WO2023074638A1 - ボロシリケートガラス - Google Patents

ボロシリケートガラス Download PDF

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Publication number
WO2023074638A1
WO2023074638A1 PCT/JP2022/039577 JP2022039577W WO2023074638A1 WO 2023074638 A1 WO2023074638 A1 WO 2023074638A1 JP 2022039577 W JP2022039577 W JP 2022039577W WO 2023074638 A1 WO2023074638 A1 WO 2023074638A1
Authority
WO
WIPO (PCT)
Prior art keywords
glass
less
bent
borosilicate
borosilicate glass
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2022/039577
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
貴人 梶原
茂輝 澤村
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AGC Inc
Original Assignee
Asahi Glass Co Ltd
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 Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Priority to JP2023556438A priority Critical patent/JPWO2023074638A1/ja
Priority to CN202280072393.XA priority patent/CN118159507A/zh
Priority to DE112022004163.3T priority patent/DE112022004163T5/de
Publication of WO2023074638A1 publication Critical patent/WO2023074638A1/ja
Priority to US18/646,873 priority patent/US20240293999A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • 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
    • B32B1/00—Layered products having a non-planar shape
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10082—Properties of the bulk of a glass sheet
    • B32B17/101—Properties of the bulk of a glass sheet having a predetermined coefficient of thermal expansion [CTE]
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10082—Properties of the bulk of a glass sheet
    • B32B17/10119—Properties of the bulk of a glass sheet having a composition deviating from the basic composition of soda-lime glass, e.g. borosilicate
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    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B32B17/10431—Specific parts for the modulation of light incorporated into the laminated safety glass or glazing
    • B32B17/1044—Invariable transmission
    • B32B17/10449—Wavelength selective transmission
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10807—Making laminated safety glass or glazing; Apparatus therefor
    • B32B17/10889—Making laminated safety glass or glazing; Apparatus therefor shaping the sheets, e.g. by using a mould
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B23/00—Re-forming shaped glass
    • C03B23/02—Re-forming glass sheets
    • C03B23/023—Re-forming glass sheets by bending
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10082—Properties of the bulk of a glass sheet
    • B32B17/10091—Properties of the bulk of a glass sheet thermally hardened
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10128—Treatment of at least one glass sheet
    • B32B17/10137—Chemical strengthening
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10743—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing acrylate (co)polymers or salts thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/1077—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing polyurethane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10779—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing polyester
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10788—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing ethylene vinylacetate
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    • B32B2307/10—Properties of the layers or laminate having particular acoustical properties
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    • B32B2315/00—Other materials containing non-metallic inorganic compounds not provided for in groups B32B2311/00 - B32B2313/04
    • B32B2315/08—Glass
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    • B32B2605/00—Vehicles
    • B32B2605/08—Cars
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01S—RADIO DIRECTION-FINDING; RADIO NAVIGATION; DETERMINING DISTANCE OR VELOCITY BY USE OF RADIO WAVES; LOCATING OR PRESENCE-DETECTING BY USE OF THE REFLECTION OR RERADIATION OF RADIO WAVES; ANALOGOUS ARRANGEMENTS USING OTHER WAVES
    • G01S13/00—Systems using the reflection or reradiation of radio waves, e.g. radar systems; Analogous systems using reflection or reradiation of waves whose nature or wavelength is irrelevant or unspecified
    • G01S13/88—Radar or analogous systems specially adapted for specific applications
    • G01S13/93—Radar or analogous systems specially adapted for specific applications for anti-collision purposes
    • G01S13/931—Radar or analogous systems specially adapted for specific applications for anti-collision purposes of land vehicles
    • G01S2013/9327—Sensor installation details
    • G01S2013/93276—Sensor installation details in the windshield area

Definitions

  • the present invention relates to borosilicate glass, bent glass, manufacturing methods thereof, laminated glass, and vehicle window glass. More specifically, the present invention relates to borosilicate glass capable of manufacturing bent glass with excellent heat shielding properties, bent glass, a method for manufacturing the same, laminated glass, and vehicle window glass.
  • a window glass for a vehicle it is possible to reduce the energy consumption of an air conditioner by suppressing the transfer of heat from the outside of the vehicle to the inside of the vehicle due to the temperature difference between the inside and outside of the vehicle. Therefore, vehicle window glass is required to have high heat shielding properties.
  • window glass having a heat-shielding property examples include soda-lime glass used in conventional window glass for automobiles, etc., but other than that, alkali borosilicate glass as described in Patent Documents 1 to 3, etc. is also an alternative candidate.
  • the present inventors have discovered a borosilicate glass that has a specific glass composition and that reduces the average transmittance of light in a specific wavelength range when subjected to bending treatment at a predetermined temperature, or by small-angle X-ray scattering measurement. It has been found that borosilicate glass with a reduced maximum scattering intensity can be used to produce bent glass with excellent heat shielding properties.
  • the present invention provides a new borosilicate glass that can be manufactured into bent glass having excellent heat shielding properties, a bent glass made of the borosilicate glass, a method for manufacturing the same, a laminated glass, and a vehicle window glass. .
  • the borosilicate glass according to the embodiment of the present invention is represented by mol% based on oxides, 70.0% ⁇ SiO 2 ⁇ 85.0% 5.0% ⁇ B2O3 ⁇ 20.0 % 0.70% ⁇ Al 2 O 3 ⁇ 10.0% 0.0% ⁇ Li 2 O ⁇ 5.0% 0.0% ⁇ Na 2 O ⁇ 10.0% 0.0% ⁇ K2O ⁇ 5.0 % 0.0% ⁇ MgO ⁇ 5.0% 0.0% ⁇ CaO ⁇ 5.0% 0.0% ⁇ SrO ⁇ 5.0% 0.10% ⁇ Fe2O3 ⁇ 1.0 % including The total amount of SiO2 , Al2O3 and B2O3 is 85.0% or more , substantially free of BaO, PbO and As2O3 , In flat glass, when the thickness is converted to 1.50 mm, the average transmittance of light with a wavelength of 900 nm to 1300 nm is T b [%], Average of light with a wavelength of 900 nm to 1300 nm when the flat glass is heated at a
  • the borosilicate glass according to the embodiment of the present invention is represented by mol% based on oxides, 70.0% ⁇ SiO 2 ⁇ 85.0% 5.0% ⁇ B2O3 ⁇ 20.0 % 0.70% ⁇ Al 2 O 3 ⁇ 10.0% 0.0% ⁇ Li 2 O ⁇ 5.0% 0.0% ⁇ Na 2 O ⁇ 10.0% 0.0% ⁇ K2O ⁇ 5.0 % 0.0% ⁇ MgO ⁇ 5.0% 0.0% ⁇ CaO ⁇ 5.0% 0.0% ⁇ SrO ⁇ 5.0% 0.10% ⁇ Fe2O3 ⁇ 1.0 % including The total amount of SiO2 , Al2O3 and B2O3 is 85.0% or more , substantially free of BaO, PbO and As2O3 , In flat glass, when the thickness is converted to 1.50 mm, the average transmittance of light with a wavelength of 900 nm to 1300 nm is T b [%], When the flat glass is heated to 630 ° C., the bending time is 6 minutes, and the thickness is converted to
  • the borosilicate glass according to the embodiment of the present invention is represented by mol% based on oxides, 70.0% ⁇ SiO 2 ⁇ 85.0% 5.0% ⁇ B2O3 ⁇ 20.0 % 0.70% ⁇ Al 2 O 3 ⁇ 10.0% 0.0% ⁇ Li 2 O ⁇ 5.0% 0.0% ⁇ Na 2 O ⁇ 10.0% 0.0% ⁇ K2O ⁇ 5.0 % 0.0% ⁇ MgO ⁇ 5.0% 0.0% ⁇ CaO ⁇ 5.0% 0.0% ⁇ SrO ⁇ 5.0% 0.10% ⁇ Fe2O3 ⁇ 1.0 % including The total amount of SiO2 , Al2O3 and B2O3 is 85.0% or more , substantially free of BaO, PbO and As2O3 , In the flat glass, the maximum value of the normalized scattering intensity in the range of 0.10 to 2.0 (nm -1 ) of the scattering vector q measured by small angle X-ray scattering (SAXS) is 0.35 or more, When the flat glass is heated at a temperature T 12 or higher at
  • the borosilicate glass according to one aspect of the present invention is a flat glass, defined by ISO-13837:2008 convention A when the thickness is converted to 1.50 mm, and measured at a wind speed of 4 m / s.
  • the solar transmittance is Tts1
  • the flat glass is heated at a temperature T12 or higher at which the glass viscosity is 10 12 [dPa s] and bent, and the thickness is converted to 1.50 mm.
  • Tts2 is the total solar transmittance defined by ISO-13837:2008 convention A and measured at a wind speed of 4 m/s, (Tts1 ⁇ Tts2)/Tts1 ⁇ 0.002 may be satisfied.
  • the borosilicate glass according to one aspect of the present invention may be float glass.
  • the borosilicate glass according to one aspect of the present invention may be fusion draw glass.
  • the borosilicate glass according to one aspect of the present invention may have a temperature T12 of 650° C. or less at which the glass viscosity becomes 10 12 [dPa ⁇ s].
  • the borosilicate glass according to one aspect of the present invention may be substantially free of Er 2 O 3 .
  • the borosilicate glass according to one aspect of the present invention may have a transmittance of 78.0% or more for light with a wavelength of 500 nm when the thickness is converted to 1.50 mm.
  • the borosilicate glass according to one aspect of the present invention may have a transmittance of 90.0% or less for light with a wavelength of 1000 nm when the thickness is converted to 1.50 mm.
  • the borosilicate glass according to one aspect of the present invention may have an average transmittance of 78.0% or more for light with a wavelength of 450 nm to 700 nm when the thickness is converted to 1.50 mm.
  • the borosilicate glass according to one aspect of the present invention may have an average transmittance of 90.0% or less for light with a wavelength of 900 nm to 1300 nm when the thickness is converted to 1.50 mm.
  • the Fe 2 O 3 content may be 0.15% or more in terms of mol% based on oxides.
  • the bent glass according to the embodiment of the present invention is made of the above borosilicate glass.
  • bent glass according to one aspect of the present invention may be single-bent glass.
  • bent glass according to one aspect of the present invention may be double bent glass.
  • bent glass according to one aspect of the present invention may have a minimum radius of curvature of 500 mm or more and 100000 mm or less.
  • the bent glass according to one aspect of the present invention has a total solar transmittance of 90 as defined by ISO-13837:2008 convention A and measured at a wind speed of 4 m/s when the thickness is converted to 1.50 mm. % or less.
  • the borosilicate glass is heated and formed into the bent glass.
  • a laminated glass according to an embodiment of the present invention includes a first glass plate, a second glass plate, and an interlayer sandwiched between the first glass plate and the second glass plate, At least one of the first glass plate and the second glass plate is the borosilicate glass.
  • the total thickness of the first glass plate, the second glass plate and the interlayer film is 6.00 mm or less, and is defined by ISO-9050:2003 using a D65 light source.
  • the visible light transmittance Tv may be 70% or more.
  • a vehicle window glass according to an embodiment of the present invention has the borosilicate glass or bent glass described above.
  • a vehicle window glass according to another embodiment of the present invention is made of the above laminated glass.
  • bent glass having excellent heat shielding properties can be produced.
  • bent glass, laminated glass, and vehicle window glass made of the borosilicate glass have excellent heat shielding properties.
  • FIG. 1 is a cross-sectional view of an example of laminated glass according to an embodiment of the present invention.
  • FIG. 2 is a conceptual diagram showing a state in which the laminated glass of the embodiment of the present invention is used as an automobile window glass.
  • FIG. 3 is an enlarged view of part S in FIG. 4 is a cross-sectional view taken along line YY of FIG. 3.
  • FIGS. 5(a) and 5(b) are graphs showing measurement results of transmission/reflection spectra of light with a wavelength of 200 nm to 2500 nm before and after bending in glass A and glass E of Examples.
  • FIG. 6 is a graph showing the results of SAXS before and after bending in glass A and glass E of Examples.
  • the vertical axis means the normalized scattering intensity and the horizontal axis means the scattering vector q.
  • the glass substantially does not contain a certain component means that it is not contained except for unavoidable impurities, and that the component is not actively added. Specifically, it means that the content of each of these components is about 100 ppm or less in the glass.
  • the borosilicate glass according to the embodiment of the present invention is represented by mol% based on oxides, 70.0% ⁇ SiO 2 ⁇ 85.0% 5.0% ⁇ B2O3 ⁇ 20.0 % 0.70% ⁇ Al 2 O 3 ⁇ 10.0% 0.0% ⁇ Li 2 O ⁇ 5.0% 0.0% ⁇ Na 2 O ⁇ 10.0% 0.0% ⁇ K2O ⁇ 5.0 % 0.0% ⁇ MgO ⁇ 5.0% 0.0% ⁇ CaO ⁇ 5.0% 0.0% ⁇ SrO ⁇ 5.0% 0.10% ⁇ Fe2O3 ⁇ 1.0 % including The total amount of SiO2, Al2O3 and B2O3 is 85.0 % or more and substantially free of BaO, PbO and As2O3 , In flat glass, when the thickness is converted to 1.50 mm, the average transmittance of light with a wavelength of 900 nm to 1300 nm is T b [%], Average of light with a wavelength of 900 nm to 1300 nm when the flat glass is
  • the borosilicate glass of another embodiment of the present invention is represented by mol% based on oxides, 70.0% ⁇ SiO 2 ⁇ 85.0% 5.0% ⁇ B2O3 ⁇ 20.0 % 0.70% ⁇ Al 2 O 3 ⁇ 10.0% 0.0% ⁇ Li 2 O ⁇ 5.0% 0.0% ⁇ Na 2 O ⁇ 10.0% 0.0% ⁇ K2O ⁇ 5.0 % 0.0% ⁇ MgO ⁇ 5.0% 0.0% ⁇ CaO ⁇ 5.0% 0.0% ⁇ SrO ⁇ 5.0% 0.10% ⁇ Fe2O3 ⁇ 1.0 % including The total amount of SiO2 , Al2O3 and B2O3 is 85.0% or more , substantially free of BaO, PbO and As2O3 , In the flat glass, the maximum value of the normalized scattering intensity in the range of 0.10 to 2.0 (nm -1 ) of the scattering vector q measured by small angle X-ray scattering (SAXS) is 0.35 or more, When the flat glass is heated at a temperature T 12 or higher
  • the borosilicate glass in the present embodiment is an oxide glass containing silicon dioxide as a main component and containing a boron component.
  • the boron component in the borosilicate glass is boron oxide (generic term for boron oxides such as diboron trioxide ( B2O3 ) ) , and the ratio of boron oxide in the glass is expressed in terms of B2O3 .
  • composition range of each component in the borosilicate glass of this embodiment will be described below.
  • composition range of each component is hereinafter represented by mol % based on the oxide unless otherwise specified.
  • SiO2 is an essential component of the borosilicate glass of this embodiment.
  • the content of SiO2 is 70.0% or more and 85.0% or less.
  • SiO 2 contributes to improving the Young's modulus, thereby making it easier to ensure the strength required for automotive applications and the like. If the amount of SiO2 is small, it becomes difficult to ensure weather resistance, and the average coefficient of linear expansion becomes too large, causing thermal stress due to the temperature distribution of the glass sheet during bending, which may lead to thermal cracking of the glass sheet. It may become difficult to control the shape of the glass after bending. On the other hand, if the amount of SiO 2 is too large, the viscosity of the glass increases when the glass is melted, which may make it difficult to manufacture the glass.
  • the content of SiO 2 in the borosilicate glass of the present embodiment is preferably 72.0% or more, more preferably 74.0% or more, even more preferably 75.0% or more, and particularly preferably 76.0% or more.
  • the content of SiO 2 in the borosilicate glass of the present embodiment is preferably 84.0% or less, more preferably 83.5% or less, even more preferably 82.5% or less, and even more preferably 82.0% or less.
  • 81.0% or less is particularly preferable, and 80.0% or less is most preferable.
  • B 2 O 3 is an essential component of the borosilicate glass of this embodiment.
  • the content of B 2 O 3 is 5.0% or more and 20.0% or less.
  • B 2 O 3 contributes to improving glass strength and solubility.
  • B 2 O 3 contributes to the improvement of millimeter-wave transmittance of the glass.
  • the radio wave transmittance of millimeter waves means evaluation of radio wave transmittance including quasi-millimeter waves and millimeter waves, and means, for example, the radio wave transmittance of glass for radio waves with a frequency of 10 GHz to 90 GHz.
  • the absorption of iron ions in the glass is controlled by utilizing the microstructural change of the glass that accompanies the heat treatment as described later, and excellent heat shielding properties are achieved as a vehicle window glass. can.
  • the content of B 2 O 3 in the borosilicate glass of the present embodiment is preferably 6.0% or more, more preferably 6.5% or more, still more preferably 7.0% or more, and particularly 7.5% or more. Preferably, 8.0% or more is most preferable.
  • the B 2 O 3 content in the borosilicate glass of the present embodiment is preferably 18.0% or less, more preferably 16.0% or less, still more preferably 14.0% or less, and particularly preferably 13.0% or less. , 12.0% or less is most preferred.
  • Al 2 O 3 is an essential component of the borosilicate glass of this embodiment.
  • the content of Al 2 O 3 is 0.70% or more and 10.0% or less. If the content of Al 2 O 3 is small, it becomes difficult to ensure weather resistance, and the average coefficient of linear expansion becomes too large, which may cause thermal cracking of the glass sheet. On the other hand, if the content of Al 2 O 3 is too high, the viscosity during melting of the glass and the viscosity during bending (temperatures T 11 and T 12 ) may increase, making glass production difficult.
  • the content of Al 2 O 3 is preferably 1.0% or more, more preferably 1.5% or more, further preferably 2.0% or more, further preferably 2.5%, in order to suppress phase separation and improve weather resistance of the glass. Above is particularly preferred, and above 3.0% is most preferred.
  • the content of Al 2 O 3 is preferably 9.0% or less from the viewpoint of keeping the temperatures T 11 and T 12 of the borosilicate glass low to facilitate the production of bent glass and from the viewpoint of increasing the transmittance of millimeter waves. , is more preferably 8.5% or less, further preferably 8.0% or less, particularly preferably 7.5% or less, and most preferably 7.0% or less.
  • T 11 indicates the temperature at which the glass viscosity is 10 11 [dPa ⁇ s]
  • T 12 indicates the temperature at which the glass viscosity is 10 12 [dPa ⁇ s].
  • SiO 2 +Al 2 O 3 +B 2 O 3 of the borosilicate glass of the present embodiment that is, the total of SiO 2 content, Al 2 O 3 content and B 2 O 3 content is 85.0% or more and 98.0 % or less.
  • permeability of a millimeter wave improves.
  • SiO 2 +Al 2 O 3 +B 2 O 3 is 97.0% or less. It is preferably 96.0% or less, more preferably 95.0% or less.
  • SiO 2 +Al 2 O 3 +B 2 O 3 of the borosilicate glass of the present embodiment is preferably 88.0% or more, more preferably 89.0% or more, and even more preferably 90.0% or more.
  • Li 2 O is an optional component of the borosilicate glass of this embodiment.
  • the content of Li 2 O is 0.0% or more and 5.0% or less.
  • Li 2 O is a component that improves the meltability of the glass, facilitates increasing the Young's modulus, and contributes to improving the strength of the glass. Inclusion of Li 2 O lowers the viscosity of the glass, thereby improving the formability of window glass for vehicles, particularly windshields.
  • Li 2 O When Li 2 O is contained in the borosilicate glass of the present embodiment, it may be 0.20% or more, preferably 0.50% or more, more preferably 1.0% or more, and 1.5% or more. More preferably, 2.0% or more is particularly preferable, and 2.2% or more is most preferable.
  • the content of Li 2 O is preferably 4.5% or less, more preferably 4.0% or less, even more preferably 3.5% or less, particularly preferably 3.0% or less, and 2.5% or less. is most preferred.
  • Na 2 O is an optional component of the borosilicate glass of this embodiment.
  • the content of Na 2 O is 0.0% or more and 10.0% or less.
  • Na 2 O is a component that improves the solubility of glass, and is preferably contained in an amount of 0.10% or more.
  • the inclusion of Na 2 O lowers the viscosity of the glass, thereby improving the formability of the window glass for vehicles, particularly the windshield.
  • Na 2 O is contained, it is preferably 0.20% or more, more preferably 0.40% or more, still more preferably 0.50% or more, particularly preferably 1.0% or more, and 2.0% or more. Most preferred.
  • the content of Na 2 O is preferably 9.0% or less, more preferably 8.0% or less, still more preferably 7.5% or less, particularly preferably 7.0% or less, and 6.5% or less. Most preferred.
  • K 2 O is an optional component of the borosilicate glass of this embodiment.
  • the content of K 2 O is 0.0% or more and 5.0% or less.
  • K 2 O is a component that improves the solubility of glass, and may be contained in an amount of 0.10% or more.
  • the content of K 2 O is preferably 0.30% or more, more preferably 0.60% or more, still more preferably 1.0% or more, even more preferably 1.5% or more, and 2.0% or more. Especially preferred, 2.4% or more is most preferred.
  • the K 2 O content is preferably 4.5% or less, more preferably 4.0% or less, even more preferably 3.5% or less, and particularly preferably 3.0% or less.
  • the content of R 2 O in the borosilicate glass of the present embodiment may be 3.0% or more and 15% or less.
  • the content of R 2 O is preferably 3.0% or more, more preferably 4.0% or more, from the viewpoint of improving glass meltability and bending glass formability (reduction of T 11 and reduction of T 12 ). , more preferably 5.0% or more, particularly preferably 6.0% or more, most preferably 7.0% or more.
  • the content of R 2 O is high, the average linear expansion coefficient becomes too large, and thermal stress is generated due to the temperature distribution of the glass sheet during bending, and the glass sheet may be thermally cracked or the glass after bending may be damaged. Shape control may become difficult.
  • the content of R 2 O is preferably 15% or less, more preferably 13% or less, even more preferably 12% or less, particularly preferably 11% or less, and most preferably 10% or less.
  • R2O represents the total amount of Li2O , Na2O and K2O .
  • MgO is an optional component of the borosilicate glass of this embodiment.
  • the content of MgO is 0.0% or more and 5.0% or less.
  • MgO is a component that promotes melting of glass raw materials and improves weather resistance and Young's modulus. When MgO is contained, it is preferably 0.10% or more, more preferably 0.50% or more, and even more preferably 1.0% or more. Further, if the content of MgO is 5.0% or less, devitrification becomes difficult. In addition, increases in relative permittivity ( ⁇ r ) and dielectric loss tangent (tan ⁇ ) can be suppressed.
  • the MgO content is preferably 4.0% or less, more preferably 3.0% or less, even more preferably 2.5% or less, particularly preferably 2.0% or less, and most preferably 1.5% or less.
  • CaO is an optional component of the borosilicate glass of the present embodiment, and may be included in a certain amount to improve the solubility of the raw material for glass.
  • the content of CaO is 0.0% or more and 5.0% or less. When CaO is contained, it is preferably 0.10% or more, more preferably 0.50% or more, and even more preferably 1.0% or more. This improves the meltability of glass raw materials and the formability of bent glass (reduction of T11 and reduction of T12 ).
  • the CaO content is preferably 4.0% or less, and 3.0% or less. is more preferred, 2.5% or less is even more preferred, 2.0% or less is particularly preferred, and 1.5% or less is most preferred.
  • SrO is an optional component of the borosilicate glass of the present embodiment, and can be included in a certain amount to improve the solubility of the glass raw material.
  • the content of SrO is 0.0% or more and 5.0% or less. When SrO is contained, it is preferably 0.10% or more, more preferably 0.20% or more, and even more preferably 0.30% or more. This improves the meltability of glass raw materials and the formability of bent glass (reduction of T11 and reduction of T12 ).
  • the SrO content is preferably 4.0% or less in order to prevent the glass from becoming brittle and to prevent an increase in the dielectric constant ( ⁇ r ) and dielectric loss tangent (tan ⁇ ) of the glass.
  • the content of SrO is more preferably 3.0% or less, further preferably 2.0% or less, particularly preferably 1.0% or less, and most preferably not substantially contained.
  • the content of RO in the borosilicate glass of the present embodiment may be 0.0% or more and 5.0% or less.
  • the content of RO is preferably 0.10% or more, more preferably 0.25% or more, still more preferably 0.50% or more, and particularly 0.75% or more from the viewpoint of improving the solubility and Young's modulus of the glass.
  • Preferably, 1.0% or more is most preferable.
  • the average linear expansion coefficient becomes too large, and thermal stress is generated due to the temperature distribution of the glass sheet during bending, which may cause thermal cracking of the glass sheet and change the shape of the glass after bending. Control may become difficult.
  • there is a possibility that the radio wave transmittance of millimeter waves is lowered.
  • the RO content is preferably 5.0% or less, more preferably 4.5% or less, even more preferably 4.0% or less, particularly preferably 3.5% or less, and most preferably 3.0% or less. preferable.
  • RO represents the total amount of MgO, CaO and SrO.
  • Fe 2 O 3 is an essential component of the borosilicate glass of this embodiment, and is contained to impart heat shielding properties.
  • the content of Fe 2 O 3 is 0.10% or more and 1.0% or less.
  • the content of Fe 2 O 3 here means the total amount of iron including FeO, which is an oxide of ferrous iron, and Fe 2 O 3 , which is an oxide of trivalent iron.
  • the content of Fe 2 O 3 in the borosilicate glass of the present embodiment is preferably 0.15% or more, more preferably 0.17% or more, and even more preferably 0.19% or more.
  • the content of Fe 2 O 3 is preferably 0.80% or less, more preferably 0.50% or less, even more preferably 0.40% or less.
  • the iron ions contained in the Fe 2 O 3 preferably satisfy 0.18 ⁇ [Fe 2+ ]/([Fe 2+ ]+[Fe 3+ ]) ⁇ 0.80 on a mass basis. If the redox ([Fe 2+ ]/([Fe 2+ ]+[Fe 3+ ])) is too low, the heat shielding properties of the glass plate will deteriorate. On the other hand, if the redox is too high, there is a possibility that the absorption of ultraviolet rays will decrease.
  • [Fe 2+ ] and [Fe 3+ ] mean the contents of Fe 2+ and Fe 3+ contained in the borosilicate glass of this embodiment, respectively.
  • “[Fe 2+ ]/([Fe 2+ ]+[Fe 3+ ])” is the ratio of the content of Fe 2+ to the total content of Fe 2+ and Fe 3+ in the borosilicate glass of the present embodiment.
  • [Fe 2+ ]/([Fe 2+ ]+[Fe 3+ ]) is obtained by the following method. After decomposing the crushed glass with a mixed acid of hydrofluoric acid and hydrochloric acid at room temperature, a certain amount of the decomposing solution was put into a plastic container, and a hydroxylammonium chloride solution was added to decompose Fe 3+ in the sample solution into Fe 2+ . be reduced to A 2,2′-dipyridyl solution and an ammonium acetate buffer are then added to develop the Fe 2+ color. The coloring solution is adjusted to a constant amount with ion-exchanged water, and the absorbance at a wavelength of 522 nm is measured with an absorptiometer.
  • the Fe 2+ amount is obtained by calculating the concentration from the calibration curve prepared using the standard solution. Since Fe 3+ in the sample solution was reduced to Fe 2+ , this Fe 2+ amount means “[Fe 2+ ]+[Fe 3+ ]” in the sample.
  • the borosilicate glass of this embodiment does not substantially contain BaO, PbO and As2O3 .
  • BaO By being substantially free of BaO, an increase in the specific gravity of the glass is avoided and low brittleness and strength are maintained. Also, it is possible to prevent the glass from becoming brittle.
  • PbO and As 2 O 3 are not substantially included, it is possible to prevent adverse effects on the human body and the environment.
  • the average transmittance of light with a wavelength of 900 nm to 1300 nm is T b [%]
  • the flat glass has a glass viscosity of When heated at a temperature T of 12 or higher, which is 10 12 [dPa s], and bent, when the thickness is converted to 1.50 mm, the average transmittance of light with a wavelength of 900 nm to 1300 nm is Ta [%]. Then, the following formula (1) is satisfied. T b ⁇ T a >0 (1)
  • Formula (1) means that the average transmittance of light with a wavelength of 900 nm to 1300 nm decreases when flat glass is heated at T12 or higher, which is the bending temperature of glass, and bent. Bending forming of the glass becomes possible by heating the flat glass at T12 or higher.
  • the borosilicate glass of this embodiment has a scattering intensity due to small-angle X-ray scattering (SAXS) before the bending process, and a peak at a specific scattering vector q have When such a peak is observed, an interference effect called inter-particle interference occurs due to a large proportion of heterogeneous phases.
  • SAXS small-angle X-ray scattering
  • inter-particle interference occurs due to a large proportion of heterogeneous phases.
  • the light absorption of the borosilicate glass in this embodiment is due to Fe ions, and the light absorption behavior is greatly affected by the Fe structure in the glass structure.
  • a change in light absorption behavior occurs due to the structure around the Fe ions, resulting in a change in transmittance.
  • the microstructure in the glass changes by applying heat to the glass when the glass is bent, and the absorption behavior of Fe ions caused by Fe 2 O 3 changes.
  • the average transmittance of light in the above wavelength band is reduced.
  • the bent glass with improved heat shielding properties can be obtained. Obtainable.
  • the conditions for bending the glass for example, flat glass is heated to 630° C. and the bending time is set to 6 minutes.
  • the flat glass may be bent by press molding for a predetermined time while maintaining the heating temperature at T12 or higher, for example, using a mold. .
  • the flat glass may be cooled after maintaining the bent state at a heating temperature of T12 or higher, for example, for a bending time of 0.1 seconds or longer.
  • the temperature conditions for the heating temperature to be T12 or higher may vary depending on the glass composition, and may be adjusted, for example, within the range of 600 °C to 700°C. good.
  • the bending time may be 1 second or longer, 5 seconds or longer, 10 seconds or longer, 30 seconds or longer, 1 minute or longer, 5 minutes or longer, or 10 minutes or longer. .
  • T b ⁇ T a is preferably 0.50% or more, more preferably 0.70% or more, and even more preferably 0.90% or more.
  • the borosilicate glass of another embodiment of the present invention is a flat glass with a scattering vector q measured by small-angle X-ray scattering (SAXS) in the range of 0.10 to 2.0 (nm ⁇ 1 ) with a normalized scattering intensity of is 0.35 or more, and when the flat glass is heated at a temperature T 12 or more at which the glass viscosity becomes 10 12 [dPa ⁇ s] and is bent, the scattering vector q by SAXS measurement is 0.35. The maximum value of normalized scattering intensity in the range of 10 to 2.0 (nm ⁇ 1 ) is reduced.
  • SAXS small-angle X-ray scattering
  • the maximum value of the normalized scattering intensity is 0.35 or more when the scattering vector q is in the range of 0.10 to 2.0 (nm ⁇ 1 ). decreases. This is because, as described above, the borosilicate glass of the present embodiment undergoes a structural change in the glass due to the bending process, resulting in a reduction in heterogeneous structures.
  • the light absorption of the borosilicate glass in this embodiment is due to Fe ions, and the light absorption behavior is greatly affected by the Fe structure in the glass structure. As a result of the change in the fine structure in the glass as described above, a change in light absorption behavior occurs due to the structure around the Fe ions, resulting in a change in transmittance.
  • the fine structure in the glass changes when heat is applied to the glass when the glass is bent, and the absorption behavior of Fe ions caused by Fe 2 O 3 changes. It is possible to obtain a bent glass having a reduced average transmittance of light in the wavelength band and thus improved heat shielding properties.
  • the bending process reduces the maximum value of the normalized scattering intensity in the range of 0.10 to 2.0 (nm ⁇ 1 ) of the scattering vector q by SAXS measurement.
  • the ratio (S a /S b ) of the maximum value of the normalized scattering intensity after the bending process (S a ) to the maximum value of the normalized scattering intensity ( S b ) before the bending process is expressed as
  • the change rate of the maximum value of the normalized scattering intensity before and after, that is, 1-(S a /S b ) is preferably 0.05 or more, more preferably 0.10 or more, further preferably 0.30 or more, and 0 0.50 or greater is particularly preferred, and 0.80 or greater is most preferred.
  • the borosilicate glass of the present embodiment is defined by ISO-13837:2008 convention A when the thickness is converted to 1.50 mm in flat glass, and the total solar transmittance measured at a wind speed of 4 m / s is Tts1, when the flat glass is heated at a temperature T 12 or higher at which the glass viscosity becomes 10 12 [dPa s] and bent, the thickness is converted to 1.50 mm ISO-13837: 2008 convention
  • Tts2 is the total solar transmittance defined by A and measured at a wind speed of 4 m/s, it is preferable to satisfy the following formula (2). (Tts1-Tts2)/Tts1 ⁇ 0.002 (2)
  • the above formula (2) means that when flat glass is bent at the above predetermined temperature, the rate of change in total solar transmittance before and after bending of the glass is large. As described above, this means that the bending process causes a structural change in the glass and reduces the heterogeneous structure, thereby lowering the total solar transmittance.
  • the degree of change in the total solar transmittance represented by the above formula (2) is a certain value or more, that is, the change in coloring due to bending at a predetermined temperature increases.
  • the total solar transmittance can be reduced by performing the bending process, and as a result, the heat shielding property can be improved.
  • (Tts1-Tts2)/Tts1 is preferably 0.004 or more, more preferably 0.008 or more, still more preferably 0.010 or more, and particularly preferably 0.015 or more.
  • the visible light transmittance of the glass plate before bending is Tv1 when the thickness is converted to 1.50 mm in flat glass, and the glass viscosity is 10 12 [dPa s ], the following formula (3) may be satisfied when the visible light transmittance of the glass plate after heating at 12 or higher and bending is Tv2.
  • the above visible light transmittance shall be measured by the method specified in ISO-9050:2003 using a D65 light source.
  • the above formula (3) means that when the flat glass is bent at the above predetermined temperature, the visible light transmittance increases before and after the glass is bent. As described above, this means that the bending process causes a structural change in the glass and reduces heterogeneous structures, thereby suppressing scattering in the visible light range and improving the visible light transmittance. As described above, according to the borosilicate glass of the present embodiment, the visible light transmittance is improved by performing the bending treatment, and as a result, the visibility can be improved.
  • the borosilicate glass of this embodiment absorbs light in the near-infrared region when water is present in the glass. Therefore, the borosilicate glass of the present embodiment preferably contains a certain amount of moisture in order to improve heat shielding properties.
  • Moisture in glass can generally be expressed by a value called ⁇ -OH value, and the ⁇ -OH value is preferably 0.050 mm ⁇ 1 or more, more preferably 0.10 mm ⁇ 1 or more, and further preferably 0.15 mm ⁇ 1 or more. preferable.
  • ⁇ -OH is obtained by the following formula from the transmittance of glass measured using FT-IR (Fourier transform infrared spectrophotometer).
  • ⁇ -OH (1/X) log 10 (T A /T B ) [mm ⁇ 1 ]
  • X sample thickness [mm]
  • T A Transmittance [%] at reference wave number 4000 cm ⁇ 1
  • T B Minimum transmittance [%] near hydroxyl group absorption wave number 3600 cm ⁇ 1
  • the ⁇ -OH value of the borosilicate glass of the present embodiment is preferably 0.70 mm ⁇ 1 or less, more preferably 0.60 mm ⁇ 1 or less, further preferably 0.50 mm ⁇ 1 or less, further preferably 0.40 mm ⁇ 1 The following are particularly preferred.
  • [Al 2 O 3 ]/([SiO 2 ]+[B 2 O 3 ]) is preferably 0.050 or less, more preferably 0.045 or less, and 0.040 or less. More preferred. Thereby, a low dielectric constant can be maintained.
  • [Al 2 O 3 ], [SiO 2 ], and [B 2 O 3 ] are respectively Al 2 O 3 , SiO 2 , and B 2 O 3 contained in the borosilicate glass of this embodiment. means the content of Further, “[Al 2 O 3 ] / ( [ SiO 2 ]+[B 2 O 3 ])” is the Al 2 O 3 content ratio.
  • [Al 2 O 3 ]/([SiO 2 ]+[B 2 O 3 ]) is preferably 0.005 or more, more preferably 0.008 or more, and more preferably 0.010 or more. More preferred.
  • the borosilicate glass of this embodiment may have a density of 2.0 g/cm 3 or more and 2.5 g/cm 3 or less. Moreover, the Young's modulus of the borosilicate glass of the present embodiment may be 50 GPa or more and 80 GPa or less.
  • the borosilicate glass of the present embodiment preferably contains a certain amount or more of SiO 2 in order to ensure weather resistance.
  • the density of the borosilicate glass of the present embodiment can be 2.0 g/cm 3 or more.
  • the borosilicate glass of this embodiment preferably has a density of 2.1 g/cm 3 or more. Further, when the borosilicate glass of the present embodiment has a density of 2.5 g/cm 3 or less, it is less likely to become brittle and a reduction in weight is achieved.
  • the density of the borosilicate glass of this embodiment is preferably 2.4 g/cm 3 or less.
  • the borosilicate glass of the present embodiment has a high Young's modulus and high rigidity, and is more suitable for vehicle window glass and the like.
  • the borosilicate glass of the present embodiment preferably has a Young's modulus of 55 GPa or more, more preferably 60 GPa or more, and even more preferably 62 GPa or more.
  • the dielectric constant ( ⁇ r ) and dielectric loss tangent (tan ⁇ ) of the glass increase. is 78 GPa or less, preferably 76 GPa or less, and more preferably 74 GPa or less.
  • the borosilicate glass of the present embodiment preferably has a small average coefficient of linear expansion, which suppresses the occurrence of thermal stress caused by the temperature distribution of the glass plate, and makes the glass plate less susceptible to thermal cracking.
  • the average linear expansion coefficient of the borosilicate glass of the present embodiment from 50° C. to 350° C. is preferably 25 ⁇ 10 ⁇ 7 /K or more, more preferably 28 ⁇ 10 ⁇ 7 /K or more, and 30 ⁇ 10 ⁇ 7 /K or more. K or more is more preferable, 32 ⁇ 10 ⁇ 7 /K or more is particularly preferable, and 35 ⁇ 10 ⁇ 7 /K or more is most preferable.
  • the average coefficient of linear expansion of the borosilicate glass of the present embodiment is too large, it may be caused by the temperature distribution of the glass plate during the glass plate forming process, the slow cooling process, or the windshield, roof glass, or rear glass forming process. The thermal stress generated by the glass plate is likely to occur, and there is a risk that thermal cracking of the glass plate may occur.
  • the average coefficient of linear expansion of the borosilicate glass of the present embodiment is too large, the difference in expansion between the glass plate and the support member becomes large, causing distortion and possibly breaking the glass plate.
  • the average coefficient of linear expansion of the borosilicate glass of the present embodiment from 50° C. to 350° C. may be 60 ⁇ 10 ⁇ 7 /K or less, preferably 58 ⁇ 10 ⁇ 7 /K or less, and 56 ⁇ 10 ⁇ 7 /K or less is more preferable, 54 ⁇ 10 ⁇ 7 /K or less is more preferable, 52 ⁇ 10 ⁇ 7 /K or less is particularly preferable, and 50 ⁇ 10 ⁇ 7 /K or less is most preferable.
  • T12 is preferably 650°C or lower, more preferably 640°C or lower, even more preferably 630°C or lower, particularly preferably 620°C or lower, and most preferably 610°C or lower.
  • the borosilicate glass of the present embodiment has a T11 of preferably 680° C. or lower, more preferably 670° C. or lower, even more preferably 660° C. or lower, particularly preferably 650° C. or lower, and most preferably 640° C. or lower.
  • T 12 and T 11 are in the above ranges, the energy required for bending heat treatment can be kept low, and bending heat treatment can be performed under the same conditions as soda lime glass used for general automotive glass, and the tact time is improved. lead to shortening.
  • the borosilicate glass of the present embodiment preferably has a Tg of 400° C. or higher and 650° C. or lower.
  • Tg represents the glass transition point of glass. If the Tg is within this predetermined temperature range, the glass can be bent within the range of normal manufacturing conditions. If the Tg of the borosilicate glass of the present embodiment is lower than 400°C, there is no problem with formability, but the alkali content or alkaline earth content is too high, resulting in an excessive average linear expansion coefficient of the glass. It becomes easy to cause problems such as deterioration of weather resistance. Further, if the Tg of the borosilicate glass of the present embodiment is lower than 400°C, the glass may devitrify in the forming temperature range and may not be formed.
  • the T g of the borosilicate glass of the present embodiment is more preferably 450° C. or higher, still more preferably 470° C. or higher, and particularly preferably 490° C. or higher. On the other hand, if the Tg is too high, a high temperature is required during glass bending, making production difficult.
  • the T g of the borosilicate glass of the present embodiment is more preferably 600° C. or lower, more preferably 580° C. or lower, particularly preferably 550° C. or lower, and most preferably 530° C. or lower.
  • the borosilicate glass of the present embodiment contains components ( hereinafter, also referred to as “other components”).
  • Other components are, for example, ZrO2 , Y2O3 , TiO2 , CeO2 , ZnO, Nd2O5 , P2O5 , GaO2 , GeO2, MnO2 , CoO , Cr2O3 , V 2 O 5 , Se, Au 2 O 3 , Ag 2 O, CuO, CdO, SO 3 , Cl, F, SnO 2 , Sb 2 O 3 and the like, and may be metal ions or oxides.
  • the total content is preferably 5.0% or less, more preferably 3.0% or less, and particularly preferably 2.0% or less.
  • the borosilicate glass of this embodiment preferably does not substantially contain Er 2 O 3 . This makes it possible to suppress the absorption of visible light, particularly light in the blue to green range (wavelength 400 nm to 550 nm). In this case, the transmittance of light with a wavelength of 500 nm can be 78.0% or more when the thickness of the borosilicate glass of this embodiment is converted to 1.50 mm.
  • the borosilicate glass of this embodiment may contain Cr2O3 .
  • Cr 2 O 3 can act as an oxidizing agent to control the amount of FeO.
  • its content is preferably 0.0020% or more, more preferably 0.0040% or more. Since Cr 2 O 3 has coloring properties with respect to light in the visible range, there is a possibility that the visible light transmittance may decrease.
  • the borosilicate glass of the present embodiment contains Cr 2 O 3 , it is preferably 1.0% or less, more preferably 0.50% or less, even more preferably 0.30% or less, and particularly preferably 0.10% or less. .
  • the borosilicate glass of this embodiment may contain SnO2 .
  • SnO 2 can act as a reducing agent to control the amount of FeO.
  • its content is preferably 0.010% or more, more preferably 0.040% or more, still more preferably 0.060% or more, and 0.080% or more.
  • the SnO 2 content in the borosilicate glass of the present embodiment is preferably 1.0% or less, more preferably 0.50% or less, more preferably 0.50% or less, in order to suppress defects derived from SnO 2 during glass plate production. 30% or less is more preferable, and 0.20% or less is particularly preferable.
  • the borosilicate glass of this embodiment may contain P2O5 .
  • P 2 O 5 improves the solubility of the borosilicate glass of this embodiment in the float process, but tends to cause defects in the glass in the float bath. Therefore, the content of P 2 O 5 in the borosilicate glass of the present embodiment is preferably 5.0% or less, more preferably 1.0% or less, still more preferably 0.10% or less, and 0.050% or less. is particularly preferred, and less than 0.010% is most preferred.
  • ZrO 2 may be contained to improve chemical durability, and when ZrO 2 is contained, its content is preferably 0.5% or more.
  • the content is more preferably 1.8% or less, more preferably 1.5% or less, because the average coefficient of linear expansion may increase.
  • the borosilicate glass of this embodiment preferably has sufficient visible light transmittance.
  • the visible light transmittance of the borosilicate glass of the present embodiment can be calculated from the formula specified in JIS R3106 (2019) using a spectrophotometer or the like.
  • the transmittance of light with a wavelength of 500 nm when converted to a thickness of 1.50 mm is preferably 78.0% or more, and 80.0% or more. More preferably, 82.0% or more is even more preferable. Further, the transmittance of light of the above wavelength is, for example, 90.0% or less.
  • the average transmittance of light with a wavelength of 450 nm to 700 nm when the thickness is converted to 1.50 mm is preferably 78.0% or more, and 80.0%. % or more is more preferable, and 82.0% or more is even more preferable. Further, the average transmittance of light of the above wavelength is, for example, 90.0% or less.
  • the average transmittance here means an average value of transmittances measured at intervals of 1 nm.
  • the borosilicate glass of the present embodiment preferably has a transmittance of 90.0% or less, more preferably 85.0% or less, and more preferably 80.0% or less for light having a wavelength of 1000 nm when converted to a thickness of 1.50 mm. % or less is more preferable. Further, the transmittance of light of the above wavelength is, for example, 50.0% or more.
  • the borosilicate glass of the present embodiment preferably has an average transmittance of 90.0% or less, more preferably 85.0% or less, for light having a wavelength of 900 nm to 1300 nm when converted to a thickness of 1.50 mm. 80.0% or less is more preferable. Also, the average transmittance of light of the above wavelength is, for example, 50.0% or more.
  • the average transmittance here means an average value of transmittances measured at intervals of 1 nm.
  • the thickness of the borosilicate glass of the present embodiment is preferably 1.50 mm or more, more preferably 1.80 mm or more, even more preferably 2.00 mm or more, and particularly preferably 2.20 mm or more. 2.50 mm or more is most preferable.
  • it is preferably 4.50 mm or less, more preferably 4.00 mm or less, even more preferably 3.80 mm or less, and particularly preferably 3.70 mm or less.
  • the borosilicate glass of the present embodiment preferably has a high transmittance of millimeter waves.
  • the borosilicate glass of the present embodiment has a low tan ⁇ .
  • the borosilicate glass of the present embodiment can also adjust the dielectric constant ( ⁇ r ) by similarly adjusting the composition, suppresses the reflection of radio waves at the interface with the interlayer, and has a high radio wave transmittance for millimeter waves. achievable.
  • the dielectric constant ( ⁇ r ) of the borosilicate glass of this embodiment at a frequency of 10 GHz is preferably 6.0 or less. If the relative dielectric constant ( ⁇ r ) at a frequency of 10 GHz is 6.0 or less, the difference in relative dielectric constant ( ⁇ r ) from the intermediate film becomes small, and the reflection of radio waves at the interface with the intermediate film can be suppressed.
  • the dielectric constant ( ⁇ r ) of the borosilicate glass of the present embodiment at a frequency of 10 GHz is more preferably 5.5 or less, still more preferably 5.3 or less, and particularly preferably 5.0 or less.
  • the lower limit of the dielectric constant ( ⁇ r ) of the borosilicate glass of the present embodiment at a frequency of 10 GHz is not particularly limited, but is, for example, 3.8 or more.
  • the dielectric loss tangent (tan ⁇ ) of the borosilicate glass of this embodiment at a frequency of 10 GHz is preferably 0.010 or less. If the dielectric loss tangent (tan ⁇ ) at a frequency of 10 GHz is 0.010 or less, radio wave transmittance can be increased.
  • the dielectric loss tangent (tan ⁇ ) of the borosilicate glass of the present embodiment at a frequency of 10 GHz is more preferably 0.009 or less, still more preferably 0.0085 or less, even more preferably 0.008 or less, particularly preferably 0.0075 or less, and 0 0.007 or less is most preferred.
  • the lower limit of the dielectric loss tangent (tan ⁇ ) at a frequency of 10 GHz of the borosilicate glass of the present embodiment is not particularly limited, but is, for example, 0.003 or more.
  • the dielectric constant ( ⁇ r ) and dielectric loss tangent (tan ⁇ ) of the borosilicate glass of this embodiment at a frequency of 10 GHz can be measured by, for example, the split-post dielectric resonator method (SPDR method).
  • SPDR method split-post dielectric resonator method
  • a nominal fundamental frequency of 10 GHz type split post dielectric resonator manufactured by QWED, a vector network analyzer E8361C manufactured by Keysight, and 85071E option 300 permittivity calculation software manufactured by Keysight can be used.
  • the method for producing the borosilicate glass of the present embodiment is not particularly limited, for example, float glass formed by a known float method or fusion draw glass formed by a fusion draw method is preferable.
  • a molten glass base is floated on a molten metal such as tin, and a glass plate with a uniform thickness and width is formed under strict temperature control.
  • molten glass is continuously poured down from a molded body to form a strip-shaped glass ribbon, and a glass plate with uniform thickness and width is formed.
  • the average cooling rate in the method for producing borosilicate glass of the present embodiment is preferably 1°C/min or more.
  • the average cooling rate in the method for producing borosilicate glass means the average cooling rate when slowly cooling the formed glass.
  • the average cooling rate is 1° C./min or more, a heterogeneous phase is generated during cooling, and the heat shielding property can be improved during production of bent glass described later.
  • the above average cooling rate can be calculated as follows.
  • the composition of the borosilicate glass for which the average cooling rate is to be calculated is analyzed, and a plurality of glasses having the same composition are produced with different average cooling rates.
  • the refractive indices of a plurality of prepared glasses are measured to prepare a calibration curve between the average cooling rate and the refractive index.
  • the average cooling rate can be calculated from the calibration curve.
  • the refractive index can be measured, for example, by the V-block method.
  • the average cooling rate is more preferably 5°C/min or more, still more preferably 10°C/min or more, even more preferably 20°C/min or more, particularly preferably 30°C/min or more, and particularly preferably 35°C/min or more.
  • 40° C./min or more is most preferred.
  • the upper limit of the average cooling rate is not particularly limited, but is preferably 400°C/min or less, more preferably 350°C/min or less, even more preferably 300°C/min or less, particularly preferably 250°C/min or less, and 200°C. /min or less is most preferred. If the average cooling rate is 400° C./min or less, it is easy to form a thick glass.
  • a bent glass according to an embodiment of the present invention is made of the above borosilicate glass. That is, it is formed by bending the borosilicate glass.
  • the bent glass of the present embodiment may be bent glass obtained by molding the flat plate-shaped borosilicate glass into a curved shape by gravity molding, press molding, or the like.
  • the bent glass of the present embodiment is glass that is curved with a predetermined curvature, and may be a single curved glass that is curved only in one of the vertical and horizontal directions, or may be curved in both the vertical and horizontal directions. Double curved glass may be used.
  • the bent glass of this embodiment preferably has a minimum radius of curvature of 500 mm or more and 100000 mm or less.
  • the radius of curvature of the bent glass is calculated by shape simulation based on the amount of warpage inherent in the sample obtained by self-weight deflection correction in the double-sided differential mode using a laser displacement meter (Dyvoce manufactured by Kozu Seiki Co., Ltd.). , the radius of curvature is obtained from the shape obtained by the simulation.
  • the borosilicate glass is heated and bent to shape the bent glass.
  • a method for forming bent glass there is a method in which a heated glass plate is placed on a forming die and pressed from above with a pressing means to form a bend.
  • a flat glass plate is placed on a mold having a bending surface corresponding to a desired curved surface, and in this state, the mold is carried into a heating furnace, and the glass plate is softened in the heating furnace.
  • a method of heating to near the point temperature is also included. According to this molding method, the glass sheet bends along the bending surface of the mold due to its own weight as it softens, so that the glass sheet having the desired curved surface can be manufactured.
  • bending by the above-described pressing means is preferable.
  • the bending method by the pressing means is not particularly limited, and for example, the method described in International Publication No. WO 2016/093031 or the like can be appropriately employed.
  • a bending method using the above pressing means will be exemplified below.
  • the borosilicate glass of this embodiment is transported to a press area by a transport conveyor or the like. Subsequently, in the press area, the borosilicate glass is heated to a temperature at which it can be bent and softened.
  • the temperature at which bending is possible is, for example, the temperature T12 or higher at which the glass viscosity becomes 10 12 [dPa ⁇ s].
  • the heating may be performed by a heater or the like in a heating furnace in the process of conveying to the press area by a conveyer or the like.
  • the bending time under the condition that the heating temperature ( ⁇ T 12 ) is maintained can be set to 1 second or longer, for example.
  • a lower pressing die (female die) and an upper pressing die (male die) are arranged at predetermined positions in the press area. Corresponds to the curved shape of borosilicate glass that is bent in the orthogonal direction.
  • the female die can move up and down between a standby position below the conveyer and a pressing position above the conveyer.
  • the borosilicate glass is press-molded by rising from the position to the press position above the transfer conveyor.
  • the press-molded borosilicate glass is transported to the cooling area by a transport shuttle or the like.
  • the borosilicate glass is cooled by, for example, blowing cooling air onto the borosilicate glass.
  • the average cooling rate in the method for manufacturing bent glass of this embodiment is preferably 400°C/min or more.
  • the average cooling rate in the method of manufacturing bent glass means the average cooling rate when slowly cooling the press-molded borosilicate glass.
  • the average cooling rate is more preferably 450°C/min or higher, even more preferably 500°C/min or higher, and particularly preferably 600°C/min or higher.
  • the upper limit of the average cooling rate is not particularly limited, but from the viewpoint of the performance of the cooling equipment, it is preferably 3000 ° C./min or less, more preferably 2500 ° C./min or less, further preferably 2000 ° C./min or less, and 1800 ° C./min or less. is particularly preferred, and 1600° C./min or less is most preferred.
  • bent glass is formed.
  • the bending of the borosilicate glass of the present embodiment has been described above, the bending may be performed in the state of the laminated glass described later.
  • a laminated glass according to an embodiment of the present invention includes a first glass plate, a second glass plate, and an intermediate film sandwiched between the first glass plate and the second glass plate. At least one of the two glass plates is the borosilicate glass or the bent glass.
  • FIG. 1 is a diagram showing an example of the laminated glass 10 according to this embodiment.
  • the laminated glass 10 has a first glass plate 11 , a second glass plate 12 , and an intermediate film 13 sandwiched between the first glass plate 11 and the second glass plate 12 .
  • the laminated glass 10 according to the present embodiment is not limited to the aspect of FIG. 1, and can be modified without departing from the gist of the invention.
  • the intermediate film 13 may be formed of one layer as shown in FIG. 1, or may be formed of two or more layers.
  • the laminated glass 10 according to the present embodiment may have three or more glass plates, and in that case, an organic resin or the like may be interposed between adjacent glass plates.
  • the laminated glass 10 according to the present embodiment will be described as having only two glass plates, the first glass plate 11 and the second glass plate 12, and sandwiching the intermediate film 13 therebetween.
  • the borosilicate glass or the bent glass is used for both the first glass plate 11 and the second glass plate 12 .
  • the first glass plate 11 and the second glass plate 12 may be made of borosilicate glass or bent glass of the same composition, or may be made of borosilicate glass or bent glass of different compositions.
  • the type of the glass plate is not particularly limited, and conventionally known glass plates used for vehicle window glass and the like can be used. Available. Specific examples include alkali aluminosilicate glass and soda lime glass. These glass plates may be colored to such an extent that their transparency is not impaired, or may be uncolored.
  • one of the first glass plate 11 and the second glass plate 12 may be alkali aluminosilicate glass containing 1.0% or more of Al 2 O 3 .
  • alkali aluminosilicate glass By using the alkali aluminosilicate glass for the first glass plate 11 or the second glass plate 12, chemical strengthening becomes possible as described later, and the strength can be increased.
  • Alkali aluminosilicate glass also has the advantage of being easier to chemically strengthen than borosilicate glass.
  • the Al 2 O 3 content of the alkali aluminosilicate glass is more preferably 2.0% or more, more preferably 2.5% or more.
  • the content of Al 2 O 3 is preferably 20% or less, and 15%. The following are more preferred.
  • the alkali aluminosilicate glass preferably has an R 2 O content of 10% or more, more preferably 12% or more, and even more preferably 13% or more. Further, in the alkali aluminosilicate glass, if the content of R 2 O is high, the transmittance of millimeter waves may decrease, so the content of R 2 O is preferably 25% or less, more preferably 20% or less. Preferably, 19% or less is more preferable.
  • R2O represents the total amount of Li2O , Na2O and K2O .
  • alkali aluminosilicate glass examples include glasses having the following compositions. 61% ⁇ SiO 2 ⁇ 77% 1.0% ⁇ Al 2 O 3 ⁇ 20% 0.0% ⁇ B2O3 ⁇ 10 % 0.0% ⁇ MgO ⁇ 15% 0.0% ⁇ CaO ⁇ 10% 0.0% ⁇ SrO ⁇ 1.0% 0.0% ⁇ BaO ⁇ 1.0% 0.0% ⁇ Li 2 O ⁇ 15% 2.0% ⁇ Na 2 O ⁇ 15% 0.0% ⁇ K2O ⁇ 6.0 % 0.0% ⁇ ZrO2 ⁇ 4.0 % 0.0% ⁇ TiO2 ⁇ 1.0 % 0.0% ⁇ Y2O3 ⁇ 2.0 % 10% ⁇ R2O ⁇ 25 % 0.0% ⁇ RO ⁇ 20% (R 2 O represents the total amount of Li 2 O, Na 2 O and K 2 O, and RO represents the total amount of MgO, CaO, SrO and BaO.)
  • soda lime glass containing less than 1.0% of Al 2 O 3 may be used as the soda lime glass.
  • glasses having the following compositions can be exemplified. 60% ⁇ SiO 2 ⁇ 75% 0.0% ⁇ Al 2 O 3 ⁇ 1.0% 2.0% ⁇ MgO ⁇ 11% 2.0% ⁇ CaO ⁇ 10% 0.0% ⁇ SrO ⁇ 3.0% 0.0% ⁇ BaO ⁇ 3.0% 10% ⁇ Na 2 O ⁇ 18% 0.0% ⁇ K2O ⁇ 8.0 % 0.0% ⁇ ZrO2 ⁇ 4.0 % 0.0010% ⁇ Fe2O3 ⁇ 5.0 %
  • the lower limit of the thickness of the first glass plate 11 or the second glass plate 12 is preferably 0.50 mm or more, more preferably 0.70 mm or more, still more preferably 1.00 mm or more, and particularly preferably 1.50 mm or more.
  • the thickness of the first glass plate 11 or the second glass plate 12 is 0.50 mm or more, sound insulation and strength can be improved.
  • the thickness of the first glass plate 11 and the thickness of the second glass plate 12 may be the same or different.
  • the thickness of the first glass plate 11 and the second glass plate 12 may be constant over the entire surface, and the thickness of one or both of the first glass plate 11 and the second glass plate 12 may vary from place to place as desired, such as forming a wedge shape with varying .
  • One or both of the first glass plate 11 and the second glass plate 12 may be subjected to strengthening treatment in order to improve strength.
  • the strengthening method may be physical strengthening or chemical strengthening.
  • thermal strengthening treatment of the glass plate can be mentioned.
  • a uniformly heated glass sheet is rapidly cooled from a temperature near the softening point, and compressive stress is generated on the glass surface due to the temperature difference between the glass surface and the inside of the glass.
  • Compressive stress is generated uniformly over the entire surface of the glass, forming a compressive stress layer with a uniform depth over the entire surface of the glass.
  • Thermal strengthening is more suitable for strengthening thick glass sheets than chemical strengthening.
  • Examples of chemical strengthening methods include the ion exchange method.
  • a glass plate is immersed in a treatment liquid (eg potassium nitrate molten salt), and ions with a small ionic radius (eg Na ions) contained in the glass are exchanged with ions with a large ionic radius (eg K ions). , causing a compressive stress on the glass surface. Compressive stress is generated uniformly over the entire surface of the glass sheet, and a compressive stress layer having a uniform depth is formed over the entire surface of the glass sheet.
  • a treatment liquid eg potassium nitrate molten salt
  • the magnitude of the compressive stress on the surface of the glass plate (hereinafter also referred to as the surface compressive stress CS) and the depth DOL of the compressive stress layer formed on the surface of the glass plate are the glass composition, the chemical strengthening treatment time, and the chemical strengthening treatment, respectively. Can be adjusted by temperature.
  • Examples of chemically strengthened glass include those obtained by chemically strengthening the alkali aluminosilicate glass described above.
  • the intermediate film 13 according to this embodiment is sandwiched between the first glass plate 11 and the second glass plate 12 .
  • the laminated glass 10 of the present embodiment is provided with the intermediate film 13, so that the first glass plate 11 and the second glass plate 12 are firmly adhered to each other, and when the scattered pieces collide with the glass plate, the impact force is reduced. can be mitigated.
  • various organic resins commonly used in laminated glass conventionally used as laminated glass for vehicles can be used.
  • PE polyethylene
  • EVA ethylene vinyl acetate copolymer
  • PP polypropylene
  • PS polystyrene
  • PMA methacrylic resin
  • PVC polyvinyl chloride
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • CA diallyl phthalate resin
  • UP urea resin
  • MF melamine resin
  • UP melamine resin
  • UP unsaturated polyester
  • PVB polyvinyl butyral
  • PVF polyvinyl formal
  • PVAL polyvinyl alcohol
  • PVc vinyl acetate resin
  • IO ionomer
  • TPX polymethylpentene
  • PVDC vinylidene chloride
  • PVDF polysulfone
  • PVDF polyvinylidene fluoride
  • the thickness of the intermediate film 13 is preferably 0.30 mm or more, more preferably 0.50 mm or more, and even more preferably 0.70 mm or more, from the viewpoint of impact force relaxation and sound insulation.
  • the thickness of the intermediate film 13 is preferably 1.00 mm or less, more preferably 0.90 mm or less, and even more preferably 0.80 mm or less, from the viewpoint of suppressing a decrease in visible light transmittance.
  • the thickness of the intermediate film 13 is preferably in the range of 0.30 mm to 1.00 mm, more preferably in the range of 0.70 mm to 0.80 mm.
  • the thickness of the intermediate film 13 may be uniform over the entire surface, or may vary from place to place as necessary.
  • the laminated glass 10 may crack when the laminated glass 10 is produced through the heating process described later. and warping may occur, resulting in poor appearance. Therefore, it is preferable that the difference between the linear expansion coefficients of the intermediate film 13 and the first glass plate 11 or the second glass plate 12 is as small as possible.
  • the difference between the linear expansion coefficients of the intermediate film 13 and the first glass plate 11 or the second glass plate 12 may be represented by the difference between the average linear expansion coefficients in a predetermined temperature range.
  • the predetermined average linear expansion coefficient difference may be set within a temperature range below the glass transition point of the resin material.
  • the difference in coefficient of linear expansion between the first glass plate 11 or the second glass plate 12 and the resin material may be set by a predetermined temperature below the glass transition point of the resin material.
  • the intermediate film 13 may use an adhesive layer containing an adhesive, and although the adhesive is not particularly limited, for example, an acrylic adhesive, a silicone adhesive, or the like can be used.
  • the adhesive is not particularly limited, for example, an acrylic adhesive, a silicone adhesive, or the like can be used.
  • the intermediate film 13 is an adhesive layer, there is no need for a heating step in the bonding process of the first glass plate 11 and the second glass plate 12, so there is little risk of cracking or warping.
  • layers other than the first glass plate 11, the second glass plate 12, and the intermediate film 13 are formed within the range that does not impair the effects of the present invention.
  • it may be provided with a coating layer imparting a water-repellent function, a hydrophilic function, an anti-fogging function, etc., an infrared reflective film, or the like.
  • the position where the other layers are provided is not particularly limited, and may be provided on the surface of the laminated glass 10, and provided so as to be sandwiched between the first glass plate 11, the second glass plate 12, or the intermediate film 13. good too.
  • the laminated glass 10 of the present embodiment may be provided with a black ceramic layer or the like arranged in a band shape on part or all of the peripheral portion for the purpose of concealing the attachment portion to the frame or the like, the wiring conductor, etc. good.
  • the manufacturing method of the laminated glass 10 of the embodiment of the present invention can be the same as that of the conventionally known laminated glass.
  • the first glass plate 11, the intermediate film 13, and the second glass plate 12 are laminated in this order, and the first glass plate 11 and the second glass plate 12 are laminated in this order, and the first glass plate 11 and the second glass plate 12 become the intermediate films.
  • a laminated glass 10 having a configuration of being bonded via 13 is obtained.
  • the intermediate film 13 is formed on the first glass plate 11 and the second glass plate 12 .
  • a step of inserting between two glass plates 12 and applying heat and pressure may be performed. Through such steps, the laminated glass 10 having a configuration in which the first glass plate 11 and the second glass plate 12 are bonded via the intermediate film 13 may be obtained.
  • the total thickness of the first glass plate 11, the second glass plate 12 and the interlayer 13 is 6.00 mm or less, and is defined by ISO-9050:2003 using a D65 light source.
  • the visible light transmittance Tv is preferably 70.0% or more, more preferably 71.0% or more, still more preferably 72.0% or more, and particularly preferably 75.0% or more.
  • the visible light transmittance Tv is, for example, 80.0% or less.
  • each thickness of the first glass plate 11 and the second glass plate 12 may be 2.00 mm.
  • the total thickness of the first glass plate 11, the second glass plate 12 and the intermediate film 13 may be 2.50 mm or more, 3.00 mm or more, 3.50 mm or more, or 4.00 mm or more. It may be 4.50 mm or more.
  • the total thickness of the first glass plate 11, the second glass plate 12 and the intermediate film 13 is 6.00 mm or less, defined by ISO-13837:2008 convention A, and the wind speed
  • the total solar transmittance Tts measured at 4 m/s is preferably 75.0% or less.
  • the total solar transmittance Tts of the laminated glass 10 according to the embodiment of the present invention is 75.0% or less, sufficient heat shielding properties can be obtained.
  • the total solar radiation transmittance Tts is more preferably 70.0% or less, further preferably 68.0% or less, and particularly preferably 66.0% or less.
  • the total solar transmittance Tts is, for example, 50.0% or more.
  • each thickness of the first glass plate 11 and the second glass plate 12 may be 2.00 mm. Furthermore, the total thickness of the first glass plate 11, the second glass plate 12 and the intermediate film 13 may be 2.50 mm or more, 3.00 mm or more, 3.50 mm or more, or 4.00 mm or more. It may be 4.50 mm or more.
  • the vehicle window glass of this embodiment includes the above borosilicate glass or the above bent glass. Further, the vehicle window glass of the present embodiment may be made of the above laminated glass.
  • FIG. 2 is a conceptual diagram showing a state in which the laminated glass 10 of this embodiment is attached to an opening 110 formed in front of an automobile 100 and used as an automobile window glass.
  • a housing (case) 120 containing an information device and the like for ensuring the safety of driving the vehicle may be attached to the inner surface of the laminated glass 10 used as the window glass of the vehicle.
  • the information device housed in the housing is a device that uses a camera, radar, etc. to prevent rear-end collisions with vehicles, pedestrians, obstacles, etc. in front of the vehicle, and to notify the driver of danger.
  • it is an information receiving device and/or an information transmitting device, etc., and includes a millimeter wave radar, a stereo camera, an infrared laser, etc., and transmits and receives signals.
  • the "signal" refers to electromagnetic waves including millimeter waves, visible light, infrared light, and the like.
  • FIG. 3 is an enlarged view of the S portion in FIG. 2, and is a perspective view showing a portion where the housing 120 is attached to the laminated glass 10 of this embodiment.
  • the housing 120 houses a millimeter wave radar 201 and a stereo camera 202 as information devices.
  • the housing 120 containing the information device is usually attached to the outside of the rearview mirror 150 and the inside of the laminated glass 10, but may be attached to other parts.
  • FIG. 4 is a cross-sectional view in a direction including the YY line in FIG. 3 and perpendicular to the horizontal line.
  • the first glass plate 11 is arranged on the outside of the vehicle.
  • the incident angle ⁇ of the radio waves 300 used for communication of the information device such as the millimeter wave radar 201 with respect to the main surface of the first glass plate 11 can be evaluated, for example, from 0° to 60° as described above. .
  • Raw materials were put into a platinum crucible so as to obtain the glass composition (unit: mol %) shown in Table 1, and melted at 1650° C. for 3 hours to obtain molten glass.
  • the molten glass was poured onto a carbon plate and slowly cooled. Both sides of the obtained sheet glass were polished to obtain sheet glass A to glass L having a thickness of 1.50 mm.
  • glass A and glass B are comparative examples
  • glass C to glass L are comparative examples.
  • glass A to glass L were subjected to bending treatment under the following conditions to produce bent glasses of Examples 1 to 12 shown in Table 2.
  • Plain glass Glass A to Glass L
  • a thickness of 1.50 mm is brought into an electric furnace and is pressed using a mold with a curved surface while maintaining a heating temperature of 630 ° C. (both T 12 or higher). Then, the pressed state was held for 6 minutes and bent. After that, the press was released to maintain the shape of the bent glass, and cooled by blowing cooling air.
  • Viscosity T11 , T12 , Tg: A beam bending method was used to measure the temperature T 11 when the viscosity ⁇ was 10 11 dPa ⁇ s and the temperature T 12 when the viscosity ⁇ was 10 12 dPa ⁇ s. Further, the glass transition point (Tg) is a value measured using TMA and obtained according to the standard of JIS R3103-3 (2001). (4) Average coefficient of linear expansion from 50°C to 350°C (CTE_50-350°C): It was measured using a differential thermal dilatometer (TMA) and obtained from the standard of JIS R3102 (1995).
  • TMA differential thermal dilatometer
  • Optical properties Using a Perkinelmer spectrophotometer LAMBDA950, the transmission and reflection spectra of light with a wavelength of 200 nm to 2500 nm are measured, and based on ISO9050: 2003, the transmittance of light with a wavelength of 500 nm, the transmittance of light with a wavelength of 1000 nm, and the wavelength of 450 nm ⁇ The average transmittance of light with a wavelength of 700 nm and the average transmittance of light with a wavelength of 900 nm to 1300 nm were obtained.
  • Tv1 and Tv2 a Perkinelmer spectrophotometer LAMBDA950 was used.
  • Tts1, Tts2 The total solar transmittance Tts1 of the glass plate before bending when the thickness is converted to 1.50 mm, and the total solar transmittance Tts2 of the glass plate after bending are defined in ISO-13837: 2008 convention A, and the wind speed is 4 m. /s.
  • Tts was measured using Perkinelmer spectrophotometer LAMBDA950.
  • SAXS measurement SAXS measurements of glass A and glass E before and after bending were performed under the following conditions.
  • the borosilicate glasses of glass C to glass L have T b ⁇ T a greater than 0, and can improve the heat shielding properties when bending glass is obtained. Further, according to FIG. 5, it can be seen that the average transmittance of light with a wavelength of 900 nm to 1300 nm changes before and after the glass D is bent.
  • the borosilicate glass of glass C to glass L has a transmittance of light with a wavelength of 1000 nm when the thickness is 1.50 mm, and an average transmittance of light with a wavelength of 900 nm to 1300 nm is 90% or less. It was found to have good heat shielding properties due to its low transmittance of infrared light.
  • the borosilicate glasses of Glass C to Glass L have a dielectric constant ( ⁇ r ) of 6.0 or less at a frequency of 10 GHz and a dielectric loss tangent (tan ⁇ ) of 0.010 or less at a frequency of 10 GHz. It showed radio wave transparency. Thus, it was found that the borosilicate glasses of glass C to glass L have high millimeter wave transmittance, satisfy a predetermined heat shielding property, and have a certain visible light transmittance.
  • the borosilicate glass of glass A and glass B had T b ⁇ T a of 0 or less, and could not sufficiently improve the heat shielding properties when obtaining bent glass.
  • the maximum value of the scattering intensity is 0.34 in the range of the scattering vector q from 0.10 to 2.0 (nm ⁇ 1 ). , was less than 0.35.
  • the maximum value of the scattering intensity was 12.5 in the range of the scattering vector q from 0.10 to 2.0 (nm -1 ), which was found to be 0.35 or more. rice field.
  • a decrease in the scattering intensity was observed when the glass D was subjected to the bending treatment (Example 4), and the rate of change 1 ⁇ (S a /S b ) of the maximum value before and after the bending treatment was 0.0. was 87.
  • the bending process caused a structural change in the glass, a decrease in the heterogeneous structure, and a decrease in the average transmittance of light with a wavelength of 900 nm to 1300 nm, so that the bent glass with improved heat shielding properties was obtained. It was thought.

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DE112022004163.3T DE112022004163T5 (de) 2021-10-27 2022-10-24 Borosilikatglas
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WO2026075247A1 (ja) * 2024-10-04 2026-04-09 Ａｇｃ株式会社 ガラス板および合わせガラス

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CN121020978A (zh) * 2025-09-02 2025-11-28 齐鲁工业大学(山东省科学院) 一种抗热冲击玻璃及其制备方法和应用

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JPH07109147A (ja) 1993-10-15 1995-04-25 Nippon Sheet Glass Co Ltd 紫外線吸収灰色ガラス
CN107001135B (zh) 2014-12-10 2020-02-11 Agc 株式会社 夹层玻璃的制造方法
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JPH04285026A (ja) * 1991-03-11 1992-10-09 Nippon Sheet Glass Co Ltd 着色ガラス
JP2016500642A (ja) * 2012-10-30 2016-01-14 ユーロケラ ソシエテ オン ノームコレクティフ 誘導調理機器のためのガラスプレート
US20160354996A1 (en) * 2015-06-03 2016-12-08 Precision Glass Bending Corporation Bent, veneer-encapsulated heat-treated safety glass panels and methods of manufacture
WO2018030094A1 (ja) * 2016-08-10 2018-02-15 日本電気硝子株式会社 車両用合わせガラス
JP2020512253A (ja) * 2016-11-22 2020-04-23 コーニング インコーポレイテッド 自動車および建築用のガラス物品および積層体
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WO2025142914A1 (ja) * 2023-12-27 2025-07-03 Ａｇｃ株式会社 合わせガラス
WO2026075247A1 (ja) * 2024-10-04 2026-04-09 Ａｇｃ株式会社 ガラス板および合わせガラス

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