layer 19 is not particularly limited as long as it can improve the scratch resistance of the surface, but a dielectric having a refractive index of 1.9 to 2.4 is preferable.
  • the constituent material of the protective layer 19 is preferably a zirconium titanium oxide film from the viewpoint of scratch resistance.
  • the thickness of the protective layer 19 is preferably 1 nm or more. By setting the thickness of the protective layer 19 to 1 nm or more, the scratch resistance can be effectively improved.
  • the thickness of the protective layer 19 is more preferably 2 nm or more. Further, the thickness of the protective layer 19 is preferably 10 nm or less, more preferably 7 nm or less, and even more preferably 5 nm or less from the viewpoint of suppressing an excessive decrease in visible light transmittance.
  • the adhesive layer 18 is regarded as a part of the second dielectric layer 16 when it is a dielectric having a refractive index of 1.9 to 2.1 when it is a finished product. Further, when the adhesive layer 18 is a dielectric having a refractive index of 1.9 to 2.1 and the protective layer 19 is a dielectric having a refractive index of 1.9 to 2.1, The protective layer 19 is also regarded as a part of the second dielectric layer 16.
  • FIG. 3 shows a second configuration example of the laminate 10.
  • the second configuration example is a preferable configuration example of the heat-treated product.
  • the light absorption layer 15 preferably has a nitride layer 152.
  • the metal oxide layer 17 and the 2nd dielectric material layer 16 are formed by oxidation of a metal film that functions as a barrier film.
  • the light absorption layer 15 (nitride layer 152), the metal oxide layer 17 and the second dielectric layer 16 are formed by forming a nitride layer 152 on the silver layer 14 and forming the nitride layer 152 on the nitride layer 152. It can be formed by forming a metal film and forming the second dielectric layer 16 on the metal film. That is, when the second dielectric layer 16 is formed, the metal film can be oxidized to form the metal oxide layer 17. In this case, the metal film functions as a barrier film that suppresses oxidation of the silver layer 14 when the second dielectric layer 16 is formed.
  • the nitride layer 152 has a function of suppressing the reaction between the silver layer 14 and the upper layer thereof during heat treatment or the like and maintaining absorption as an optical property. With such a configuration, the light absorption layer 15 (nitride layer 152) can be formed while suppressing the oxidation of the silver layer 14, and the productivity is improved.
  • the thickness of the nitride layer 152 is preferably 1 nm or more from the viewpoint of effectively reducing the visible light transmittance by assisting the absorption of visible light and suppressing deterioration of the silver layer 14, and 1.5 nm or more. Is more preferable.
  • Examples of the constituent material of the nitride layer 152 include a nitride of at least one element selected from silicon, aluminum, and chromium.
  • the metal oxide layer 17 is formed by oxidation of a metal film that functions as a barrier film when the second dielectric layer 16 is formed.
  • the metal film is preferably made of a metal having absorption in the visible light region.
  • the metal include metals such as titanium, zirconium, hafnium, niobium, nickel, chromium, and alloys containing at least one of these metals.
  • the alloy include a titanium zirconium alloy, a titanium hafnium alloy, a nickel chromium alloy, a nickel aluminum alloy, and a nickel iron alloy.
  • the thickness of the metal oxide layer 17 is usually about 1 to 3 nm.
  • an adhesive layer 18 and a protective layer are provided in this order from the second dielectric layer 16 side as necessary.
  • the adhesive layer 18 is provided as necessary in order to improve the adhesion between the second dielectric layer 16 and the protective layer.
  • the constituent material of the adhesive layer 18 is not particularly limited as long as the adhesion between the second dielectric layer 16 and the protective layer can be improved, but a nitride or dielectric having a refractive index of 1.9 to 2.5 is preferable. In particular, an oxide of titanium is preferable.
  • the adhesive layer 18 is formed as a nitride film, for example, and then oxidized when forming the protective layer to become an oxide film.
  • a thickness of 0.5 nm or more is preferable. By setting the thickness to 0.5 nm or more, the adhesiveness between the second dielectric layer 16 and the protective layer can be effectively improved.
  • the thickness of the adhesive layer 18 is usually sufficient if it is 5 nm.
  • the protective layer may disappear when a heat treatment for strengthening or bending is performed, and may not exist in the finished product.
  • An example of such a protective layer is a carbon film containing carbon as a main component.
  • the thickness of the protective layer is preferably 1 nm or more. By setting the thickness of the protective layer to 1 nm or more, the scratch resistance can be effectively improved.
  • the thickness of the protective layer is more preferably 2 nm or more. Further, the thickness of the protective layer is preferably 10 nm or less, more preferably 7 nm or less, and further preferably 5 nm or less.
  • a protective layer similar to that in the first configuration example can be provided.
  • the adhesive layer 18 is regarded as a part of the second dielectric layer 16 if it is a dielectric having a refractive index of 1.9 to 2.1 when it is a finished product.
  • the adhesive layer 18 is a dielectric having a refractive index of 1.9 to 2.1
  • the protective layer is a dielectric having a refractive index of 1.9 to 2.1.
  • the protective layer is also considered part of the second dielectric layer 16.
  • FIG. 4 shows a third configuration example of the laminate 10.
  • the third configuration example is another preferable configuration example of the heat-treated product.
  • a metal layer 151 can be further provided as the light absorption layer 15 between the nitride layer 152 and the metal oxide layer 17 in the second configuration example.
  • the metal oxide layer 17 is preferably made of an oxide of the same metal as that contained in the metal layer 151.
  • the configurations of the second dielectric layer 16, the adhesive layer 18, and the protective layer can be basically the same as those of the second configuration example.
  • the light absorption layer 15 (the nitride layer 152 and the metal layer 151), the metal oxide layer 17, and the second dielectric layer 16 are formed by forming the nitride layer 152 on the silver layer 14,
  • the metal layer can be formed on the nitride layer 152 so as to be thicker than that in the configuration example 2, and the second dielectric layer 16 can be formed on the metal film. That is, when the second dielectric layer 16 is formed, a part of the metal film on the second dielectric layer 16 side can be oxidized to form the metal oxide layer 17, and the silver layer 14 of the metal film can be formed.
  • the metal layer 151 can be formed by leaving the remaining portion on the side without being oxidized.
  • the metal film is used for forming the metal layer 151 as the light absorption layer 15 and also used as a barrier film for suppressing oxidation of the silver layer 14 when forming the second dielectric layer 16.
  • the light absorption layer 15 (the metal layer 151 and the nitride layer 152) can be formed while suppressing the oxidation of the silver layer 14, and the productivity can be improved.
  • the thickness of the metal layer 151 is not particularly limited, and is preferably determined as appropriate according to the thickness of the nitride layer 152 so that the thickness of the light absorption layer 15 is 6 nm or less as a whole.
  • the constituent material of the metal layer 151 can be the same constituent material as the constituent material of the metal layer 151 of the configuration example 1 or the constituent material of the metal film of the configuration example 2.
  • the laminate 10 preferably has the following optical characteristics.
  • the optical characteristics of the present invention can be obtained by measuring with a “C light source 2 ° visual field” as a light source.
  • the post-heat-treated product preferably has the following optical characteristics.
  • the solar heat gain coefficient (SHGC) is preferably 0.37 to 0.43.
  • Solar heat gain is a measure of how much heat from sunlight is blocked. That is, the solar heat gain rate (SHGC) is the ratio of the energy released to the indoor side with respect to the energy incident from the outdoor side in the multi-layer glass or single plate glass.
  • the solar heat acquisition rate is represented by a numerical value between 0 and 1. The smaller the solar heat gain rate, the less solar heat is transmitted.
  • the solar heat gain rate (SHGC) is an index used by National Fenestration Rating Council.
  • a solar radiation acquisition rate is calculated
  • the transparent substrate 11 and the counter substrate of the laminate 10 are preferably glass plates, and the hollow layer is preferably an air layer.
  • the laminated body 10 is disposed so as to be on the outdoor side, and the laminated film 12 is disposed on the hollow layer side.
  • the thickness of the transparent substrate 11 and the counter substrate is preferably about 3 to 6 mm, and the thickness of the hollow layer is preferably about 6 to 18 mm.
  • the visible light transmittance (T v ) is preferably 66 to 72%, and the visible light reflectance (R v1 ) on the transparent substrate 11 side (hereinafter simply referred to as the substrate side) is preferably 20 to 25%, and the laminated film 12 side
  • the visible light reflectance (R v2 ) (hereinafter referred to simply as “film side”) is preferably 13 to 20%.
  • the reflectance difference (R v1 ⁇ R v2 ) between the visible light reflectance (R v1 ) on the substrate side and the visible light reflectance (R v2 ) on the film side is preferably 3.5% or more, and is preferably 4.0% or more. Is more preferable.
  • the visible light transmittance (T v ) and the visible light reflectance (R v ) are both defined in JIS R3106: 1998.
  • the transmitted light and reflected light of the laminate 10 preferably have the following color tone. That is, in the L * a * b * color system, the transmitted light preferably has a * of ⁇ 4 to ⁇ 1 and b * of 3 to 8.
  • the reflected light on the substrate side preferably has a * of ⁇ 4 to 1 and b * of ⁇ 13 to ⁇ 8.
  • the reflected light on the film side preferably has a * of -1 to 7 and b * of -20 to -11.
  • a glass plate for a building is required to have a low solar heat acquisition rate from the viewpoint of cooling efficiency and the like, and the colors of transmitted light and reflected light are important from the viewpoint of design. Since the laminated body 10 of the embodiment has a low solar heat acquisition rate and has predetermined optical characteristics, it is preferably used for a glass plate for buildings, particularly a glass plate for high-rise buildings, specifically a window. It is suitably used for applications such as glass.
  • a dielectric film that becomes the first dielectric layer 13 a silver film that becomes the silver layer 14, a metal film that becomes the metal layer 151 and the metal oxide layer 17 on the transparent substrate 11.
  • a dielectric film to be the second dielectric layer 16 an adhesive film to be the adhesive layer 18, and a protective film to be the protective layer 19, if necessary, can be sequentially formed.
  • the film forming method is not particularly limited, but a sputtering method is preferably used.
  • Sputtering methods include DC sputtering using a metal target, AC and RF sputtering using metal and non-metal targets. In all cases, magnetron sputtering can be used. Sputtering is performed in an inert gas or in a reactive gas as required.
  • Each film is formed as follows, for example.
  • the dielectric film to be the first dielectric layer 13 is, for example, reactive sputtering in an oxidizing atmosphere containing argon and oxygen using a metal target made of metal contained in the dielectric film as a sputtering target.
  • the film is formed by
  • the silver film to be the silver layer 14 is formed by sputtering in a non-oxidizing atmosphere consisting only of argon containing no oxygen, for example, using a silver target containing silver as a main component as a sputtering target.
  • the metal film to be the metal layer 151 and the metal oxide layer 17 for example, a metal target made of metal contained in the metal film is used as a sputtering target, and sputtering is performed in a non-oxidizing atmosphere made only of argon not containing oxygen.
  • the film is formed by
  • the metal film is partly oxidized to form the metal oxide layer 17 when the dielectric film to be the second dielectric layer 16 is formed, and the remaining part is not oxidized to the metal layer 151. Therefore, the metal film is preferably formed thicker than the metal layer 151.
  • the thickness of the metal film oxidized to become the metal oxide layer 17 is about 1 to 3 nm. Therefore, the thickness of the metal film is preferably 1 nm or more thicker than the thickness of the metal layer 151.
  • the dielectric film to be the second dielectric layer 16 is, for example, sputtered in an oxidizing atmosphere containing argon and oxygen using a metal target made of metal contained in the electric film as a sputtering target. Form a film. During the film formation, as described above, a part of the metal film is oxidized to become the metal oxide layer 17, and the remaining part is not oxidized to become the metal layer 151.
  • the adhesive film to be the adhesive layer 18 is formed, for example, by sputtering in an atmosphere containing argon and nitrogen using a metal target such as titanium as a sputtering target.
  • the protective film to be the protective layer 19 is formed, for example, by performing sputtering in an oxidizing atmosphere containing argon and oxygen using a metal target such as titanium as a sputtering target.
  • a dielectric film to be the first dielectric layer 13 a silver film to be the silver layer 14, a nitride film to be the nitride layer 152, a metal layer 151, a metal film to be the metal oxide layer 17, and a dielectric film to be the second dielectric layer 16 are sequentially formed, and then heat treatment for strengthening or bending can be performed. If necessary, an adhesive film to be the adhesive layer 18 and a protective film to be the protective layer 19 are sequentially formed on the second dielectric layer 16.
  • the heat treatment is preferably performed, for example, in air at 650 to 750 ° C. for 1 to 10 minutes.
  • membrane similar to a non-heat-treated product it can form into a film fundamentally similarly to a non-heat-treated product.
  • the thickness of the metal film is such that all of the metal film is oxidized when the dielectric film to be the second dielectric layer 16 is formed.
  • the thickness of the metal film is set so that all of the metal film is not oxidized during the formation of the dielectric film to be the second dielectric layer 16.
  • the nitride film to be the nitride layer 152 is formed by sputtering in an atmosphere containing argon and nitrogen, for example, using a metal target made of metal contained in the nitride film as a sputtering target.
  • the protective film serving as the protective layer 19 is formed by sputtering in a non-oxidizing atmosphere using, for example, a carbon target as a sputtering target.
  • a carbon film is formed as a protective film, it disappears by a subsequent heat treatment for strengthening or bending.
  • FIG. 5 shows one embodiment of the double glazing.
  • the multilayer glass 20 is disposed so that the laminate 10 and the counter substrate 21 are spaced apart from each other with a spacer 22 interposed therebetween.
  • a primary sealant 23 seals between the laminate 10 and the spacer 22 and between the counter substrate 21 and the spacer 22.
  • the peripheral edge between the laminated body 10 and the counter substrate 21 is sealed by the secondary sealing material 24.
  • a desiccant 27 for suppressing condensation in the hollow layer 26 through the through hole 25 is disposed inside the spacer 22.
  • the hollow layer 26 is filled with air or argon gas.
  • the laminate 10 is disposed on the outdoor side with respect to the counter substrate 21.
  • the laminated body 10 is arrange
  • a laminated body is suitable for buildings, it is not necessarily limited to buildings, and can be used for vehicles such as automobiles as far as applicable.
  • the configuration of the laminated film is not limited to the above-described configuration, and other layers can be included as necessary and within the limits not departing from the object of the present invention.
  • Example 1 Film formation was performed by the sputtering method with the film configuration shown in Table 1, and a laminate (non-heat-treated product) having the configuration shown in FIG. 2 was manufactured. Note that the configurations and thicknesses shown in Table 1 are the configurations and thicknesses when the respective films are formed, and do not necessarily match the configurations and thicknesses in the final form.
  • the dielectric film (1) is the first dielectric layer 13
  • the silver film is the silver layer 14
  • the metal film is partly oxidized to become the metal oxide layer 17, and the remainder is not oxidized and is a metal layer.
  • the dielectric film (2) becomes the second dielectric layer 16
  • the adhesive film becomes the adhesive layer 18 by oxidation
  • the protective film becomes the protective layer 19.
  • the metal oxide layer 17, the adhesive layer 18, and the protective layer 19 all have a refractive index outside the range of 1.9 to 2.1. Therefore, the second dielectric layer 16 is not included.
  • the sputtering apparatus As the sputtering apparatus, an in-line type sputtering apparatus equipped with a target for forming each film in the sputtering chamber was used. A 3 mm thick soda lime glass plate was introduced into this in-line type sputtering apparatus, and evacuated in the load lock chamber until the degree of vacuum was 2 ⁇ 10 ⁇ 6 Torr or less. Subsequently, a glass plate was introduced into the sputtering chamber, and films were sequentially formed with the film configurations shown in Table 1.
  • a tin-zinc oxide film (a ratio of tin to 50% by mass with respect to the total amount of tin and zinc) and an aluminum zinc oxide film (aluminum with respect to the total amount of aluminum and zinc) Is a silver film, a titanium film as the metal film, and an aluminum zinc oxide film as the dielectric film (2) (the ratio of aluminum to the total amount of aluminum and zinc is 5.0).
  • a zirconium titanium oxide film (the ratio of titanium oxide to the total amount of zirconium oxide and titanium oxide is 45% by mass) It was deposited, to produce a laminate.
  • the tin-zinc oxide film uses a zinc-tin alloy target (the ratio of tin to 50% by mass with respect to the total amount of zinc and tin) and introduces argon (Ar) and oxygen (O 2 ). (The ratio of the gas pressure of argon and oxygen (P Ar / PO 2 ) was 10/9), and the power density was 3.6 W / cm 2 .
  • the aluminum zinc oxide film uses an alloy target of zinc and aluminum (a ratio of aluminum with respect to the total amount of zinc and aluminum is 5.0 atomic%) and introduces argon (Ar) and oxygen (O 2 ) (the ratio of the gas pressure of argon and oxygen (P Ar / P O2 ) is 10/9), and the power density was 3.6 W / cm 2 .
  • the silver film was formed using a silver target with an introduction gas of Ar 100% and a power density of 1.4 W / cm 2 .
  • the titanium film was formed using a titanium target with an introduction gas of Ar 100% and a power density of 0.7 W / cm 2 .
  • the titanium nitride film uses a titanium target, and the introduced gas is a mixed gas of argon (Ar) and oxygen (O 2 ) (the ratio of the gas pressure of argon and oxygen (P Ar / P O2 ) is 70/30).
  • the film was formed with a power density of 3.6 W / cm 2 .
  • the zirconium-titanium oxide film uses an alloy target of zirconium and titanium (the ratio of titanium to the total amount of zirconium and titanium is 45% by mass), and the introduced gas is argon (Ar) and oxygen (O 2 ). (The ratio of the gas pressure of argon and oxygen (P Ar / PO 2 ) was 10/9), and the power density was 3.6 W / cm 2 .
  • Example 2 As shown in Table 1, a laminate (non-heat treated product) was manufactured in the same manner as in Example 1 except that no titanium nitride film was provided.
  • Example 3 Film formation and heat treatment were performed by the sputtering method with the film configuration shown in Table 2, and a laminate (heat treatment product) having the metal layer 151 and the nitride layer 152 as the light absorption layer 15 as shown in FIG. 4 was manufactured. The heat treatment was performed in air at 730 ° C. for 6 minutes.
  • the dielectric film (1) is the first dielectric layer 13
  • the silver film is the silver layer 14
  • the nitride film is the nitride layer 152
  • the metal film is partially oxidized to form the metal oxide layer 17
  • the remainder is not oxidized and becomes the metal layer 151 of the light absorption layer 15
  • the dielectric film (2) becomes the second dielectric layer 16
  • the adhesive film becomes the adhesive layer 18 by oxidation.
  • the protective film is formed as a protective layer, but disappears by the subsequent heat treatment.
  • the protective film was formed by using a carbon target with an introduction gas of Ar 100% and a power density of 2.1 W / cm 2 . Other layers were formed under the same conditions as in Example 1.
  • Example number 5 the visible light transmittance (T v ), the visible light reflectance (R v1 ) on the substrate side, and the visible light reflectance (R v2 ) on the film side Asked.
  • the solar heat gain rate (SHGC) when it was set as the multilayer glass as shown in FIG. 5 was calculated
  • Table 3 shows the results of the visible light transmittance (T v ), the visible light reflectance (R v1 , R v2 ), and the solar heat gain rate (SHGC).
  • the visible light transmittance (T v ) and the visible light reflectance (R v ) were measured by measuring the visible light transmittance at a wavelength of 300 to 2500 nm using a Hitachi U-4100 spectrophotometer, and specified in JIS R3106: 1998. Calculated according to
  • the transmitted light and reflected light were calculated in accordance with JIS Z 8729 by measuring a * and b * in the L * a * b * color system based on JIS Z 8722.
  • the solar heat acquisition rate is a glass plate (thickness 6 mm) for the transparent substrate 11 of the laminated film 12, and a glass plate (thickness 6 mm) for the counter substrate 21. It calculated
  • the laminates of Examples 1 to 3 having a predetermined laminate structure have a visible light transmittance (T v ) of 66 to 72% and a visible light reflectance on the substrate side.
  • T v1 visible light transmittance
  • R v2 visible light reflectance
  • R v2 visible light reflectance
  • reflectance difference R v1 ⁇ R v2
  • a * of transmitted light is -4 to -1 and b * are 3 to 8
  • a * of the reflected light on the substrate side is -4 to 1 and b * is -13 to -8
  • a * of the reflected light on the film side is -1 to 7 and b * satisfies ⁇ 20 to ⁇ 13
  • SHGC solar radiation acquisition rate
  • Example 1 Comparative Example 1 As shown in Table 4, a laminate (non-heat treated product) was manufactured in the same manner as in Example 1 by changing the thicknesses of the dielectric films (1) and (2) and the metal film.
  • the thickness after the formation of all films is as shown below.
  • the thicknesses of the dielectric films (1), (2), the silver film, and the protective film (zirconium titanium oxide and carbon) after film formation are all the same as the thickness immediately after the film formation. .
  • the thickness of the entire metal film (titanium) after film formation is oxidized and increased during the film formation of other films, and is therefore about twice the thickness immediately after film formation.
  • the thickness of the adhesive film after the entire film is formed is oxidized and increased at the time of forming other films, so that the thickness is less than 1.5 times that immediately after the film formation.
  • the thickness immediately after the film formation and the thickness after the heat treatment is as shown below.
  • the thicknesses of the dielectric films (1), (2), the silver film, and the protective film (zirconium titanium oxide) after the heat treatment are all the same as the thickness immediately after the film formation. Since the thickness of the metal film (titanium) after the heat treatment is oxidized and increased during the heat treatment, it is about twice the thickness immediately after the film formation. Since the thickness of the adhesive film after the heat treatment is increased by oxidation during the heat treatment, the thickness is less than 1.5 times that immediately after the film formation.
  • the protective film (carbon) disappears due to oxidation during heat treatment.
  • SYMBOLS 10 Laminated body, 11 ... Transparent substrate, 12 ... Laminated film, 13 ... 1st dielectric layer, 14 ... Silver layer, 15 ... Light absorption layer, 16 ... 2nd dielectric layer, 17 ... Metal oxide layer 18 ... Adhesive layer, 19 ... Protective layer, 20 ... Multi-layer glass, 21 ... Counter substrate, 22 ... Spacer, 23 ... Primary sealing material, 24 ... Secondary sealing material, 25 ... Through hole, 26 ... Hollow layer, 27 ... Desiccant, 151 ... Metal layer, 152 ... Nitride layer.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Architecture (AREA)
  • Civil Engineering (AREA)
  • Laminated Bodies (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

L'invention concerne un corps stratifié comprenant un substrat transparent et un film stratifié qui est disposé sur le substrat transparent. Le film stratifié comprend, dans l'ordre depuis le côté du substrat transparent, une première couche diélectrique, une couche d'argent, une couche absorbant la lumière et une seconde couche diélectrique. La première couche diélectrique présente un indice de réfraction de 1,9-2,1 et une épaisseur géométrique de 20-30 nm. La couche d'argent comprend de l'argent comme composant principal et présente une épaisseur géométrique de 11-18 nm. La couche d'absorption de lumière présente une épaisseur géométrique de 1-6 nm. La seconde couche diélectrique présente un indice de réfraction de 1,9-2,1 et une épaisseur géométrique de 35-48 nm.
PCT/JP2014/050248 2013-01-11 2014-01-09 Corps stratifié et verre multicouche WO2014109369A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013003503 2013-01-11
JP2013-003503 2013-01-11

Publications (1)

Publication Number Publication Date
WO2014109369A1 true WO2014109369A1 (fr) 2014-07-17

Family

ID=51167016

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/050248 WO2014109369A1 (fr) 2013-01-11 2014-01-09 Corps stratifié et verre multicouche

Country Status (1)

Country Link
WO (1) WO2014109369A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018179908A1 (fr) * 2017-03-31 2018-10-04 パナソニックＩｐマネジメント株式会社 Procédé de fabrication d'unité de panneau en verre et procédé de fabrication de fenêtre en verre
WO2019167900A1 (fr) * 2018-02-28 2019-09-06 Tdk株式会社 Conducteur transparent, corps de commande de lumière et corps de génération de chaleur transparent

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003104758A (ja) * 2001-09-27 2003-04-09 Nippon Sheet Glass Co Ltd 熱線遮蔽ガラス及びこれを用いた複層ガラス
JP2004217432A (ja) * 2003-01-09 2004-08-05 Asahi Glass Co Ltd 積層体および構造体
JP2006503724A (ja) * 2002-08-01 2006-02-02 サン−ゴバン グラス フランス 仕切りガラス用のプレストレスを加えることが可能な多層系
JP2012513323A (ja) * 2008-12-22 2012-06-14 サン−ゴバン グラス フランス 熱特性を有しかつ吸収層を有する多層コーティングを備えた基材
WO2012115111A1 (fr) * 2011-02-21 2012-08-30 旭硝子株式会社 Stratifié

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003104758A (ja) * 2001-09-27 2003-04-09 Nippon Sheet Glass Co Ltd 熱線遮蔽ガラス及びこれを用いた複層ガラス
JP2006503724A (ja) * 2002-08-01 2006-02-02 サン−ゴバン グラス フランス 仕切りガラス用のプレストレスを加えることが可能な多層系
JP2004217432A (ja) * 2003-01-09 2004-08-05 Asahi Glass Co Ltd 積層体および構造体
JP2012513323A (ja) * 2008-12-22 2012-06-14 サン−ゴバン グラス フランス 熱特性を有しかつ吸収層を有する多層コーティングを備えた基材
WO2012115111A1 (fr) * 2011-02-21 2012-08-30 旭硝子株式会社 Stratifié

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018179908A1 (fr) * 2017-03-31 2018-10-04 パナソニックＩｐマネジメント株式会社 Procédé de fabrication d'unité de panneau en verre et procédé de fabrication de fenêtre en verre
JPWO2018179908A1 (ja) * 2017-03-31 2020-01-23 パナソニックＩｐマネジメント株式会社 ガラスパネルユニットの製造方法、およびガラス窓の製造方法
WO2019167900A1 (fr) * 2018-02-28 2019-09-06 Tdk株式会社 Conducteur transparent, corps de commande de lumière et corps de génération de chaleur transparent
JPWO2019167900A1 (ja) * 2018-02-28 2021-03-11 Tdk株式会社 透明導電体、調光体及び透明発熱体
JP7024852B2 (ja) 2018-02-28 2022-02-24 Tdk株式会社 透明導電体、調光体及び透明発熱体

Similar Documents

Publication Publication Date Title
JP6090322B2 (ja) 積層体
JP4763569B2 (ja) 高赤外反射コーティング、薄膜コーティング堆積方法および関連技術
JP6034360B2 (ja) 多層薄膜を有する透明基材
JP5846203B2 (ja) 低放射率積層体、および複層ガラス
WO2014109368A1 (fr) Film optique multicouche, corps stratifié et verre à double vitrage
KR101950527B1 (ko) 두 개의 로이 스택을 포함하는 단열 다층 창유리
JP4108771B2 (ja) 板ガラスを複数枚使用する板ガラス製品
JP4602498B2 (ja) 薄膜積層体を備えた透明基板
JPH07149545A (ja) 日光及び／又は赤外線に作用する薄い皮膜の積層を備えた透明な基材
WO2012115111A1 (fr) Stratifié
JP6024369B2 (ja) 窓用ガラス積層体
JP6767661B2 (ja) グレー色調低放射ガラス
JP6601419B2 (ja) 積層膜付きガラス板および複層ガラス
JP2007070146A (ja) 低放射複層ガラス
JPH08104547A (ja) 断熱ガラス
WO2018051638A1 (fr) Élément de protection contre la lumière solaire
JP5463686B2 (ja) 窓用ガラス積層体
WO2014109369A1 (fr) Corps stratifié et verre multicouche
JP2018002564A (ja) グレー色調低放射ガラス
JP2017132666A (ja) グレー色調低放射ガラス、及びグレー色調低放射ガラスの製造方法
JP2008222507A (ja) 複層ガラス
JP2019182684A (ja) 低放射ガラス
JP2007197237A (ja) 低放射複層ガラス
JP2004217432A (ja) 積層体および構造体
JP6287502B2 (ja) 低放射窓材

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14737662

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14737662

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP