WO2024225086A1 - ガラス、車両用窓ガラス、センサー用ガラス及び合わせガラス - Google Patents

ガラス、車両用窓ガラス、センサー用ガラス及び合わせガラス Download PDF

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Publication number
WO2024225086A1
WO2024225086A1 PCT/JP2024/014902 JP2024014902W WO2024225086A1 WO 2024225086 A1 WO2024225086 A1 WO 2024225086A1 JP 2024014902 W JP2024014902 W JP 2024014902W WO 2024225086 A1 WO2024225086 A1 WO 2024225086A1
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Prior art keywords
glass
less
laminated
thickness
sheet
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
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PCT/JP2024/014902
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English (en)
French (fr)
Japanese (ja)
Inventor
貴人 梶原
茂輝 澤村
幹雄 長野
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AGC Inc
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Asahi Glass Co Ltd
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Publication date
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Priority to JP2025516733A priority Critical patent/JPWO2024225086A1/ja
Priority to DE112024001006.7T priority patent/DE112024001006T5/de
Priority to CN202480027959.6A priority patent/CN121039074A/zh
Publication of WO2024225086A1 publication Critical patent/WO2024225086A1/ja
Priority to US19/364,232 priority patent/US20260042701A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • 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
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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
    • B32B17/10009—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
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    • 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
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    • 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
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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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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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
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/02—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions
    • B32B3/08—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions characterised by added members at particular parts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/022—Mechanical properties
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    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • 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
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    • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
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Definitions

  • the present invention relates to glass, vehicle window glass, sensor glass, and laminated glass.
  • glass used in mobility such as vehicle glass and cover glass for sensors such as LiDAR (Light Detection and Ranging)
  • LiDAR Light Detection and Ranging
  • glass with a high Young's modulus and fracture toughness tends to become highly viscous. For this reason, such glass is not suitable for applications that require bending, such as vehicle window glass or cover glass for sensors such as LiDAR.
  • the glass described in Patent Document 1 has a Young's modulus of 85 GPa or more and a high fracture toughness value of 0.86 MPa ⁇ m 1/2 or more, but a high annealing point of 800° C. or more.
  • Patent Document 2 discloses glass with excellent bend formability that can also be used for windshields, but the Young's modulus is low at 70 GPa.
  • the present invention aims to provide glass, vehicle window glass, sensor glass, and laminated glass that have excellent fracture toughness and excellent bending formability.
  • the present invention is as follows. [1] In mole percent based on oxide, SiO2 : 60-72% Al2O3 : 3.0-9.0 % B2O3 : 0.0-4.0 % MgO: 3.0-15% CaO: 0.0-5.0% SrO: 0.0-5.0% BaO: 0.0-2.0% Li 2 O: 1.0-10% Na 2 O: 6.0-16% K2O : 0.0-3.0% ZrO 2 :0.0-1.0% TiO2 : 0.0-1.0% Y2O3 : 0.0-1.0 % R 2 O: 11-25% RO:7.0 ⁇ 20% (wherein RO is at least one selected from MgO, CaO, SrO and BaO, and R 2 O is at least one selected from Li 2 O, Na 2 O and K 2 O).
  • a vehicle window glass comprising the glass according to any one of [1] to [9].
  • a glass for sensors comprising the glass according to any one of [1] to [9].
  • a glass window comprising a first glass plate, a second glass plate, and an interlayer film sandwiched between the first glass plate and the second glass plate, The first glass plate is the glass according to any one of [1] to [9].
  • a glass window comprising a first glass plate, a second glass plate, and an interlayer film sandwiched between the first glass plate and the second glass plate, The first glass plate and the second glass plate are the glass according to any one of [1] to [9].
  • the laminated glass according to [12], wherein the second glass sheet is soda-lime glass.
  • the laminated glass according to [12], wherein the second glass sheet is an aluminosilicate glass.
  • the laminated glass according to [12] wherein the second glass sheet has been subjected to a chemical strengthening treatment.
  • the present invention provides glass, vehicle window glass, sensor glass, and laminated glass that have excellent fracture toughness and excellent bending formability.
  • FIG. 1 is a graph showing the relationship between H/L and fracture toughness value.
  • FIG. 2 is a diagram showing the relationship between H/L and density.
  • FIG. 3 is a cross-sectional view of an example of a laminated glass according to an embodiment of the present invention.
  • FIG. 4 is a conceptual diagram showing a state in which the laminated glass according to one embodiment of the present invention is used as a window glass for a vehicle.
  • FIG. 5 is an enlarged view of a portion S in FIG.
  • FIG. 6 is a cross-sectional view taken along line YY in FIG.
  • the oxide-based mole percent is: SiO2 : 60-72% Al2O3 : 3.0-9.0 % B2O3 : 0.0-4.0 % MgO: 3.0-15% CaO: 0.0-5.0% SrO: 0.0-5.0% BaO: 0.0-2.0% Li 2 O: 1.0-10% Na 2 O: 6.0-16% K2O : 0.0-3.0% ZrO 2 :0.0-1.0% TiO2 : 0.0-1.0% Y2O3 : 0.0-1.0 % R 2 O: 11-25% RO:7.0 ⁇ 20% (wherein RO is at least one selected from MgO, CaO, SrO and BaO, and R 2 O is at least one selected from Li 2 O, Na 2 O and K 2 O).
  • composition range of each component is expressed in mole percent based on the oxide unless otherwise specified.
  • substantially free of each component means that it is not contained except as an inevitable impurity mixed in from the raw materials, etc., that is, it is not intentionally contained.
  • SiO 2 is a component that constitutes the network structure of glass and is an essential component of the glass of this embodiment.
  • the content of SiO 2 is 60 to 72%.
  • the content of SiO 2 is 60% or more, so that the structure of the glass is strengthened and the Young's modulus and fracture toughness value can be increased.
  • the density of the glass can be easily reduced, and moisture resistance and chemical durability can be ensured.
  • the average linear expansion coefficient is suppressed from increasing, and thermal cracking of the glass can be suppressed.
  • the content of SiO 2 is preferably 63% or more, more preferably 64% or more, even more preferably 65% or more, particularly preferably 66% or more, and most preferably 67% or more.
  • the SiO 2 content is preferably 71% or less, more preferably 70% or less, even more preferably 69% or less, and particularly preferably 68% or less.
  • Al 2 O 3 is a component that constitutes the network structure of glass and is an essential component of the glass of this embodiment.
  • the glass of this embodiment contains 3.0 to 9.0% Al 2 O 3.
  • Al 2 O 3 is 3.0% or more, the Young's modulus can be increased.
  • weather resistance, moisture resistance, and chemical durability are improved.
  • the average linear expansion coefficient does not become too large, so that thermal cracking of the glass can be suppressed, and chemical strengthening treatment using ion exchange is possible.
  • the content of Al 2 O 3 is preferably 3.2% or more, more preferably 3.4% or more, even more preferably 3.6% or more, particularly preferably 3.8% or more, and most preferably 4.0% or more.
  • the glass of this embodiment by containing Al 2 O 3 at 9.0% or less, an increase in viscosity during glass melting is suppressed, and bending formability is improved, as well as formability of vehicle glass, particularly windshields, cover glass for sensors, etc.
  • the content of Al 2 O 3 is preferably 7.0% or less, more preferably 6.5% or less, further preferably 6.0% or less, particularly preferably 5.5% or less, and most preferably 5.0% or less.
  • B 2 O 3 is a component that constitutes the network structure of glass and reduces the viscosity of glass to improve its melting property and bending formability. It also contributes to improving the fracture toughness value.
  • the glass of this embodiment contains 0.0 to 4.0% of B 2 O 3.
  • glass containing B 2 O 3 and an alkali metal is difficult to manufacture because the alkali metal is likely to volatilize during glass manufacture and corrodes the furnace material of the kiln.
  • the content of B 2 O 3 is too high, in addition to the above-mentioned influence on the manufacturing equipment, the homogeneity of the glass is also reduced and the optical quality is deteriorated, which may make it unsuitable for sensor applications.
  • the content of B 2 O 3 is preferably small, preferably 3.5% or less, more preferably 3.0% or less, even more preferably 2.5% or less, particularly preferably 2.0% or less, and most preferably substantially not contained.
  • substantially free of B 2 O 3 means that the content of B 2 O 3 in the glass is 0.050 mol % or less.
  • the content of B 2 O 3 may be 0.20% or more, 0.50% or more, 0.80% or more, 1.0% or more, or 1.2% or more.
  • MgO is a component that reduces the viscosity of glass and improves its solubility, and also contributes to improving the Young's modulus and the surface fracture energy described below.
  • the glass of this embodiment contains 3.0 to 15% MgO. By including 3.0% or more MgO in the glass of this embodiment, the viscosity of the glass can be reduced and the melting of the glass raw materials can be promoted. In addition, the Young's modulus can be increased.
  • the MgO content is preferably 4.0% or more, more preferably 5.0% or more, even more preferably 6.0% or more, particularly preferably 7.0% or more, and most preferably 8.0% or more.
  • the glass of this embodiment if the MgO content is 15% or less, the glass is less susceptible to devitrification and the viscosity of the glass is prevented from increasing excessively, improving the formability of vehicle glass, particularly windshields and cover glass for sensors.
  • the MgO content is preferably 14% or less, more preferably 13% or less, even more preferably 12% or less, and particularly preferably 11% or less.
  • CaO is a component that reduces the viscosity of glass and improves bending formability.
  • the glass of this embodiment contains 0.0 to 5.0% CaO.
  • the CaO content is preferably 0.20% or more, more preferably 0.40% or more, even more preferably 0.60% or more, particularly preferably 0.80% or more, and most preferably 1.0% or more.
  • the CaO content in the glass of this embodiment is preferably 4.5% or less, more preferably 4.0% or less, particularly preferably 3.5% or less, and most preferably 3.0% or less.
  • SrO is a component that reduces the viscosity of glass and improves bending formability.
  • the glass of this embodiment contains 0.0 to 5.0% SrO.
  • SrO is a component that reduces the viscosity of glass and improves bending formability.
  • the glass of this embodiment contains 0.0 to 5.0% SrO.
  • the SrO content is preferably 0.20% or more, more preferably 0.40% or more, even more preferably 0.60% or more, particularly preferably 0.80% or more, and most preferably 1.0% or more.
  • the SrO content is preferably 4.5% or less, more preferably 4.0% or less, even more preferably 3.5% or less, even more preferably 3.0% or less, particularly preferably 2.5% or less, and most preferably 2.0% or less.
  • BaO is a component that reduces the viscosity of the glass and improves bending formability.
  • the glass of this embodiment contains 0.0 to 2.0% BaO. By including BaO in the glass of this embodiment, the viscosity of the glass is reduced.
  • the BaO content is preferably 0.10% or more, more preferably 0.20% or more, even more preferably 0.30% or more, particularly preferably 0.40% or more, and most preferably 0.50% or more.
  • the BaO content is preferably 1.8% or less, more preferably 1.6% or less, even more preferably 1.4% or less, particularly preferably 1.2% or less, and most preferably 1.0% or less.
  • Li 2 O is a component that improves the solubility of glass and reduces the viscosity, and also makes it easier to increase the Young's modulus and contributes to the average linear expansion coefficient of glass. Furthermore, the strength of the glass can be increased by performing a chemical strengthening treatment by ion exchange with Na ions.
  • the content of Li 2 O is 1.0 to 10%.
  • the viscosity of the glass can be reduced.
  • the content of Li 2 O is preferably 1.5% or more, more preferably 2.0% or more, even more preferably 2.5% or more, particularly preferably 3.0% or more, and most preferably 3.5% or more.
  • the Li 2 O content is preferably 9.0% or less, more preferably 8.0% or less, even more preferably 7.0% or less, and particularly preferably 6.0% or less.
  • Na 2 O is a component that improves the solubility of glass and reduces the viscosity, and also makes it easier to increase the Young's modulus and contributes to the average linear expansion coefficient of glass. Furthermore, the strength of glass can be increased by performing a chemical strengthening treatment by ion exchange with K ions.
  • the content of Na 2 O is 6.0 to 16%.
  • the viscosity of glass can be reduced by containing 6.0% or more of Na 2 O.
  • the Young's modulus and the average linear expansion coefficient can be increased.
  • the content of Na 2 O is preferably 7.0% or more, more preferably 8.0% or more, even more preferably 9.0% or more, and particularly preferably 10% or more.
  • the Na 2 O content is preferably 15% or less, more preferably 14% or less, even more preferably 13% or less, and particularly preferably 12% or less.
  • K 2 O is a component that improves the melting property of glass and reduces the viscosity, and also makes it easier to increase the Young's modulus and contributes to the average linear expansion coefficient of glass.
  • the content of K 2 O is 0.0 to 3.0%.
  • the glass of the present embodiment contains K 2 O, which can reduce the viscosity of the glass.
  • the Young's modulus and the average linear expansion coefficient can be increased.
  • the content of K 2 O is preferably 0.10% or more, more preferably 0.20% or more, even more preferably 0.30% or more, particularly preferably 0.40% or more, and most preferably 0.50% or more.
  • K 2 O has the effect of increasing the average linear expansion coefficient and density compared to Li 2 O and Na 2 O. If the content of K 2 O is 3.0% or less, it is possible to suppress thermal cracking of glass caused by an excessive increase in the average linear expansion coefficient.
  • the content of K 2 O is preferably 2.5% or less, more preferably 2.0% or less, and even more preferably 1.5% or less.
  • ZrO2 is a component that improves chemical durability and Young's modulus.
  • the glass of this embodiment contains 0.0 to 1.0% ZrO2 .
  • the content is preferably 0.010% or more, more preferably 0.050% or more, even more preferably 0.10% or more, and particularly preferably 0.20% or more.
  • the content of ZrO 2 is preferably 0.80% or less, more preferably 0.70% or less, further preferably 0.60% or less, and particularly preferably 0.50% or less.
  • TiO2 is a component that improves chemical durability and Young's modulus.
  • the glass of this embodiment contains 0.0 to 1.0% TiO2 .
  • the content is preferably 0.010% or more, more preferably 0.025% or more, even more preferably 0.050% or more, particularly preferably 0.10% or more, and most preferably 0.20% or more.
  • the TiO2 content is preferably 0.90% or less, more preferably 0.80% or less, even more preferably 0.70% or less, and particularly preferably 0.60% or less.
  • Y 2 O 3 is a component that improves the Young's modulus.
  • the glass of this embodiment contains 0.0 to 1.0% Y 2 O 3.
  • the content is preferably 0.010% or more, more preferably 0.050% or more, even more preferably 0.10% or more, and particularly preferably 0.20% or more.
  • the Y 2 O 3 content is preferably 0.90% or less, more preferably 0.80% or less, further preferably 0.70% or less, and particularly preferably 0.60% or less.
  • the total content of Li 2 O, Na 2 O and K 2 O (hereinafter sometimes referred to as R 2 O) is 11 to 25%.
  • R 2 O is 11% or more, the Young's modulus is increased and the viscosity of the glass is reduced, thereby improving the formability of vehicle glass, particularly windshields and cover glass for sensors.
  • R 2 O is preferably 12% or more, more preferably 13% or more, even more preferably 14% or more, and particularly preferably 15% or more.
  • R2O is 25% or less, the increase in density can be suppressed and the fracture toughness value can be improved. In addition, the weather resistance and moisture resistance can also be improved.
  • R2O is preferably 23% or less, more preferably 20% or less, even more preferably 19% or less, particularly preferably 18% or less, and most preferably 17% or less.
  • the glass of this embodiment preferably has a ratio of the content of Li2O to R2O ( Li2O / R2O ) of 0.050 or more.
  • Li2O / R2O is 0.050 or more
  • the glass has a high Young's modulus and fracture toughness, a low density, and excellent melting property and bending formability.
  • Li2O / R2O is more preferably 0.080 or more, even more preferably 0.10 or more, even more preferably 0.12 or more, particularly preferably 0.15 or more, and most preferably 0.17 or more.
  • Li 2 O/R 2 O is preferably 0.60 or less, more preferably 0.50 or less, even more preferably 0.45 or less, particularly preferably 0.42 or less, and most preferably 0.38 or less.
  • the ratio of the total content of Na2O and Li2O to R2O is preferably 0.70 or more.
  • (Na2O+ Li2O )/R2O is 0.70 or more, the glass has a high Young's modulus and fracture toughness, a low density, and excellent melting property and bending formability.
  • ( Na2O + Li2O )/ R2O is more preferably 0.80 or more, even more preferably 0.85 or more, even more preferably 0.90 or more, particularly preferably 0.92 or more, and most preferably 0.94 or more.
  • the total content of MgO, CaO, SrO and BaO (hereinafter sometimes referred to as RO) is 7.0 to 20%.
  • RO is preferably 8.0% or more, more preferably 9.0% or more, and even more preferably 10% or more.
  • RO is 20% or less
  • the increase in density of the glass can be suppressed and the crack resistance of the glass can be improved. It can also suppress moisture resistance and devitrification of the glass.
  • RO is preferably 19% or less, more preferably 18% or less, even more preferably 17% or less, even more preferably 16% or less, particularly preferably 15% or less, and most preferably 14% or less.
  • the glass of this embodiment preferably has a ratio of the MgO content to the RO content (MgO/RO) of 0.20 or more.
  • MgO/RO is 0.20 or more, the glass has a high Young's modulus and fracture toughness, a low density, and excellent melting properties and bending formability.
  • MgO/RO is more preferably 0.25 or more, even more preferably 0.33 or more, even more preferably 0.50 or more, particularly preferably 0.70 or more, and most preferably 0.75 or more.
  • MgO/RO is preferably 1.0 or less, more preferably 0.98 or less, even more preferably 0.95 or less, particularly preferably 0.90 or less, and most preferably 0.85 or less.
  • the ratio (H/L) of the H value to the L value calculated by the following formula is preferably 0.10 or less.
  • H [ K2O ]+[CaO]+[SrO]+ [ BaO]+[ ZrO2 ]+[ TiO2 ]+[ Y2O3 ]
  • L [ SiO2 ]+[ Al2O3 ] +[MgO]+[ Li2O ]+[ Na2O ] (Note that [ ] means the content of each component in the brackets expressed as mole percent on an oxide basis.)
  • the H value is the sum of the contents of ZrO2 , TiO2 , and Y2O3 , which are components that contribute to improving Young's modulus and fracture toughness but tend to increase the viscosity of glass, and K2O , CaO, SrO, and BaO, which are components that contribute to increasing density.
  • the L value is the sum of the contents of SiO2 and Al2O3 , which are network components, and MgO, Li2O , and Na2O , which are components that contribute to improving Young's modulus and fracture toughness but increase density only slightly.
  • H/L the ratio of H value to L value
  • Fe 2 O 3 is a component that improves the heat insulating properties of glass and also contributes to the color of glass, so it may be contained in the glass of this embodiment.
  • the total iron content converted into Fe 2 O 3 is preferably 0.0025 to 1.2%.
  • the total iron content converted into Fe 2 O 3 here refers to the total amount of iron including FeO, which is an oxide of divalent iron, and Fe 2 O 3, which is an oxide of trivalent iron.
  • the inclusion of Fe 2 O 3 makes the glass suitable for applications requiring heat insulation properties. Furthermore, the inclusion of Fe 2 O 3 can suppress the load on the melting furnace caused by heat radiation reaching the bottom surface of the melting furnace during glass melting.
  • the total iron content, calculated as Fe 2 O 3, in the glass of the present embodiment is preferably 0.0025% or more, more preferably 0.0040% or more, even more preferably 0.039% or more, still more preferably 0.097% or more, particularly preferably 0.11% or more, particularly preferably 0.15% or more, and most preferably 0.17% or more.
  • the total iron content converted to Fe2O3 is preferably 1.0% or less, more preferably 0.80% or less, even more preferably 0.60% or less, particularly preferably 0.50% or less, and most preferably 0.40% or less.
  • the total iron content converted to Fe2O3 is preferably 0.0030% or more, more preferably 0.0032% or more, even more preferably 0.0034% or more, even more preferably 0.0036% or more , particularly preferably 0.0038% or more, particularly preferably 0.0040% or more, and most preferably 0.0042% or more.
  • the total iron content converted to Fe2O3 is preferably 0.020% or less, more preferably 0.010% or less, even more preferably 0.0080% or less, particularly preferably 0.0070% or less, and most preferably 0.0060% or less.
  • the mass ratio (%) of divalent iron calculated as Fe2O3 to the total iron calculated as Fe2O3 is preferably 15% or more.
  • the value of Fe-Redox is the ratio of the Fe2 + content calculated as Fe2O3 to the total iron content calculated as Fe2O3 .
  • the Fe-Redox is 15% or more, the content of Fe2 + having absorption in the near infrared region can be increased, so that heat is easily transferred to the glass melt during glass production, improving manufacturability.
  • the transmittance in the near infrared region is reduced, improving the heat insulating property, making the glass suitable for applications requiring heat insulating property, such as glass for vehicles.
  • Fe-Redox is more preferably 20% or more, further preferably 22% or more, and particularly preferably 24% or more.
  • Fe-Redox is preferably 50% or less. By having Fe-Redox of 50% or less, deterioration of the melting equipment can be suppressed, and when SO 3 is used as a fining agent, amber coloring can be suppressed and a decrease in visible light transmittance can be suppressed.
  • Fe-Redox is more preferably 45% or less, further preferably 40% or less, and particularly preferably 38% or less.
  • Fe-Redox is more preferably 16% or more, even more preferably 17% or more, and particularly preferably 18% or more. Also, Fe-Redox is preferably 35% or less. By having Fe-Redox 35% or less, it is possible to suppress a decrease in transmittance in the near-infrared range. Fe-Redox is more preferably 32% or less, even more preferably 30% or less, and particularly preferably 28% or less.
  • Fe-Redox can be adjusted by the raw material composition, melting temperature, and melting atmosphere.
  • Fe-Redox can be adjusted by controlling the degree of oxidation-reduction of the glass melt by using reducing agents such as coke or ammonium chloride as raw materials.
  • the glass of this embodiment may contain components other than those listed above (hereinafter also referred to as "other components").
  • Examples of other components include CeO2 , Nd2O5 , GaO2 , GeO2 , MnO2 , NiO, Cr2O3 , V2O5 , Au2O3 , Ag2O , CuO , CdO, MoO3 , SO3 , Cl, F, SnO2 , and Sb2O3 , and may be metal ions or oxides .
  • Other components may be contained in a total amount of, for example, 3.0% or less for various purposes (e.g., clarification and coloring, chemical durability, etc.). If the total content of other components is 3.0% or less, the properties required for vehicle glass and cover glass for sensors such as LiDAR can be maintained.
  • the total content of other components is preferably 2.5% or less, more preferably 2.0% or less, even more preferably 1.5% or less, particularly preferably 1.0% or less, and most preferably 0.50% or less.
  • the contents of As 2 O 3 and PbO are each preferably less than 0.0010%, and more preferably substantially none are contained.
  • the formation of NiS can cause glass breakage, so the NiO content is preferably 0.0080% or less.
  • the NiO content in the glass of this embodiment is more preferably 0.0040% or less, even more preferably 0.0020% or less, and it is particularly preferable that the glass is substantially free of NiO.
  • the glass of this embodiment may contain CeO 2. Since CeO 2 has absorption in the ultraviolet region, it reduces the ultraviolet transmittance Tuv and improves UV cut performance. It also acts as an oxidizing agent and can control Fe-Redox. When the glass of this embodiment contains CeO 2 , its content is preferably 0.010% or more, more preferably 0.020% or more, even more preferably 0.040% or more, and particularly preferably 0.070% or more. CeO 2 absorbs light in the ultraviolet region, which may cause solarization and reduce the transmittance in the visible region. Therefore, the content of CeO 2 is preferably 0.25% or less, more preferably 0.18% or less, even more preferably 0.14% or less, and particularly preferably 0.10% or less.
  • the glass of the present embodiment may contain Cr 2 O 3.
  • Cr 2 O 3 acts as an oxidizing agent and can control Fe-Redox.
  • the content is preferably 0.0020% or more, more preferably 0.0040% or more. Since Cr 2 O 3 has coloring for light in the visible range, there is a risk of a decrease in visible light transmittance. In addition, there is a risk of a decrease in the amount of Fe 2+ , which decreases the heat insulating property. Therefore, when the glass of the present embodiment contains Cr 2 O 3 , it is preferably 0.020% or less, more preferably 0.016% or less, even more preferably 0.012% or less, and particularly preferably 0.0080% or less.
  • the glass of this embodiment may contain SnO2 .
  • SnO2 acts as a reducing agent to control Fe-Redox. It also acts as a clarifier.
  • its content is preferably 0.010% or more, more preferably 0.040% or more, even more preferably 0.060% or more, and particularly preferably 0.080% or more.
  • the content of SnO2 in the glass of this embodiment is preferably 0.40% or less, more preferably 0.30% or less, even more preferably 0.20% or less, and particularly preferably 0.15% or less.
  • the glass of this embodiment may contain SO 3.
  • SO 3 acts as a fining agent to improve the bubble quality of the glass.
  • its content is preferably 0.0010% or more, more preferably 0.0040% or more, even more preferably 0.0070% or more, and particularly preferably 0.015% or more.
  • SO 3 may cause amber coloring, causing the glass to turn brown, and the visible light transmittance may decrease.
  • it is preferably 0.070% or less, more preferably 0.060% or less, even more preferably 0.050% or less, and particularly preferably 0.040% or less.
  • the glass of the present embodiment may contain Cl.
  • Cl acts as a fining agent to improve the bubble quality of the glass.
  • the content is preferably 0.080% or more, more preferably 0.15% or more, even more preferably 0.20% or more, particularly preferably 0.25% or more, and most preferably 0.30% or more. If the Cl content is high, Cl2 gas volatilized from the glass melt may corrode the surrounding members.
  • the content is preferably 1.0% or less, more preferably 0.80% or less, even more preferably 0.60% or less, and particularly preferably 0.50% or less.
  • the glass of this embodiment preferably has a fracture toughness value K IC of 0.76 MPa ⁇ m 1/2 or more as measured by the SEPB method.
  • the fracture toughness value K IC is an index of the strength of the glass, and the larger the fracture toughness value K IC, the less likely the cracks will progress, indicating a higher resistance to cracking. Therefore, when the fracture toughness value K IC is 0.76 MPa ⁇ m 1/2 or more, sufficient resistance to cracking is obtained, making the glass suitable for use as a cover glass for vehicles or sensors.
  • the fracture toughness value K IC is more preferably 0.78 MPa ⁇ m 1/2 or more, even more preferably 0.80 MPa ⁇ m 1/2 or more, even more preferably 0.82 MPa ⁇ m 1/2 or more, particularly preferably 0.84 MPa ⁇ m 1/2 or more, particularly preferably 0.86 MPa ⁇ m 1/2 or more, particularly preferably 0.88 MPa ⁇ m 1/2 or more, and most preferably 0.90 MPa ⁇ m 1/2 or more.
  • the fracture toughness value K IC is measured using a pre-crack introduction fracture test method (SEPB method: Single-Edge-Precracked-Beam method) based on JIS R1607:2015 "Fracture toughness test method for fine ceramics”.
  • SEPB method Single-Edge-Precracked-Beam method
  • the following methods can be used: increasing the content of SiO2 , increasing the proportion of RO with a small atomic number of alkaline earth metal components, and increasing the proportion of R2O with a small atomic number of alkali metal components.
  • SiO2 is a component that forms a network structure, increasing the content strengthens the glass structure, thereby improving the fracture toughness value.
  • the smaller the atomic number of the alkaline earth metal component of RO the higher the Young's modulus, and as a result, the higher the fracture toughness value.
  • R2O also shows the same tendency as RO, the smaller the atomic number of the alkali metal component.
  • the fracture toughness value K IC (MPa ⁇ m 1/2 ) can be calculated from Young's modulus E (GPa), surface fracture energy ⁇ (J/m 2 ) and Poisson's ratio ⁇ (unitless) according to the following formula.
  • the fracture toughness value K IC increases as the Young's modulus E and the surface fracture energy ⁇ increase.
  • the Young's modulus of the glass of this embodiment is preferably 75 GPa or more. With a Young's modulus of 75 GPa or more, the glass has high rigidity and improves fracture toughness, making it more suitable as a window glass for a vehicle or a cover glass for a sensor such as LiDAR.
  • the Young's modulus of the glass of this embodiment is more preferably 76 GPa or more, even more preferably 77 GPa or more, particularly preferably 78 GPa or more, and most preferably 79 GPa or more.
  • the Young's modulus is preferably 87 GPa or less, more preferably 86 GPa or less, even more preferably 85 GPa or less, and particularly preferably 84 GPa or less.
  • methods include adjusting the type and amount of RO and R 2 O, increasing the content of MgO and Li 2 O, and adding Y 2 O 3 , TiO 2 , and ZrO 2.
  • the Young's modulus can be measured by an ultrasonic pulse method based on JIS R1602:1995 "Testing method for elastic modulus of fine ceramics.”
  • the surface fracture energy of the glass of the present embodiment is preferably 3.6 J/m2 or more .
  • the surface fracture energy is more preferably 3.7 J/ m2 or more, even more preferably 3.8 J/ m2 or more, particularly preferably 3.9 J/m2 or more , and most preferably 4.0 J/ m2 or more.
  • the surface fracture energy can be determined by measuring the fracture toughness value, Young's modulus, and Poisson's ratio and calculating from the relationship in formula (1) above.
  • the rigidity modulus of the glass of this embodiment is preferably 31 GPa or more. If the rigidity modulus is 31 GPa or more, the glass is less likely to deform when subjected to an external force.
  • the rigidity modulus of the glass is more preferably 32 GPa or more, and further preferably 33 GPa or more.
  • the rigidity modulus is preferably 38 GPa or less, more preferably 37 GPa or less, even more preferably 36 GPa or less, and particularly preferably 35 GPa or less.
  • the rigidity modulus can be measured by the ultrasonic pulse method based on JIS R1602:1995 "Test method for elastic modulus of fine ceramics.”
  • the Poisson's ratio of the glass of this embodiment is preferably 0.26 or less. If the Poisson's ratio is 0.26 or less, the stress generated when an external force is applied to the glass can be reduced. In addition, the fracture toughness value can be improved.
  • the Poisson's ratio is more preferably 0.25 or less, further preferably 0.24 or less, and particularly preferably 0.23 or less.
  • Poisson's ratio can be measured using the ultrasonic pulse method based on JIS R1602:1995 "Test method for elastic modulus of fine ceramics.”
  • the temperature T2 at which the glass viscosity ⁇ , which is a criterion for the solubility of the glass, is 10 2 [dPa ⁇ s], is preferably 1650° C. or less.
  • Methods for setting T2 at 1650°C or lower include, for example, a method of increasing the contents of R2O and RO in the glass components and reducing the content of Al2O3 , a method of including Li2O among R2O , and a method of reducing the content of SiO2 .
  • T2 is more preferably 1600° C. or less, even more preferably 1575° C. or less, even more preferably 1550° C. or less, particularly preferably 1525° C. or less, and most preferably 1500° C. or less. From the viewpoint of maintaining the fracture toughness of the glass and preventing the average linear expansion coefficient of the glass from becoming too large, T2 is preferably 1400° C. or more, more preferably 1425° C. or more, and even more preferably 1450° C. or more.
  • the temperature T4 at which the glass viscosity ⁇ , which is a criterion for formability during float forming, is 10 4 [dPa ⁇ s] is preferably 1200° C. or less.
  • T4 is 1200° C. or less, the glass is suitable for sheet forming by the float method.
  • Methods for setting T4 at 1200°C or less include, for example, a method of increasing the contents of R2O and RO in the glass components and reducing the content of Al2O3 , a method of including Li2O among R2O , and a method of reducing the content of SiO2 .
  • T4 is more preferably 1175° C. or less, even more preferably 1150° C. or less, even more preferably 1125° C. or less, particularly preferably 1100° C. or less, and most preferably 1075° C. or less. From the viewpoint of maintaining the fracture toughness of the glass and preventing the average linear expansion coefficient of the glass from becoming too large, T4 is preferably 950° C. or more, more preferably 975° C. or more, even more preferably 1000° C. or more, and particularly preferably 1025° C. or more.
  • the temperature T11 at which the glass viscosity ⁇ , which is a criterion for bending workability, is 1011 [dPa ⁇ s] is preferably not more than 640° C.
  • T11 is not more than 640° C., bending forming at a low temperature becomes possible.
  • Examples of methods for setting T11 at 640° C. or lower include a method of increasing the contents of R 2 O and RO in the glass components and reducing the content of Al 2 O 3 , a method of incorporating Li 2 O among R 2 O, and a method of reducing the content of SiO 2 .
  • T11 is more preferably 635°C or less, further preferably 630°C or less, even more preferably 625°C or less, particularly preferably 620°C or less, particularly preferably 615°C or less, and most preferably 610°C or less.
  • T11 is preferably 570° C. or higher, more preferably 575° C. or higher, even more preferably 580° C. or higher, particularly preferably 585° C. or higher, and most preferably 590° C. or higher.
  • the temperature T12 at which the glass viscosity ⁇ , which is a criterion for bending workability, is 1012 [dPa ⁇ s] is preferably not more than 610° C.
  • T12 is not more than 610° C.
  • Methods for setting T12 at 610°C or lower include, for example, increasing the contents of R2O and RO in the glass components and reducing the content of Al2O3 , incorporating Li2O among R2O , and reducing the content of SiO2 .
  • T12 is more preferably 605° C. or less, even more preferably 600° C. or less, even more preferably 595° C. or less, especially preferably 590° C. or less, particularly preferably 585° C. or less, and most preferably 580° C. or less.
  • T12 is preferably 540° C. or more, more preferably 545° C. or more, even more preferably 550° C. or more, particularly preferably 555° C. or more, and most preferably 560° C. or more.
  • the density of the glass of this embodiment is preferably 2.68 g/cm 3 or less.
  • the density of 2.68 g/cm 3 or less it is possible to improve Young's modulus, fracture toughness, sound insulation, etc. while suppressing increases in fuel consumption and electricity consumption due to weight increase.
  • glasses having high Young's modulus and fracture toughness have high density and tend to require high bending temperatures, but by adjusting the composition and contents of R 2 O and RO in the glass components, it is possible to achieve a high Young's modulus, fracture toughness, and excellent bending formability while reducing density.
  • the density of the glass of this embodiment is more preferably 2.66 g/cm3 or less, even more preferably 2.60 g/cm3 or less , still more preferably 2.55 g/cm3 or less , especially preferably 2.53 g/cm3 or less , particularly preferably 2.51 g/cm3 or less , and most preferably 2.49 g/cm3 or less .
  • the density of the glass of the present embodiment is preferably 2.40 g/cm 3 or more, more preferably 2.42 g/cm 3 or more, particularly preferably 2.43 g/cm 3 or more, and most preferably 2.44 g/cm 3 or more.
  • the glass transition temperature (T g ) of the glass of this embodiment is preferably in the range of 460° C. or more and less than 600° C. If T g is within this predetermined temperature range, the glass can be bent under normal manufacturing conditions. If the T g of the glass of this embodiment is 460° C. or more, the alkali metal content or the alkaline earth metal content does not become too large, and the average linear expansion coefficient of the glass can be suppressed from increasing. In addition, moisture resistance and devitrification of the glass are suppressed, and formability is improved. T g is more preferably 480° C. or more, even more preferably 490° C. or more, and particularly preferably 500° C. or more.
  • the Tg is preferably less than 600° C., more preferably 590° C. or less, even more preferably 585° C. or less, still more preferably 580° C. or less, particularly preferably 575° C. or less, and most preferably 570° C. or less.
  • the yield point of the glass of the present embodiment is preferably 670° C. or less. When the yield point is within the above range, excellent bending formability can be obtained.
  • the yield point of the glass is more preferably 660° C. or less, further preferably 650° C. or less, particularly preferably 640° C. or less, and most preferably 630° C. or less.
  • the yield point is preferably 580°C or higher. If the yield point is 580°C or higher, the bending temperature can be prevented from becoming too low, and the black ceramic printed on the windshield can be fired simultaneously with bending.
  • the yield point is more preferably 585°C or higher, even more preferably 590°C or higher, particularly preferably 595°C or higher, and most preferably 600°C or higher.
  • the yield point can be measured using a differential thermal dilatometer (TMA).
  • the glass of this embodiment preferably has an average coefficient of linear expansion (CTE) of 100 ⁇ 10 ⁇ 7 /° C. or less at 50 to 350° C.
  • CTE average coefficient of linear expansion
  • the glass of this embodiment is made into bent glass, the difference in thermal expansion caused by differences in thermal history within the surface can be suppressed, and bent glass with good dimensional and surface precision can be obtained.
  • the average linear expansion coefficient of the glass of this embodiment at 50 to 350° C. is preferably 100 ⁇ 10 ⁇ 7 /° C. or less, more preferably 95 ⁇ 10 ⁇ 7 /° C. or less, even more preferably 92 ⁇ 10 ⁇ 7 /° C. or less, and particularly preferably 90 ⁇ 10 ⁇ 7 /° C. or less.
  • the glass of this embodiment preferably has an average linear expansion coefficient of 70 ⁇ 10 -7 /°C or more.
  • the difference in thermal expansion with the black ceramic is reduced, and cracking of the black ceramic can be suppressed.
  • the average linear expansion coefficient is more preferably 72 ⁇ 10 -7 /°C or more, even more preferably 74 ⁇ 10 -7 /°C or more, particularly preferably 76 ⁇ 10 -7 /°C or more, particularly preferably 78 ⁇ 10 -7 /°C or more, particularly preferably 80 ⁇ 10 -7 /°C or more, and most preferably 82 ⁇ 10 -7 /°C or more.
  • the glass of the present embodiment When the glass of the present embodiment is used for vehicle glass, the glass of the present embodiment preferably has a solar radiation transmittance Te of 90% or less as specified by ISO-9050:2003 when converted to a thickness of 2.00 mm. If Te is 90% or less, excellent heat shielding properties can be obtained. Te is more preferably 88% or less, even more preferably 86% or less, even more preferably 84% or less, particularly preferably 82% or less, and most preferably 80% or less.
  • the lower limit of Te is not particularly limited, but is usually 30% or more, preferably 32% or more, more preferably 34% or more, and particularly preferably 36% or more. In order to set Te within the above range, it can be achieved by adjusting the content of Fe 2 O 3 to 0.030% or more.
  • Tv visible light transmittance
  • the glass of this embodiment When the glass of this embodiment is used as a vehicle glass, the glass of this embodiment has a transmittance of 1.00 mm when measured by a spectrophotometer using a D65 light source in accordance with the provisions of ISO-9050:2003, when converted to a thickness of 2.00 mm.
  • the visible light transmittance Tv calculated by measuring the transmittance is preferably 75% or more. Since the Tv is 75% or more, the glass has excellent transparency, and is therefore suitable for use as glass for vehicles, particularly windshields and doors. This is more suitable for glass.
  • Tv is more preferably 78% or more, further preferably 80% or more, and even more preferably 82% or more. 84% or more is particularly preferred, and 86% or more is the most preferred.
  • the upper limit of Tv is Although not limited thereto, for example, it is 92% or less.
  • the Tv can be set within the above range by adjusting the glass composition, particularly the contents of SiO2 and Fe2O3 .
  • the glass of the present embodiment When the glass of the present embodiment is used as a vehicle glass, the glass of the present embodiment preferably has low ultraviolet transmittance, and when converted to a thickness of 2.00 mm, the glass has a transmittance of 1.0 ⁇ m as defined by ISO-9050:2003.
  • the ultraviolet transmittance Tuv is preferably 70% or less. By having Tuv of 70% or less, deterioration of components such as interlayers and seats in the vehicle interior can be suppressed when the glass of the present embodiment is used in laminated glass.
  • Tuv is more preferably 68% or less, even more preferably 66% or less, even more preferably 64% or less, particularly preferably 62% or less, and most preferably 60% or less.
  • the lower limit of Tuv is, for example, 10% or more. It is.
  • Tuv can be set within the above range by adjusting the glass composition, in particular SiO 2 , Fe 2 O 3 , TiO 2 , CeO 2 or Fe-Redox.
  • the glass of this embodiment When the glass of this embodiment is used as the cover glass for LiDAR, it is preferable that the glass of this embodiment has a high transmittance at wavelengths of 905 nm or 1550 nm, which are used in LiDAR. Therefore, the glass of this embodiment has a transmittance at wavelengths of 905 nm or 1550 nm, when converted to a thickness of 4.0 mm, of preferably 86% or more, more preferably 87% or more, even more preferably 88% or more, even more preferably 89% or more, particularly preferably 90% or more, and most preferably 91% or more.
  • the shape of the glass of the present embodiment is not particularly limited, but when the glass of the present embodiment is used for vehicle glass, the area of the main surface is preferably 0.25 m 2 or more, more preferably 0.45 m 2 or more, and even more preferably 0.90 m 2 or more.
  • the area of the glass is in the above range, it can be used for various vehicle models.
  • the area of the main surface of the glass of the present embodiment is preferably 10 m 2 or less, more preferably 7 m 2 or less, and even more preferably 5 m 2 or less.
  • the shape of the glass of this embodiment is not particularly limited, but the area of the main surface is preferably 0.00010 m 2 or more, more preferably 0.010 m 2 or more, even more preferably 0.020 m 2 or more, particularly preferably 0.040 m 2 or more, and most preferably 0.090 m 2 or more.
  • the area of the glass is within the above range, it can be used with various LiDAR cover glasses.
  • the area of the main surface of the glass of this embodiment is preferably 1.0 m 2 or less, more preferably 0.90 m 2 or less, and even more preferably 0.80 m 2 or less.
  • the glass of this embodiment preferably has a surface roughness Ra of 5.0 nm or less, a thickness of 2.5 mm, and a critical impact destruction speed of 35 km/h or more when it is struck by a tungsten carbide alloy having a tip curvature radius of 200 ⁇ m, an apex angle of 120°, and a weight of 1.365 g.
  • a critical impact destruction speed of 35 km/h or more can improve resistance to flying stones.
  • the critical impact destruction speed is more preferably 36 km/h or more, even more preferably 37 km/h or more, even more preferably 38 km/h or more, even more preferably 39 km/h or more, particularly preferably 40 km/h or more, and most preferably 42 km/h or more.
  • the upper limit of the critical impact destruction speed is, for example, 120 km/h or less.
  • the surface roughness Ra can be measured based on JIS B0601:2001.
  • the glass of the embodiment preferably has a critical impact fracture speed of 53 km/h or more when a tungsten carbide alloy having a tip curvature radius of 200 ⁇ m, an apex angle of 120°, and a weight of 1.365 g is collided with the glass.
  • a critical impact fracture speed of 53 km/h or more can improve resistance to flying stones.
  • the critical impact fracture speed is more preferably 54 km/h or more, even more preferably 55 km/h or more, and particularly preferably 56 km/h or more.
  • the upper limit of the critical impact fracture speed is, for example, 120 km/h or less.
  • the critical impact fracture speed can be measured by the method described in the examples below.
  • the thickness of the glass of this embodiment is preferably 2.5 mm or more.
  • the thickness of the glass is preferably 2.5 mm or more.
  • the thickness of the glass is more preferably 2.8 mm or more, even more preferably 2.9 mm or more, even more preferably 3.0 mm or more, especially preferably 3.1 mm or more, even more preferably 3.2 mm or more, even more preferably 3.3 mm or more, particularly preferably 3.4 mm or more, and most preferably 3.5 mm or more.
  • the thickness of the glass in this embodiment is preferably 6.0 mm or less, more preferably 5.5 mm or less, even more preferably 5.0 mm or less, particularly preferably 4.8 mm or less, and most preferably 4.5 mm or less.
  • Methods for adjusting the thickness of the glass include using the float method or down-draw method described below, or grinding the glass in the thickness direction with a grindstone and then polishing it to a mirror finish with an abrasive such as cerium oxide.
  • the surface roughness Ra after molding or polishing is preferably 5.0 nm or less, more preferably 2.0 nm or less, even more preferably 1.5 nm or less, particularly preferably 1.0 nm or less, and most preferably 0.50 nm or less.
  • the glass of this embodiment is preferably float glass formed by, for example, the well-known float method.
  • molten glass base is floated on a molten metal such as tin, and strict temperature control allows the formation of glass with uniform thickness and width, as well as the production of large-area glass.
  • the glass of this embodiment may be glass formed by the known roll-out method or down-draw method, or may be glass with a polished surface and uniform thickness.
  • the down-draw method is broadly divided into the slot down-draw method and the overflow down-draw method (fusion method), but both are techniques in which molten glass is continuously allowed to flow down from a forming body to form a band-shaped glass ribbon.
  • the glass of this embodiment may be glass that has been subjected to a strengthening treatment such as air-cooling or chemical strengthening. By carrying out the above treatment, the strength of the glass can be increased.
  • air-cooled tempering is a process that forms a compressive stress layer on the surface of glass by thermal tempering. Specifically, uniformly heated glass is rapidly cooled from a temperature close to its softening point, and compressive stress is formed on the surface of the glass due to the temperature difference between the surface and the interior of the glass. Compressive stress is generated uniformly over the entire surface of the glass, and a compressive stress layer of uniform depth is formed over the entire surface of the glass. Thermal tempering is more suitable for strengthening thick glass than chemical tempering.
  • Chemical strengthening is a process in which alkali metal ions with a small ionic radius (typically Li ions or Na ions) on the glass surface are replaced by alkali metal ions with a larger ionic radius (typically Na ions or K ions) through ion exchange at a temperature below the glass transition point, forming a compressive stress layer on the glass surface.
  • Chemical strengthening can be performed by known methods, such as the ion exchange method.
  • a glass plate is immersed in a treatment liquid (e.g., potassium nitrate molten salt) and ions with a small ionic radius (e.g., Na ions) contained in the glass are replaced by ions with a large ionic radius (e.g., K ions), generating compressive stress on the glass surface.
  • a treatment liquid e.g., potassium nitrate molten salt
  • ions with a small ionic radius e.g., Na ions
  • ions with a large ionic radius e.g., K ions
  • the magnitude of the compressive stress on the surface of the glass (hereinafter also referred to as surface compressive stress CS) and the depth DOL of the compressive stress layer formed on the surface of the glass can be adjusted by the glass composition, the immersion time in the treatment solution, and the temperature of the treatment solution, respectively.
  • the glass of this embodiment may be flat, or may be bent glass formed into a curved shape by gravity forming, press forming, or the like.
  • the glass of this embodiment is glass that is curved with a specified curvature
  • it may be single-curved glass that is curved in only one direction, either up-down or left-right, or compound-curved glass that is curved in both up-down and left-right directions.
  • the minimum value of the radius of curvature is 500 mm or more and 100,000 mm or less.
  • the radius of curvature of curved glass is calculated by simulating the shape of a sample using a laser displacement meter (Dyvoce manufactured by Kohzu Seiki Co., Ltd.) based on the amount of warping that the sample originally had, which was determined by self-weight deflection correction in the double-sided differential mode, and the radius of curvature is obtained from the shape obtained by the simulation.
  • the glass of this embodiment can be made into bent glass by heating and bending the glass.
  • a more specific forming method is to heat flat glass, place it on a forming die, and press it from above with a press means to bend it.
  • Another method is to place flat glass on a mold having a bending surface that corresponds to the desired curved surface, then carry the mold into a heating furnace in which the glass is heated to a temperature close to the glass softening point.
  • the glass softens and bends under its own weight along the bending surface of the mold, producing bent glass with the desired curved surface.
  • bending using the above-mentioned press means is preferred from the viewpoint of improving productivity and improving surface accuracy after forming.
  • the bending method using the above-mentioned press means is not particularly limited, and for example, the method described in WO 2016/093031 or the like can be appropriately adopted. Below, an example of the bending method using the above-mentioned press means is described.
  • the glass of this embodiment is transported to the pressing area by a transport conveyor or the like.
  • the glass is heated to a temperature at which it can be bent and softened.
  • the temperature at which bending is possible is, for example, equal to or higher than the temperature T12 at which the glass viscosity is 10 12 [dPa ⁇ s].
  • the heating may be performed by a heater or the like in a heating furnace during the process of transporting the glass to the pressing area on a transport conveyor or the like.
  • the bending time under the condition that the heating temperature ( ⁇ T 12 ) is maintained can be set to, for example, 1 second or more.
  • a lower press mold (female mold) and an upper press mold (male mold) are arranged at predetermined positions in the press area, and the top surface shape of the female mold and the bottom surface shape of the male mold correspond to the curved shape of the glass to be bent in the conveying direction and/or the perpendicular direction.
  • the female mold can be raised and lowered between a waiting position below the conveyor and a press position above it, and after the glass is transferred from the conveyor, the female mold rises from a predetermined raised position to a press position above the conveyor with the glass placed on it, thereby press-forming the glass.
  • the pressed glass is then transported to the cooling area using a transport shuttle or similar device.
  • the glass is cooled by blowing cold air onto it, for example.
  • the laminated glass according to this embodiment includes a first glass plate, a second glass plate, and an interlayer film sandwiched between the first glass plate and the second glass plate, and the first glass plate is the glass according to this embodiment.
  • FIG. 3 is a diagram showing an example of the laminated glass 10 of 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 of this embodiment is not limited to the embodiment shown in FIG. 3, and can be modified within the scope of the present invention.
  • the intermediate film 13 may be formed in one layer as shown in FIG. 3, or in two or more layers.
  • the laminated glass 10 of this embodiment may have three or more glass plates, and in that case, an organic resin or the like may be interposed between the adjacent glass plates.
  • the laminated glass 10 of this 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.
  • the second glass plate 12 is the glass of this embodiment.
  • the first glass plate 11 and the second glass plate 12 may be glass plates of the same composition or glass plates of different compositions.
  • the type of glass plate is not particularly limited, and any conventionally known glass plate used for vehicle window glass, etc. can be used. Specific examples include alkali aluminosilicate glass, alkali aluminoborosilicate glass, and soda lime glass. These glass plates may or may not be colored to the extent that transparency is not impaired.
  • the second glass plate 12 may be an alkali aluminosilicate glass containing 1.0% or more of Al 2 O 3 , or an alkali aluminoborosilicate glass containing 1.0% or more of Al 2 O 3 and 1.0% or more of B 2 O 3.
  • the alkali aluminosilicate glass or alkali aluminoborosilicate glass as the second glass plate 12, chemical strengthening becomes possible as described later, and the strength can be increased.
  • the above-mentioned alkali aluminosilicate glass and alkali aluminoborosilicate glass preferably have an Al2O3 content of 5.0% or more, more preferably 8.0% or more, and particularly preferably 10% or more. Also, from the viewpoints of reducing the viscosity of the glass to facilitate production, the Al2O3 content is preferably 18% or less, and more preferably 15 % or less.
  • the alkali aluminosilicate glass and alkali aluminoborosilicate glass preferably have an R 2 O content of 10% or more, more preferably 12% or more, and even more preferably 13% or more.
  • the R 2 O content is preferably 22% or less, more preferably 20% or less, and even more preferably 18% or less.
  • the alkali aluminoborosilicate glass preferably has a B 2 O 3 content of 2.0% or more, more preferably 3.0% or more, and even more preferably 4.0% or more in order to increase the strength when the glass comes into contact with flying stones, vehicle keys, etc.
  • the B 2 O 3 content is preferably 9.0% or less, more preferably 8.0% or less, and even more preferably 7.0% or less.
  • alkali aluminosilicate glass examples include glasses having the following compositions, in which each component is expressed in mole percentage based on the oxide. 61% ⁇ SiO2 ⁇ 75% 1.0% ⁇ Al2O3 ⁇ 20% 0.0% ⁇ MgO ⁇ 15% 0.0% ⁇ CaO ⁇ 10% 0.0% ⁇ SrO ⁇ 1.0% 0.0% ⁇ BaO ⁇ 1.0% 0.0% ⁇ Li2O ⁇ 15% 2.0% ⁇ Na2O ⁇ 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 content of Li 2 O, Na 2 O and K 2 O, and RO represents the total content of MgO, CaO, SrO and BaO.)
  • alkali aluminoborosilicate glass examples include glasses having the following compositions, in which each component is expressed in mole percentage on an oxide basis. 61% ⁇ SiO2 ⁇ 75% 1.0% ⁇ Al2O3 ⁇ 20% 1.0% ⁇ B2O3 ⁇ 10% 0.0% ⁇ MgO ⁇ 15% 0.0% ⁇ CaO ⁇ 10% 0.0% ⁇ SrO ⁇ 1.0% 0.0% ⁇ BaO ⁇ 1.0% 0.0% ⁇ Li2O ⁇ 15% 2.0% ⁇ Na2O ⁇ 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 content of Li 2 O, Na 2 O and K 2 O, and RO represents the total content of MgO, CaO, SrO and BaO.)
  • the second glass sheet 12 may be soda-lime glass.
  • the soda-lime glass may contain 3.5% or less of Al2O3 .
  • examples of the soda-lime glass include glasses having the following compositions . Each component is expressed in mole percentage based on the oxide. 60% ⁇ SiO2 ⁇ 75% 0.0% ⁇ Al2O3 ⁇ 3.5% 2.0% ⁇ MgO ⁇ 11% 2.0% ⁇ CaO ⁇ 10% 0.0% ⁇ SrO ⁇ 3.0% 0.0% ⁇ BaO ⁇ 3.0% 10% ⁇ Na2O ⁇ 18% 0.0% ⁇ K2O ⁇ 8.0% 0.0% ⁇ ZrO2 ⁇ 4.0% 0.0010% ⁇ Fe2O3 ⁇ 5.0%
  • the thickness of the first glass plate 11 is preferably 2.5 mm or more. By making the thickness of the first glass plate 11 2.5 mm or more, the critical impact fracture speed of glass having a high fracture toughness value can be improved.
  • the thickness of the first glass plate 11 is more preferably 2.8 mm or more, even more preferably 2.9 mm or more, even more preferably 3.0 mm or more, especially preferably 3.1 mm or more, even more preferably 3.2 mm or more, even more preferably 3.3 mm or more, particularly preferably 3.4 mm or more, and most preferably 3.5 mm or more.
  • the thickness of the first glass plate 11 is preferably 6.0 mm or less, more preferably 5.5 mm or less, even more preferably 5.0 mm or less, particularly preferably 4.8 mm or less, and most preferably 4.5 mm or less.
  • the thickness of the second glass plate 12 is preferably 0.50 mm or more, more preferably 0.60 mm or more, even more preferably 0.70 mm or more, particularly preferably 0.80 mm or more, particularly preferably 0.90 mm or more, and most preferably 1.0 mm or more.
  • a thickness of 0.50 mm or more for the second glass plate 12 is preferable from the standpoint of impact resistance.
  • the thickness of the second glass sheet 12 is preferably 2.0 mm or less, more preferably 1.9 mm or less, even more preferably 1.8 mm or less, particularly preferably 1.7 mm or less, particularly preferably 1.6 mm or less, and most preferably 1.5 mm or less. If the thickness of the second glass sheet 12 is 2.0 mm or less, the weight of the laminated glass 10 will not be too large, which is preferable in terms of improving fuel efficiency when used in a vehicle.
  • the first glass plate 11 and the second glass plate 12 may have the same thickness or different thicknesses, but it is preferable that the first glass plate 11 is thicker than the second glass plate 12.
  • Methods for adjusting the thickness of the first glass plate 11 and the second glass plate 12 include a method of adjusting the thickness of the glass using a float method or a downdraw method, and a method of polishing the glass in the thickness direction using a grinding wheel and then making it into a mirror-like state using an abrasive such as cerium oxide.
  • the surface roughness Ra after molding or polishing is preferably 5.0 nm or less, more preferably 2.0 nm or less, even more preferably 1.5 nm or less, particularly preferably 1.0 nm or less, and most preferably 0.50 nm or less.
  • the thickness of the first glass sheet 11 and the second glass sheet 12 may be constant over the entire surface, or may vary from place to place as necessary, such as forming a wedge shape in which the thickness of one or both of the first glass sheet 11 and the second glass sheet 12 gradually decreases.
  • At least one of the first glass plate 11 and the second glass plate 12 may be chemically strengthened glass that has been subjected to glass strengthening in order to improve its strength.
  • the method of chemical strengthening is the same as the above-mentioned chemical strengthening treatment of glass.
  • Examples of chemically strengthened glass include the above-mentioned alkali aluminosilicate glass and the above-mentioned alkali aluminoborosilicate glass that have been subjected to chemical strengthening treatment.
  • the first glass sheet 11 and the second glass sheet 12 may have a flat shape or a curved shape having a curvature entirely or partially. If the first glass sheet 11 and the second glass sheet 12 are curved, they may have a single curved shape that is curved in only one of the vertical or horizontal directions, or a compound curved shape that is curved in both the vertical and horizontal directions. If the first glass sheet 11 and the second glass sheet 12 are curved, the radius of curvature in the vertical and horizontal directions may be the same or different. If the first glass sheet 11 and the second glass sheet 12 are curved, the radius of curvature in the vertical and/or horizontal directions is preferably 1000 mm or more. The shape of the main surface of the first glass sheet 11 and the second glass sheet 12 is made to fit the window opening of the vehicle in which they are installed.
  • the intermediate film 13 is sandwiched between the first glass plate 11 and the second glass plate 12.
  • the laminated glass 10 of this embodiment can firmly bond the first glass plate 11 and the second glass plate 12 together and can reduce the impact force when flying debris collides with the glass plates.
  • organic resins that are generally used in laminated glass used for conventional vehicles can be used.
  • organic resins include polyethylene (PE), ethylene vinyl acetate copolymer (EVA), polypropylene (PP), polystyrene (PS), methacrylic resin (PMA), polyvinyl chloride (PVC), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), cellulose acetate (CA), diallyl phthalate resin (DAP), urea resin (UP), melamine resin (MF), unsaturated polyester (UP), polyvinyl butyral (PVB), polyvinyl hol (PVB), and polyvinyl methacrylate (PMA).
  • PE polyethylene
  • EVA ethylene vinyl acetate copolymer
  • PP polypropylene
  • PS polystyrene
  • PMA methacrylic resin
  • PVC polyvinyl chloride
  • PET polyethylene terephthalate
  • PBT polybutylene terephthal
  • Marl Marl
  • PVB polyvinyl alcohol
  • PVB vinyl acetate resin
  • IO ionomer
  • TPX polymethylpentene
  • PVDC vinylidene chloride
  • PSF polysulfone
  • PVDF polyvinylidene fluoride
  • MS methacrylic-styrene copolymer resin
  • PAR polyarene
  • PASF polyarylsulfone
  • BR polybutadiene
  • PESF polyethersulfone
  • PEEK polyetheretherketone
  • EVA and PVB are preferred from the viewpoint of transparency and adhesion, and PVB is particularly preferred because it can provide sound insulation.
  • the thickness of the intermediate film 13 is preferably 0.300 mm or more, more preferably 0.500 mm or more, and even more preferably 0.700 mm or more. From the viewpoint of suppressing a decrease in visible light transmittance, the thickness of the intermediate film 13 is preferably 1.00 mm or less, more preferably 0.900 mm or less, and even more preferably 0.800 mm or less. The thickness of the intermediate film 13 is preferably in the range of 0.300 mm to 1.00 mm, and more preferably in the range of 0.700 mm to 0.800 mm.
  • the thickness of the intermediate film 13 may be constant across the entire surface, or may vary from place to place as necessary.
  • the difference in linear expansion coefficient between the interlayer 13 and the first glass sheet 11 or the second glass sheet 12 is large, when the laminated glass 10 is produced through the heating process described below, the laminated glass 10 may crack or warp, resulting in poor appearance. Therefore, it is preferable that the difference in linear expansion coefficient between the interlayer 13 and the first glass sheet 11 or the second glass sheet 12 is as small as possible.
  • the difference in linear expansion coefficient between the interlayer 13 and the first glass sheet 11 or the second glass sheet 12 may be expressed as the difference between the average linear expansion coefficients in a specified temperature range.
  • a predetermined average linear expansion coefficient difference may be set in a temperature range below the glass transition point of the resin material.
  • the difference in linear expansion coefficient between the first glass sheet 11 or the second glass sheet 12 and the resin material may be set at a predetermined temperature below the glass transition point of the resin material.
  • the intermediate film 13 may be an adhesive layer containing an adhesive.
  • the adhesive is not particularly limited, but for example, an acrylic adhesive or a silicone adhesive can be used.
  • the interlayer 13 is an adhesive layer, there is no need to go through a heating step in the process of joining the first glass plate 11 and the second glass plate 12, and therefore there is little risk of the above-mentioned cracking or warping occurring.
  • the laminated glass 10 of the present embodiment may include layers (hereinafter also referred to as "other layers") other than the first glass plate 11, the second glass plate 12, and the interlayer film 13, provided that the effects of the present invention are not impaired.
  • the laminated glass 10 may include a coating layer that imparts a water-repellent function, a hydrophilic function, an anti-fogging function, or the like, an infrared reflective film, or the like.
  • the other layers may be provided at any position without any particular limitations, and may be provided on the surface of the laminated glass 10, or may be provided so as to be sandwiched between the first glass sheet 11, the second glass sheet 12, or the intermediate film 13.
  • the laminated glass 10 of this embodiment may also include a black ceramic layer or the like arranged in a strip shape on part or all of the periphery for the purpose of concealing the attachment portion to the frame or the wiring conductors.
  • the first glass plate 11 has a surface roughness Ra of 5.0 nm or less and a thickness of 2.5 mm, and when a tungsten carbide alloy with a tip curvature radius of 200 ⁇ m, an apex angle of 120°, and a weight of 1.365 g is collided with the surface of the first glass plate 11, the critical impact destruction speed is preferably 35 km/h or more. By having a critical impact destruction speed of 35 km/h or more, the resistance to flying stones can be improved.
  • the critical impact destruction speed is more preferably 36 km/h or more, even more preferably 37 km/h or more, even more preferably 38 km/h or more, even more preferably 39 km/h or more, particularly preferably 40 km/h or more, and most preferably 42 km/h or more.
  • the upper limit of the critical impact destruction speed is, for example, 120 km/h or less.
  • the laminated glass of this embodiment preferably has a critical impact destruction speed of 35 km/h or more when a tungsten carbide alloy having a tip curvature radius of 200 ⁇ m, an apex angle of 120°, and a weight of 1.365 g is struck against the surface of the first glass plate 11.
  • the critical impact destruction speed is more preferably 37 km/h or more, even more preferably 40 km/h or more, even more preferably 45 km/h or more, even more preferably 50 km/h or more, particularly preferably 55 km/h or more, and most preferably 60 km/h or more.
  • the upper limit of the critical impact destruction speed is, for example, 120 km/h or less.
  • the total thickness of the first glass sheet 11, the second glass sheet 12, and the intermediate film 13 is preferably 4.5 mm or more.
  • the total thickness of the first glass sheet 11, the second glass sheet 12, and the intermediate film 13 is preferably 4.5 mm or more.
  • the total thickness is more preferably 4.6 mm or more, even more preferably 4.7 mm or more, even more preferably 4.8 mm or more, particularly preferably 4.9 mm or more, and most preferably 5.0 mm or more.
  • the total thickness is preferably 8.0 mm or less, more preferably 7.8 mm or less, even more preferably 7.6 mm or less, particularly preferably 7.4 mm or less, particularly preferably 7.2 mm or less, and most preferably 7.0 mm or less.
  • the total thickness of the first glass plate 11, the second glass plate 12, and the intermediate film 13 varies depending on the location, it is preferable that the total thickness at the thinnest location is 4.5 mm or more.
  • the ratio ( t1 / t2 ) of the thickness t1 of the first glass plate to the thickness t2 of the second glass plate is preferably 1.5 or more.
  • the ratio ( t1 / t2 ) is more preferably 2.0 or more, even more preferably 2.5 or more, even more preferably 3.0 or more, particularly preferably 3.5 or more, and most preferably 4.0 or more.
  • the ratio ( t1 / t2 ) is preferably 6.0 or less, more preferably 5.5 or less, and even more preferably 5.0 or less.
  • the laminated glass 10 of this embodiment preferably has a visible light transmittance Tv defined by ISO-9050:2003 using a D65 light source of 70% or more.
  • Tv is more preferably 71% or more, and even more preferably 72% or more.
  • Tv is, for example, 90% or less.
  • the laminated glass 10 of this embodiment preferably has a total solar transmittance Tts of 70% or less, as defined in ISO-13837:2008 convention A and measured at a wind speed of 4 m/s.
  • Tts is more preferably 68% or less, and even more preferably 66% or less.
  • Tts is, for example, 55% or more.
  • the laminated glass 10 of this embodiment can be manufactured by a method similar to that used for conventionally known laminated glass. For example, a first glass sheet 11, an intermediate film 13, and a second glass sheet 12 are laminated in this order, and a process of heating and pressurizing is performed to obtain a laminated glass 10 in which the first glass sheet 11 and the second glass sheet 12 are bonded together via the intermediate film 13.
  • the manufacturing method of the laminated glass 10 of this embodiment may, for example, include a process of heating and shaping the first glass sheet 11 and the second glass sheet 12, followed by a process of inserting the intermediate film 13 between the first glass sheet 11 and the second glass sheet 12 and heating and pressurizing the sheet.
  • the laminated glass 10 may be formed in which the first glass sheet 11 and the second glass sheet 12 are joined together via the intermediate film 13.
  • the glass of the present embodiment has excellent fracture toughness and excellent bending formability, and therefore can be suitably used as glass to be provided in vehicles or sensors, and more specifically, can be suitably used as a window glass in a vehicle or a cover glass for a sensor.
  • the glass of the present embodiment has excellent fracture toughness and excellent bending formability, and is therefore suitable for components such as window glass in a vehicle, specifically windshield, side glass, rear glass, roof glass, etc.
  • the glass can be suitably used as a cover glass for sensors such as LiDAR, cameras, and millimeter wave radar mounted on vehicles and unmanned or manned eVTOLs (Electric Vertical Take-Off and Landing aircraft) such as drones.
  • FIG. 4 is a conceptual diagram showing a state in which laminated glass 10 including the glass of this embodiment is attached to an opening 110 formed in the front of an automobile 100 and used as an automobile window glass.
  • Laminated glass 10 used as an automobile window glass may have a housing (case) 120 attached to the surface on the inside of the vehicle that contains an information device, etc., to ensure the safe running of the vehicle.
  • the information devices stored in the housing are devices that use cameras, radars, etc. to prevent rear-end collisions with vehicles, pedestrians, obstacles, etc. ahead of the vehicle and to alert the driver to danger.
  • they are information receiving devices and/or information transmitting devices, etc., and include millimeter wave radar, stereo cameras, infrared lasers, etc., and send and receive signals.
  • the "signals" in question are electromagnetic waves including millimeter waves, visible light, infrared light, etc.
  • FIG. 5 is an enlarged view of portion S in FIG. 4, and is a perspective view showing the portion of the laminated glass 10 of this embodiment where the housing 120 is attached.
  • the housing 120 houses a millimeter wave radar 201 and a stereo camera 202 as information devices.
  • the housing 120 that houses the information devices is usually attached on the outer side of the vehicle relative to the rearview mirror 150 and on the inner side of the vehicle relative to the laminated glass 10, but may be attached to other portions.
  • FIG. 6 is a cross-sectional view taken along line Y-Y in FIG. 5 and perpendicular to the horizontal line. It is preferable that the first glass sheet 11 of the laminated glass 10 is disposed on the exterior side of the vehicle. With the above configuration, a lightweight windshield with excellent fracture toughness can be realized. In addition, the glass of this embodiment has low viscosity, making it easy to bend when manufacturing the windshield.
  • ⁇ 2> The glass according to ⁇ 1>, having a Young's modulus of 75 GPa or more.
  • ⁇ 3> The glass according to ⁇ 1> or ⁇ 2>, having a fracture toughness value K IC measured by the SEPB method of 0.76 MPa ⁇ m 1/2 or more.
  • ⁇ 4> The glass according to any one of ⁇ 1> to ⁇ 3>, having a deformation point of 670° C. or lower.
  • ⁇ 5> The glass according to any one of ⁇ 1> to ⁇ 4>, wherein a ratio (H/L) of an H value to an L value calculated by the following formula is 0.10 or less.
  • ⁇ 7> The glass according to any one of ⁇ 1> to ⁇ 6>, wherein the glass has a critical impact fracture speed of 35 km/h or more when a tungsten carbide cemented carbide having a tip curvature radius of 200 ⁇ m, an apex angle of 120°, and a weight of 1.365 g is collided with the glass when the surface roughness Ra is 5.0 nm or less and the thickness is 2.5 mm.
  • ⁇ 8> The glass according to any one of ⁇ 1> to ⁇ 6>, which has a critical impact fracture speed of 53 km/h or more when collided with a tungsten carbide cemented carbide having a tip curvature radius of 200 ⁇ m, an apex angle of 120°, and a weight of 1.365 g.
  • ⁇ 9> The glass according to any one of ⁇ 1> to ⁇ 8>, having a thickness of 2.5 mm or more.
  • a vehicle window glass comprising the glass according to any one of ⁇ 1> to ⁇ 9>.
  • ⁇ 11> A glass for sensors, comprising the glass according to any one of ⁇ 1> to ⁇ 9>.
  • a glass window pane comprising a first glass plate, a second glass plate, and an intermediate film sandwiched between the first glass plate and the second glass plate,
  • the first glass plate is the glass according to any one of ⁇ 1> to ⁇ 9>.
  • ⁇ 14> The laminated glass according to ⁇ 12>, wherein a critical impact fracture speed when a tungsten carbide cemented carbide having a tip curvature radius of 200 ⁇ m, an apex angle of 120°, and a weight of 1.365 g is collided against a surface of the first glass plate is 53 km/h or more.
  • ⁇ 15> The laminated glass according to any one of ⁇ 12> to ⁇ 14>, in which a total thickness of the first glass plate, the second glass plate, and the interlayer film is 4.5 mm or more.
  • ⁇ 16> The laminated glass according to any one of ⁇ 12> to ⁇ 15>, wherein a ratio (t 1 /t 2 ) of a thickness t 1 of the first glass plate to a thickness t 2 of the second glass plate is 1.5 or more.
  • a glass window pane comprising a first glass plate, a second glass plate, and an intermediate film sandwiched between the first glass plate and the second glass plate, The first glass plate and the second glass plate are the glass plate according to any one of ⁇ 1> to ⁇ 9>.
  • ⁇ 18> The laminated glass according to any one of ⁇ 12> to ⁇ 16>, wherein the second glass plate is a soda-lime glass.
  • Temperature T2 , temperature T4 The temperature T2 at which the glass viscosity ⁇ becomes 10 2 dPa ⁇ s, which is a criterion for the solubility of glass, and the temperature T4 at which the glass viscosity ⁇ becomes 10 4 dPa ⁇ s, are measured using a rotational viscometer. did.
  • T g Glass transition temperature
  • CTE 50-350 Average coefficient of linear expansion from 50 to 350 ° C.
  • Poisson's ratio Based on JIS R1602:1995 "Elastic modulus test method for fine ceramics", the measurement was performed at 25°C using an ultrasonic pulse method (Olympus, DL35).
  • Example 12 which is a comparative example, Al 2 O 3 was less than 3.0%, CaO was more than 5.0%, and Li 2 O was less than 1.0%, so the Young's modulus and fracture toughness were lower than those of the examples.
  • Example 13 which is a comparative example, SiO 2 was less than 60%, Li 2 O was less than 1.0%, K 2 O was more than 3.0%, TiO 2 was more than 1.0%, and Y 2 O 3 was more than 1.0%, so the yield point was high.
  • Example 14 which is a comparative example, Al 2 O 3 was more than 9.0% and Li 2 O was less than 1.0%, so the T g was high. Since the yield point is higher than T g , the yield point of Example 14 was higher than 700 ° C., and it was found that the bending formability was poor.
  • Example 15 SiO2 is less than 60%, Al2O3 is more than 9.0%, Li2O is less than 1.0%, Na2O is less than 6.0%, K2O is more than 3.0%, and R2O is less than 11%, so that Tg was high. Since the yield point is higher than Tg , it was found that Example 15's yield point was higher than 702 ° C. and had poor bending formability.
  • Examples 16 and 18, which are comparative examples Al2O3 was more than 9.0% and RO was less than 7.0%, so that the yield point was high.
  • Example 17 which is a comparative example, Al2O3 was more than 9.0%, RO was less than 7.0%, and TiO2 was more than 1.0 % , so that the yield point was high.
  • Test Examples 1 to 3 were produced according to the following procedure.
  • Test Examples 1 to 3 are comparative examples, and Test Examples 4 to 7 are working examples.
  • Test Example 1 As the first glass plate and the second glass plate, glass having a thickness of 2.0 mm and a composition shown in Example 13 of Table 1 with a surface roughness Ra of 2.0 nm or less was used.
  • As the intermediate film polyvinyl butyral (PVB) having a thickness of 0.78 mm was used.
  • the first glass plate, the intermediate film, and the second glass plate were laminated in this order, and preliminary adhesion was performed at 120 ° C. for 15 minutes, and then pressure bonding was performed under conditions of 130 ° C. and 1 MPa.
  • the laminated glass of Test Example 1 was then produced by returning to room temperature and atmospheric pressure over 90 minutes.
  • the total thickness of the first glass plate, the second glass plate, and the intermediate film was 4.8 mm, and the ratio (t 1 /t 2 ) of the thickness t 1 of the first glass plate to the thickness t 2 of the second glass plate was 1.0.
  • Test Example 2 A laminated glass was produced in the same manner as in Test Example 1, except that the thicknesses of the first glass plate and the second glass plate were changed to the values shown in Table 2.
  • Test Example 3 Laminated glass was produced in the same manner as in Test Example 1, except that the thickness of the first glass plate was changed to the value shown in Table 2 and a 0.7 mm-thick soda-lime glass (manufactured by AGC, model number: AS2) was used as the second glass plate.
  • Test Examples 4 to 7 Laminated glass was produced in the same manner as in Test Example 3, except that the type of the first glass plate was changed to one shown in Table 2 (all having a surface roughness Ra of 2.0 nm or less).
  • the critical impact fracture speed Vcrt was measured by the following procedure.
  • a tungsten carbide hard alloy with a tip curvature radius of 200 ⁇ m, an apex angle of 120°, and a weight of 1.365 g was ejected at a speed of 20 km/h or more and was caused to collide with the surface of the first glass plate.
  • the progress of the crack caused by the collision of the tungsten carbide hard alloy was observed from the cross section of the laminated glass with a high-speed camera.
  • the test was carried out while changing the ejection speed, and when the crack caused on the surface of the first glass plate progressed and reached the surface of the first glass plate opposite to the surface where the tungsten carbide hard alloy was collided, it was judged to be a crack, and the collision speed at that time was taken as the critical collision fracture speed Vcrt.
  • test examples 4 to 7 which are working examples, had a higher critical impact fracture speed than the comparative example.

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PCT/JP2024/014902 2023-04-28 2024-04-12 ガラス、車両用窓ガラス、センサー用ガラス及び合わせガラス Ceased WO2024225086A1 (ja)

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DE112024001006.7T DE112024001006T5 (de) 2023-04-28 2024-04-12 Glas, fensterscheibe für fahrzeuge, glas für sensoren und laminiertes glas
CN202480027959.6A CN121039074A (zh) 2023-04-28 2024-04-12 玻璃、车辆用窗玻璃、传感器用玻璃及夹层玻璃
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CN120398412A (zh) * 2025-07-02 2025-08-01 湖南兴怀新材料科技有限公司 一种抗摔抗划伤的锂铝硅酸盐玻璃及其制备方法
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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JPH11199267A (ja) * 1997-11-12 1999-07-27 Asahi Glass Co Ltd 磁気ディスク基板用ガラス
JP2005247656A (ja) * 2004-03-05 2005-09-15 Toyo Sasaki Glass Co Ltd 高洗浄性ガラス成形品
JP2006160546A (ja) * 2004-12-06 2006-06-22 Hitachi Ltd 平面型表示装置
WO2010024283A1 (ja) * 2008-08-27 2010-03-04 日本板硝子株式会社 鱗片状ガラス及び被覆鱗片状ガラス
JP2015501280A (ja) * 2011-10-25 2015-01-15 コーニング インコーポレイテッド 改良された化学的および機械的耐久性を有するアルカリ土類アルミノケイ酸ガラス組成物
WO2018199299A1 (ja) * 2017-04-28 2018-11-01 Ａｇｃ株式会社 ガラス板および窓
JP2020525379A (ja) * 2017-06-22 2020-08-27 コーニング インコーポレイテッド 自動車用ガラス組成物、物品およびハイブリッド積層板

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Publication number Priority date Publication date Assignee Title
JPH11199267A (ja) * 1997-11-12 1999-07-27 Asahi Glass Co Ltd 磁気ディスク基板用ガラス
JP2005247656A (ja) * 2004-03-05 2005-09-15 Toyo Sasaki Glass Co Ltd 高洗浄性ガラス成形品
JP2006160546A (ja) * 2004-12-06 2006-06-22 Hitachi Ltd 平面型表示装置
WO2010024283A1 (ja) * 2008-08-27 2010-03-04 日本板硝子株式会社 鱗片状ガラス及び被覆鱗片状ガラス
JP2015501280A (ja) * 2011-10-25 2015-01-15 コーニング インコーポレイテッド 改良された化学的および機械的耐久性を有するアルカリ土類アルミノケイ酸ガラス組成物
WO2018199299A1 (ja) * 2017-04-28 2018-11-01 Ａｇｃ株式会社 ガラス板および窓
JP2020525379A (ja) * 2017-06-22 2020-08-27 コーニング インコーポレイテッド 自動車用ガラス組成物、物品およびハイブリッド積層板

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN120398412A (zh) * 2025-07-02 2025-08-01 湖南兴怀新材料科技有限公司 一种抗摔抗划伤的锂铝硅酸盐玻璃及其制备方法

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