WO2019017404A1 - Verre renforcé - Google Patents

Verre renforcé Download PDF

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Publication number
WO2019017404A1
WO2019017404A1 PCT/JP2018/026961 JP2018026961W WO2019017404A1 WO 2019017404 A1 WO2019017404 A1 WO 2019017404A1 JP 2018026961 W JP2018026961 W JP 2018026961W WO 2019017404 A1 WO2019017404 A1 WO 2019017404A1
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Prior art keywords
glass
less
content
tempered glass
mol
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PCT/JP2018/026961
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English (en)
Japanese (ja)
Inventor
円佳 小野
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Ａｇｃ株式会社
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Priority to JP2019530577A priority Critical patent/JP7136100B2/ja
Publication of WO2019017404A1 publication Critical patent/WO2019017404A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B27/00—Tempering or quenching glass products
    • C03B27/04—Tempering or quenching glass products using gas
    • 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
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • 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
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • 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
    • 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
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • 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
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum

Definitions

  • the present invention relates to tempered glass. More specifically, the present invention relates to a tempered glass used as a window glass of a building.
  • Patent Document 1 there is a movement to replace ordinary glass windows with tempered glass for safety (prevention of broken glass from falling) when natural disasters such as earthquakes, typhoons and tornadoes occur.
  • tempered glass is used as a window, the tensile stress inside the glass is strong, and there is a risk that the glass may be broken and fall when it is broken.
  • a tempered glass window is changed to a laminated glass window to prevent falling.
  • the thickness of the glass becomes large and it does not enter the existing sash, and in replacement of the window glass only It is necessary to replace every sash by all means.
  • FIG. 1 is a view showing an example of a glass having many fragments
  • FIG. 2 is a view showing an example of a glass having few fragments.
  • the present invention aims to provide a tempered glass having high strength due to compressive stress on the surface but having few fragments when broken.
  • the present invention provides a tempered glass having a mirror constant A of 2.2 MPa ⁇ m 0.5 or more, a surface compressive stress (CS) of 10 MPa or more, and a thickness t of 1.2 mm or more and 50 mm or less. .
  • the tempered glass of the present invention is suitable as a window glass for buildings because it is strong against wind pressure and impact and has few fragments when it breaks.
  • FIG. 1 is a view showing an example of a glass having many fragments.
  • FIG. 2 is a view showing an example of glass with few fragments.
  • FIG. 3 is a view schematically showing a method of cracking around the origin of fracture when a glass having no residual stress inside is broken by uniform tensile stress.
  • strengthening processing method of the tempered glass of this invention is not specifically limited, Even if it is the air-cooling tempered glass which gave the wind-cooled reinforcement process, the chemically tempered glass which gave the chemical strengthening process may be sufficient. However, when it is used as a window glass of a building, it is preferable that the glass is wind-cooled and tempered in consideration of the size of the glass which can be easily tempered and the cost.
  • glass having a large mirror constant A has a small number of fragments when broken. How to break the tempered glass depends on the characteristics of the glass before the tempering treatment. Therefore, a glass (tempered glass) obtained by subjecting a glass having a large mirror constant A before tempering treatment to tempering treatment (tempered glass) has a small number of fragments even when it is broken, so the fragments are less likely to be scattered and safety is high.
  • the mirror constant A does not change before and after the strengthening treatment, hereinafter, in the present specification, the mirror constant A of the glass before the strengthening treatment is the mirror constant A of the tempered glass (tempered glass) I assume.
  • the tempered glass of the present invention has a mirror constant A of 2.2 MPa ⁇ m 0.5 or more. This reduces the number of fragments when broken. Therefore, even if it is destroyed, the fragments are unlikely to be scattered and the safety is high.
  • Glass of the present invention preferably has a mirror constant A is 2.3 MPa ⁇ m 0.5 or more, more preferably 2.35MPa ⁇ m 0.5 or more, still be at 2.4 MPa ⁇ m 0.5 or more preferably, particularly preferably at 2.45 MPa ⁇ m 0.5 or more, and most preferably 2.5 MPa ⁇ m 0.5 or more.
  • the upper limit of the Miller constant A is not particularly limited, but is preferably 5 MPa ⁇ m 0.5 or less in order to maintain the glass structure.
  • the tempered glass of the present invention can increase the surface compressive stress CS and / or the depth DOL of the compressive stress layer by the above-mentioned characteristics. If the surface compressive stress CS and / or the depth DOL of the compressive stress layer is increased in order to increase the strength, the internal tensile stress CT increases, so the density of fragments when the glass breaks increases, which may cause a risk. It was said to increase.
  • Patent Document 1 discloses the formula (1) indicating the allowable limit of internal tensile stress of tempered glass, and the fragment density even if the strength of the chemically tempered glass is increased by adjusting the following CT ′ to a low value. Is said to be able to obtain chemically strengthened glass with less scattering of fragments.
  • CT ′ uses the values of CS and DOL ′ and has a relationship of the following formula (2).
  • CT ′ ⁇ ⁇ 38.7 ⁇ ln (t) +48.2 (1)
  • CS ⁇ DOL ′ (t ⁇ 2 ⁇ DOL ′) ⁇ CT ′ (2)
  • Equation (2) may be rewritten as equation (3).
  • CT ′ CS ⁇ DOL ′ / (t ⁇ 2 ⁇ DOL ′) (3)
  • the tempered glass of the present invention can be subjected to a tempering treatment exceeding the maximum value of CT ′ represented by the formula (1) because the fractured chip density when broken is low. Since CT ′ has the relationship of CS, DOL ′ and equation (2), when CT ′ goes up, either CS or DOL ′ can be increased and the strength is increased.
  • the tempered glass having a large CS is hard to be broken even if the surface is scratched because the surface compressive stress has an effect of narrowing the scratch.
  • the tensile stress applied to the outside of the curved surface when the glass sheet is bent is offset by the surface compressive stress, it is difficult to be broken even when the glass sheet is bent. If the DOL is large, it is possible to increase the resistance to the impact of flying objects.
  • the tempered glass of the present invention can have a surface compressive stress (CS) of 10 MPa or more for the reasons described above.
  • the tempered glass of the present invention preferably has a surface compressive stress (CS) of 15 MPa or more, more preferably 50 MPa or more, more preferably 60 MPa or more, and more preferably 70 MPa or more, 80 MPa More preferably, the pressure is 90 MPa or more, and particularly preferably 100 MPa or more.
  • the upper limit of the surface compressive stress (CS) is not particularly limited, but is preferably 2500 MPa or less because excessive compression causes local tensile stress around the microcracks and leads to overall failure.
  • the tempered glass of the present invention preferably has a product (CS ⁇ A) of surface compressive stress (CS) and mirror constant A of 22 (MPa) 2 ⁇ m 0.5 or more, 50 (MPa) 2 ⁇ m 0.5 or more Is more preferably 100 (MPa) 2 ⁇ m 0.5 or more, still more preferably 150 (MPa) 2 ⁇ m 0.5 or more, and 200 (MPa) 2 ⁇ m 0.5 or more Is particularly preferred.
  • CS ⁇ A product of surface compressive stress (CS) and mirror constant A of 22 (MPa) 2 ⁇ m 0.5 or more, 50 (MPa) 2 ⁇ m 0.5 or more Is more preferably 100 (MPa) 2 ⁇ m 0.5 or more, still more preferably 150 (MPa) 2 ⁇ m 0.5 or more, and 200 (MPa) 2 ⁇ m 0.5 or more Is particularly preferred.
  • the thickness t is 1.2 mm or more and 50 mm or less. If the thickness t is 1.2 mm or more, the temperature difference between the surface and the inside is likely to occur, and physical strengthening treatment (also referred to as air-cooling strengthening treatment, hereinafter the same) can be easily performed. If the thickness t is 50 mm or less, the weight of the entire glass is reduced and it is easy to use as a window.
  • the thickness t of the tempered glass of the present invention is preferably 1.3 mm or more, more preferably 1.5 mm or more, more preferably 1.7 mm or more, more preferably 1.9 mm or more, 2.0 mm or more It is more preferable, particularly preferably 2.1 mm or more, and most preferably 2.3 mm or more.
  • the plate thickness t is preferably 45 mm or less, more preferably 40 mm or less, more preferably 35 mm or less, still more preferably 30 mm or less, particularly preferably 25 mm or less, and most preferably 20 mm or less.
  • board thickness t direction of glass means the following.
  • the distance in the normal direction from the main surface of the glass plate to the other main surface is t, and this normal direction is defined as the t direction.
  • the position of t / 2 in the t direction from the main surface is the central portion in the thickness direction t of the glass.
  • the tensile stress becomes maximum at the position of t / 2 in the t direction from the main surface, so the value of the tensile stress in this portion is an important value that determines the fracture characteristics.
  • the fictive temperature of the tempered glass particularly the fictive temperature of the central portion in the thickness direction t, is affected by the fictive temperature of the glass before the tempering treatment.
  • the virtual temperature does not substantially differ before and after the strengthening treatment.
  • the mirror constant A of the glass is 2.2 MPa ⁇ m 0.5 or more, that the fictive temperature of the central portion in the direction of thickness t of the glass is the glass transition point Tg + 60 ° C. or less of the glass Preferred.
  • the fictive temperature at the central portion in the thickness direction t of the glass is more preferably Tg + 50 ° C. or less, and still more preferably Tg + 40 ° C. or less.
  • the virtual temperature T f in the present invention is a numerical value obtained by the refractive index method described below.
  • the specific method of obtaining the virtual temperature T f by the refractive index method is as follows. First, i pieces (i ⁇ 2) of test pieces are prepared from a glass sample whose virtual temperature is to be measured, and the cooling rate is 1000 ° C. after keeping the refractive index in equilibrium at different cooling start temperatures. Cool at least min.
  • the cooling start temperature is lower than the glass transition temperature, a sufficiently long holding time is required, so the cooling start temperature is preferably 10 ° C. to 100 ° C. higher than the glass transition temperature.
  • the refractive index n d is measured at a specific wavelength (for example, d line of He lamp, 587.6 nm).
  • the refractive index n di of the glass quenched from the cooling start temperature is plotted for each cooling start temperature T i , the constants a and b in equation (4) are determined by linear regression, and a calibration curve is created.
  • the virtual temperature T f can be cut out from the glass to be measured, the refractive index n dS of the polished test piece can be measured, and the virtual temperature T f of the glass can be determined using a calibration curve.
  • the virtual temperature of the glass before tempering can be adjusted by the following procedure.
  • a glass material having a predetermined composition is prepared and melted, and then formed into a plate glass.
  • the cooling temperature profile at the time of molding the fictive temperature of the glass can be adjusted.
  • the cooling rate near the glass transition point for example, the temperature between the annealing point and the strain point
  • this can be achieved by setting the temperature to 200 ° C./min or less.
  • the fictive temperature of glass can be adjusted by the following procedure.
  • a glass raw material of a predetermined composition After preparing and melting a glass raw material of a predetermined composition, it is formed into sheet glass by a known sheet glass forming method (for example, float method, fusion method, roll-out method). After molding, the glass is heated to a predetermined cooling start temperature, and held at that temperature. Thereafter, by adjusting the cooling rate, the fictive temperature of the glass can be adjusted. In order to lower the fictive temperature of the glass, the cooling start temperature may be lowered. In this case, it is preferable that the cooling rate be high, because the virtual temperature is close to the cooling start temperature.
  • a known sheet glass forming method for example, float method, fusion method, roll-out method.
  • the required holding time varies depending on the cooling start temperature, but is preferably 500 / (cooling start temperature-T g ) min or more, and more preferably 1000 / (cooling start temperature-T g ) min or more.
  • the cooling start temperature is preferably Tg + 100 ° C. or less. If it is Tg + 100 ° C. or less, the fictive temperature can be easily lowered even by heat treatment for a short time, so that the time required for the process can be shortened and deformation at the time of holding can be suppressed.
  • the cooling start temperature is more preferably Tg + 60 ° C. or less, still more preferably Tg + 30 ° C. or less, and particularly preferably Tg + 20 ° C. or less.
  • the cooling rate is preferably 100 ° C./min or more, more preferably 200 ° C./min or more, and still more preferably 300 ° C./min or more.
  • the glass after cooling is subjected to a strengthening treatment under predetermined conditions.
  • a strengthening treatment under predetermined conditions.
  • the center of the thickness t direction is placed in a heating furnace at Tg + 60 ° C to Tg + 110 ° C for a short time (for example, within 7 minutes) and quenched (for example, a cooling rate of 500 ° C / min or more)
  • Tg + 60 ° C to Tg + 110 ° C for a short time (for example, within 7 minutes) and quenched (for example, a cooling rate of 500 ° C / min or more)
  • the tempered glass of the present invention since the tempered glass of the present invention has a small number of fragments when broken, it can be subjected to tempering treatment exceeding the maximum value of CT ′ represented by the formula (1), and CS and DOL are high. can do.
  • the product (CT ⁇ A) of the tensile stress CT at the center in the thickness t direction and the mirror constant A is preferably 11 (MPa) 2 ⁇ m 0.5 or more, and 15 (MPa) It is more preferably 2 ⁇ m 0.5 or more, and still more preferably 20 (MPa) 2 ⁇ m 0.5 or more.
  • the compressive stress layer depth DOL can be increased by subjecting the tempered glass to a strengthening treatment exceeding the allowable limit of the internal tensile stress CT ′.
  • a tempered glass with a high DOL is difficult to break because the tip of the scratch remains in the compressive stress layer even when a deep scratch occurs.
  • the compressive stress layer depth DOL is preferably (1/10) ⁇ t mm or more, (1/8) ⁇ t mm or more Is more preferable, (1/7) ⁇ t mm or more is more preferable, and (1 / 6.5) ⁇ t mm or more is particularly preferable.
  • DOL is preferably (1/4) ⁇ t mm or less, more preferably (1 / 4.2) ⁇ t mm or less, and (1 / 4.5) ⁇ t mm or less More preferable. If DOL is (1/4) ⁇ t mm or less, the area where tensile stress occurs is (1 ⁇ 2) ⁇ t mm or less of the plate thickness, and tensile stress CT can be lowered, and many fragments are caused when the tempered glass breaks. The risk of splashing is reduced.
  • the compression stress layer depth DOL of the tempered glass of the present invention is preferably 0.150 mm or more, more preferably 0.200 mm or more, and still more preferably 0.300 mm or more.
  • the compression stress layer depth DOL is preferably 10 mm or less, more preferably 8 mm or less, more preferably 6 mm or less, still more preferably 5 mm or less, particularly preferably 4.5 mm or less, and most preferably 4 mm or less.
  • the tempered glass having a large DOL ' is difficult to be destroyed because the tip of the flaw remains in the compressive stress layer even when a deep flaw occurs.
  • the compression stress layer depth DOL 'of the tempered glass of the present invention is preferably 0.150 mm or more, more preferably 0.200 mm or more, and still more preferably 0.300 mm or more.
  • the compressive stress layer depth DOL ′ is preferably 10 mm or less, more preferably 8 mm or less, more preferably 6 mm or less, still more preferably 5 mm or less, particularly preferably 4.5 mm or less, and most preferably 4 mm or less.
  • the applicant of the present application has obtained the following findings on the relationship between the mirror constant A of glass and the physical properties of glass or the composition of glass.
  • the Poisson's ratio of glass is low.
  • the Poisson's ratio ⁇ ⁇ ⁇ of the glass is preferably 0.28 or less, more preferably 0.26 or less, and still more preferably 0.24 or less.
  • the lower limit of the Poisson's ratio ⁇ ⁇ ⁇ of the glass is not particularly limited, but is preferably 0.1 or more because an elastic deformation range at the time of impact is required to some extent. There are the following means to lower the Poisson's ratio ⁇ of the glass.
  • the network in the glass is developed and the glass has more voids. .
  • the glass has a space that contracts due to compression, it is easy to obtain a glass with a low Poisson's ratio.
  • MgO, ZrO 2 and the like are preferably used because they function as a network formation factor without significantly raising Tg.
  • the alkali metal oxide R 2 O is a generic term for Li 2 O, Na 2 O, K 2 O, and Rb 2 O (hereinafter, the same in the present specification).
  • the mirror constant A of the glass increases as the Young's modulus E of the glass increases.
  • it is effective to increase the Al 2 O 3 content in the glass.
  • the SiO 2 content in the glass is high, the network structure of the glass becomes relatively strong, and the Young's modulus of the glass is high.
  • the Young's modulus can be increased by increasing the Al 2 O 3 content and repairing the cut network structure.
  • alkaline earth metal oxide (RO) is a generic term for MgO, CaO, SrO and BaO (hereinafter, the same in the present specification).
  • the glass composition based on the above findings contains 30 to 85% of SiO 2 , 0 to 40% of Al 2 O 3 and 0 to 10% of P 2 O 5 in terms of mole percentage on an oxide basis, and is alkaline A metal oxide (R 2 O) in a total amount of 8 to 40%, an alkaline earth metal oxide (RO) in a total amount of 0 to 40%, and one substantially free of B 2 O 3 is preferable.
  • R 2 O alkaline A metal oxide
  • RO alkaline earth metal oxide
  • an alkali metal oxide Preferably contain 10 to 40% in total, 0 to 40% in total of alkaline earth metal oxides (RO), and substantially do not contain B 2 O 3 .
  • a mole percentage based on oxides, SiO 2 35 ⁇ 55%, the ratio of Al 2 O 3 and SiO 2 (Al 2 O 3 / SiO 2) is 0.3 ⁇ 0.6, P 2 O 5 and containing 0-5%, and alkali metal oxides (R 2 O) 20 ⁇ 40 % in a total amount, contains 0-15% alkaline earth metal oxide (RO) in a total volume, B 2 O It is further preferred that substantially no 3 is contained.
  • a mole percentage based on oxides, SiO 2 40 ⁇ 50%, the ratio of Al 2 O 3 and SiO 2 (Al 2 O 3 / SiO 2) is 0.5 ⁇ 0.6, P 2 O 5 and containing 0 to 1%, and alkali metal oxides (R 2 O) 20 ⁇ 30 % in a total amount, contains 5-15% alkaline earth metal oxide (RO) in a total volume, B 2 O Particularly preferred is one not substantially containing 3 .
  • Young's modulus E of glass will be 68 GPa or more, preferably 70 GPa or more, More preferably, 75 GPa or more, More preferably, 80 GPa or more.
  • the upper limit of the Young's modulus of glass is not particularly limited, it is generally 180 GPa or less.
  • SiO 2 is a main component of glass. If the content of SiO 2 is 30% or more, the weather resistance is good. The content of SiO 2 is more preferably 35% or more, further preferably 38% or more, and particularly preferably 40% or more. If the content of SiO 2 is 85% or less, devitrification hardly occurs. The content of SiO 2 is more preferably 55% or less, further preferably 50% or less, and particularly preferably 47% or less.
  • Al 2 O 3 is a component that improves the weather resistance.
  • the content of Al 2 O 3 is 0% or more. When Al 2 O 3 is contained, the weather resistance is improved.
  • the content of Al 2 O 3 is more preferably 1% or more, further preferably 3% or more, and particularly preferably 5% or more. If the content of Al 2 O 3 is 40% or less, the solubility is good.
  • the content of Al 2 O 3 is more preferably 35% or less, further preferably 32% or less, and particularly preferably 30% or less.
  • the ratio of Al 2 O 3 to SiO 2 is 0.3 or more, the structure becomes rigid due to the increase in the number of bonds.
  • Al 2 O 3 / SiO 2 0.35 or more is more preferable, and 0.4 or more is more preferable. More preferably, it is 0.5 or more. If the ratio of Al 2 O 3 to SiO 2 (Al 2 O 3 / SiO 2 ) is 0.6 or less, the viscosity of the glass at high temperatures is unlikely to be high, which is preferable.
  • Al 2 O 3 / SiO 2 is more preferably 0.55 or less, more preferably 0.52 or less.
  • P 2 O 5 is preferably not substantially contained because it is easy to form phase separation and devitrification species, but it may be contained at 10% or less in order to increase DOL.
  • the content of P 2 O 5 may be 5% or less, or 1% or less.
  • the viscosity of the glass at a high temperature is likely to decrease, so that the glass is easily melted.
  • the total amount of R 2 O is more preferably 10% or more, further preferably 12% or more, and particularly preferably 20% or more.
  • R 2 O is 40% or less in total, Young's modulus is unlikely to be low.
  • the total amount of R 2 O is preferably 35% or less, more preferably 30% or less.
  • Li 2 O is an alkali metal oxide component that does not cause a decrease in Young's modulus at room temperature while having the effect of lowering the viscosity of the glass at high temperatures. If the content of Li 2 O is 0.01% or more, the above effect appears. The content of Li 2 O is more preferably 2% or more, and still more preferably 4% or more. If Li 2 O is 20% or less, the network in the glass structure can be maintained. In addition, because the price of Li 2 O is high, the price of the glass to be obtained can be avoided. The content of Li 2 O is more preferably 15% or less, further preferably 10% or less.
  • Na 2 O is a component having the effect of lowering the viscosity of the glass at high temperature. If the content of Na 2 O is 5% or more, the above-described effect is obtained. The Na 2 O content is more preferably 10% or more, more preferably 15% or more. If the content of Na 2 O is 40% or less, the network in the glass structure can be maintained. The content of Na 2 O is more preferably 30% or less, and further preferably 20% or less.
  • K 2 O like Li 2 O and Na 2 O, is a component having the effect of lowering the viscosity of the glass at high temperature. If the content of K 2 O is 2% or more, the effect of lowering the viscosity becomes stronger. The content of K 2 O is more preferably 3% or more, and still more preferably 5% or more. If the content of K 2 O is 20% or less, the deliquescent of the glass can be reduced to some extent. The K 2 O content is more preferably 15% or less, more preferably 10% or less.
  • Rb 2 O like Li 2 O, Na 2 O, K 2 O, etc., is a component having the effect of lowering the viscosity of the glass at high temperatures. If the content of Rb 2 O is 1% or more, it is possible to increase the energy absorbing effect at the time of breakage of the glass by the mixed alkali effect. The content of Rb 2 O is more preferably 1% or more, and further preferably 2% or more. If the content of Rb 2 O is 10% or less, an excessive increase in the weight of glass can be prevented. The content of Rb 2 O is more preferably 5% or less, still more preferably 4% or less.
  • the alkaline earth metal oxide (RO) is a component that increases the Miller constant, and thus may be contained in either of physically strengthened glass and chemically strengthened glass. If RO is 3% or more in total, it leads to the rise of the Miller constant. RO may be 5% or more in total. Moreover, if RO is 40% or less in total, it is hard to devitrify. The total amount of RO is more preferably 30% or less, further preferably 25% or less, and particularly preferably 20% or less.
  • (CaO + SrO + BaO) in the alkali earth metal oxide (RO) is small, the ion exchange capacity is improved to obtain a large DOL.
  • (CaO + SrO + BaO) is preferably 5% or less in total.
  • the total amount of (CaO + SrO + BaO) is preferably 4% or less, more preferably 3% or less, and particularly preferably 1% or less.
  • (CaO + SrO + BaO) reduces the devitrification of the glass, and a stable glass can be obtained, so (CaO + SrO + BaO) is preferably 0.1% or more in total, and 0.5% or more in total. More preferably, 1% or more is more preferable.
  • MgO is a component that increases the mirror radius by increasing the Young's modulus of the glass.
  • the content of MgO is more preferably 5% or more, and further preferably 10% or more. If the content of MgO is 35% or less, problems such as devitrification can be avoided.
  • the content of MgO is more preferably 30% or less, and still more preferably 25% or less.
  • CaO is a component to improve the meltability at high temperatures or to make it difficult to cause devitrification. Therefore, devitrification can be suppressed as long as the content of CaO is 0.1% or more in any of physically strengthened glass and chemically strengthened glass.
  • the content of CaO is more preferably 0.5% or more, and further preferably 1% or more. When the content of CaO is 15% or less, both effects of improvement of the meltability and increase of the Young's modulus of the glass can be obtained.
  • content of CaO 10% or less is more preferable, and 5% or less is more preferable.
  • the content of CaO is preferably 5% or less, because the effect of enhancing DOL can be obtained by reducing the content of CaO.
  • the content of CaO is more preferably 3% or less, and further preferably 2% or less.
  • SrO is a component to improve the meltability at high temperatures or to make it difficult to cause devitrification. Therefore, in both cases of physically strengthened glass and chemically strengthened glass, if the content of SrO is 0.1% or more, devitrification prevention is effective.
  • the content of SrO is more preferably 0.2% or more, and still more preferably 0.3% or more. If the content of SrO is 15% or less, the weight increase of the glass does not become a problem.
  • the content of SrO is more preferably 10% or less, still more preferably 5% or less.
  • the content of SrO is preferably 5% or less because the effect of enhancing DOL can be obtained by reducing the content of SrO.
  • the content of SrO is more preferably 3% or less, and still more preferably 1% or less.
  • BaO is a component to improve the meltability at high temperatures or to make it difficult to cause devitrification.
  • the content of BaO is 0.1% or more, energy dissipation tends to occur easily due to the mixing effect of the alkaline earth.
  • the content of BaO is more preferably 0.2% or more, and further preferably 1% or more.
  • the content of BaO is 20% or less, the weight increase of the glass does not matter.
  • the content of BaO is more preferably 15% or less, and still more preferably 10% or less.
  • the content of BaO is preferably 5% or less.
  • the content of BaO is more preferably 3% or less, further preferably 1% or less, and particularly preferably 0.1% or less.
  • G E ⁇ 0.013 + ⁇ ⁇ ( ⁇ 6.6) + [Al 2 O 3 ] ⁇ 0.023 + ⁇ RO ⁇ 0.013 (7)
  • E Young's modulus (GPa) of the glass
  • ⁇ the Poisson's ratio of the glass
  • [Al 2 O 3 ] is the content of Al 2 O 3 in the glass (mol% on oxide basis)
  • ⁇ RO is the glass Total content of alkaline earth metal oxides in (mol% based on oxides)
  • G is more preferably 0.05 or more, further preferably 0.1 or more, and particularly preferably 0.2 or more.
  • the upper limit of G is not particularly limited, but may be 10 or less.
  • I [Al 2 O 3 ] ⁇ 0.03 + ⁇ RO ⁇ 0.014 (9) (Wherein [Al 2 O 3 ] is the Al 2 O 3 content in the glass (mol% on the basis of oxide), ⁇ RO is the total content of alkaline earth metal oxides in the glass (mol on the oxide basis) %)))
  • I is at least 0.45, the mirror constant tends to be large.
  • 0.5 or more are more preferable, 0.6 or more are more preferable, and 0.7 or more are especially preferable.
  • the upper limit of I is not particularly limited, but is preferably 2 or less in consideration of the amount of Al 2 O 3 or RO that the glass can contain.
  • the addition of Al 2 O 3 is not preferable because the Miller constant A of the glass is greatly reduced.
  • the alkaline earth metal oxide RO does not greatly change the rigidity of the entire glass, it tends to tetragonize boron, so it is better not to add much alkaline earth metal oxide RO.
  • Alkali metal oxide R 2 O not only reduces the rigidity of the entire glass but also tends to make boron tetra-coordinated, so it is better not to add too much. However, since it has the effect of increasing ⁇ LT and ⁇ HT described later, an appropriate amount is added.
  • the mirror constant A of the glass increases as the Young's modulus E of the glass increases.
  • the component to increase the Young's modulus E of the glass the same as in the case of containing substantially no glass composition of B 2 O 3.
  • the relationship between the Young's modulus E of the glass and the mirror constant A is lower than the relationship with the above-mentioned three-coordinate boron.
  • the addition of the alkaline earth metal oxide RO increases the Young's modulus E of the glass but tends to tetragonalize the boron and lowers the mirror constant A of the glass. Therefore, in the case of a glass composition containing B 2 O 3 , it is preferable not to increase the content of the alkaline earth metal oxide RO.
  • the addition of Al 2 O 3 increases the Young's modulus E of the glass, so the content is preferably higher.
  • B 2 O 3 is 0.01-40%, SiO 2 is 40-75%, Al 2 O 3 is 0-20%, P 2 in terms of mole percentage on an oxide basis. It is preferable to contain 0 to 10% of O 5 , and 8 to 40% in total of alkali metal oxides (R 2 O) and 0 to 40% in total of alkaline earth metal oxides (RO). In addition, it contains 5 to 25% of B 2 O 3 , 40 to 73% of SiO 2 , 0 to 20% of Al 2 O 3 , and 0 to 10% of P 2 O 5 in terms of mole percentage on an oxide basis.
  • SiO 2 is a main component of glass. If the content of SiO 2 is 40% or more, the weather resistance is good. The content of SiO 2 is more preferably equal to or greater than 43%, more preferably more than 46%. If the content of SiO 2 is 75% or less, devitrification is difficult. The content of SiO 2 is more preferably 70% or less, still more preferably 65% or less, still more preferably 63% or less, particularly preferably 55% or less, and most preferably 50% or less.
  • Al 2 O 3 is a component that improves the weather resistance.
  • the content of Al 2 O 3 is 0% or more. When Al 2 O 3 is contained, the weather resistance is improved.
  • the content of Al 2 O 3 is more preferably 0.1% or more, further preferably 0.3% or more, and particularly preferably 0.5% or more. If the content of Al 2 O 3 is 20% or less, the solubility is good. However, the content is preferably 15% or less, more preferably 10% or less, and particularly preferably 5% or less, since the Miller constant is rapidly reduced when Al 2 O 3 is contained.
  • Al 2 O 3 to SiO 2 is 0.01 or more, the bond cut by the alkali metal is repaired, the glass network structure becomes strong, and the hardness is improved. Do. Al 2 O 3 / SiO 2 is more preferably 0.02 or more, more preferably 0.03 or more. If the ratio of Al 2 O 3 to SiO 2 (Al 2 O 3 / SiO 2 ) is 0.5 or less, it is possible to prevent the reduction of the Miller constant. Al 2 O 3 / SiO 2 is more preferably 0.3 or less, more preferably 0.1 or less.
  • P 2 O 5 is preferably not substantially contained since it is easy to form phase separation and devitrification species, but it is contained in an amount of 10% or less in order to increase the thickness of the compressive stress layer when used as a chemically strengthened glass It is also good.
  • the content of P 2 O 5 may be 5% or less, or 1% or less.
  • B 2 O 3 has a large effect as a component to increase the mirror constant, and preferably contains 0.01% or more.
  • the content of B 2 O 3 is more preferably 1% or more, further preferably 5% or more, particularly preferably 10% or more, and most preferably 15% or more. If the content of B 2 O 3 is 40% or less, the decrease in Young's modulus can be prevented.
  • the content of B 2 O 3 is more preferably 35% or less, further preferably 30% or less, still more preferably 25% or less, particularly preferably 23% or less, and most preferably 20% or less.
  • B 2 O 3 and the ratio of the sum of R 2 O (B 2 O 3 / ⁇ R 2 O) is 0.8 or more, 3 since the coordination of boron there are many, would glass large mirror constant Cheap.
  • B 2 O 3 / ⁇ R 2 O is more preferably 1.0 or more, more preferably 1.2 or more, particularly preferably 1.3 or more. If B 2 O 3 / ⁇ R 2 O is 2.5 or less, the Tg is not too high and it is easy to handle.
  • the B 2 O 3 / ⁇ R 2 O is more preferably 2.0 or less, further preferably 1.8 or less.
  • the total amount of alkali metal oxides (R 2 O) is 8% or more, the viscosity of the glass at a high temperature is likely to decrease, and therefore, the glass becomes high in melting property.
  • the total amount of R 2 O is more preferably 10% or more, further preferably 12% or more, and particularly preferably 15% or less.
  • R 2 O is 40% or less in total, it is possible to prevent a rapid decrease in Young's modulus.
  • the total amount of R 2 O is preferably 35% or less, more preferably 30% or less.
  • Li 2 O is an alkali metal oxide component that does not cause a decrease in Young's modulus at room temperature while having the effect of lowering the viscosity of the glass at high temperatures. If the content of Li 2 O is 0.01% or more, the above effect appears. The content of Li 2 O is more preferably 2% or more, and still more preferably 4% or more. If the content of Li 2 O is 20% or less, the network in the glass structure can be maintained. In addition, because the price of Li 2 O is high, the price of the glass to be obtained can be avoided. The content of Li 2 O is more preferably 15% or less, further preferably 10% or less.
  • Na 2 O is a component having the effect of lowering the viscosity of the glass at high temperature. If the content of Na 2 O is 0.01% or more, the above-described effects are obtained. The content of Na 2 O is more preferably 1% or more, and still more preferably 5% or more. If the content of Na 2 O is 40% or less, the network in the glass structure can be maintained. The Na 2 O content is more preferably 35% or less, more preferably 30% or less.
  • K 2 O like Li 2 O and Na 2 O, is a component having the effect of lowering the viscosity of the glass at high temperature. If the content of K 2 O is 0.01% or more, the effect of lowering the viscosity becomes stronger. K 2 O is more preferably at least 2%, still more preferably at least 4%. If the content of K 2 O is 20% or less, the deliquescent of the glass can be reduced to some extent. The K 2 O content is more preferably 15% or less, more preferably 10% or less.
  • Rb 2 O like Li 2 O, Na 2 O, K 2 O, etc., is a component having the effect of lowering the viscosity of the glass at high temperatures. If the content of Rb 2 O is 0.01% or more, it is possible to increase the energy absorption effect at the time of breakage of the glass by the mixed alkali effect. The content of Rb 2 O is more preferably 2% or more, and still more preferably 3% or more. If the content of Rb 2 O is 10% or less, an excessive increase in the weight of glass can be prevented. The content of Rb 2 O is more preferably 5% or less, still more preferably 4% or less.
  • RO alkaline earth metal oxide
  • An alkaline earth metal oxide (RO) may be contained because it is a component that increases the Miller constant. In all cases of physically tempered glass and chemically tempered glass, if RO is 1% or more in total, it leads to an increase in Miller constant. RO is preferably 3% or more in total, more preferably 5% or more. Moreover, if RO is 40% or less in total, the influence of devitrification is small. The total amount of RO is more preferably 35% or less, still more preferably 30% or less, particularly preferably 25% or less, and most preferably 15% or less.
  • (CaO + SrO + BaO) is preferably 20% or less in total.
  • the total amount of (CaO + SrO + BaO) is preferably 15% or less, more preferably 10% or less, and particularly preferably 5% or less.
  • (CaO + SrO + BaO) reduces the devitrification of the glass, and a stable glass can be obtained, so (CaO + SrO + BaO) is preferably 0.1% or more in total, and 0.5% or more More preferably, 1% or more is more preferable.
  • MgO is a component that increases the mirror radius by increasing the Young's modulus of the glass.
  • the content of MgO is more preferably 3% or more, and further preferably 10% or more. If MgO is 35% or less, problems such as devitrification can be avoided. As for content of MgO, 35% or less is more preferable, and 33% or less is further more preferable.
  • the content of MgO is preferably 8% or less because the DOL can be easily increased. As for content of MgO, 5% or less is more preferable, and 4% or less is further more preferable.
  • CaO is a component to improve the meltability at high temperatures or to make it difficult to cause devitrification. Therefore, devitrification can be suppressed as long as the content of CaO is 0.1% or more in any of physically strengthened glass and chemically strengthened glass.
  • the content of CaO is more preferably 0.5% or more, and further preferably 1% or more. When the content of CaO is 15% or less, both effects of improvement of the meltability and increase of the Young's modulus of the glass can be obtained.
  • content of CaO 10% or less is more preferable, and 5% or less is more preferable.
  • the content of CaO is preferably 8% or less because DOL can be easily increased. 5% or less is more preferable, 3% or less is more preferable, and 2% or less is particularly preferable.
  • SrO is a component to improve the meltability at high temperatures or to make it difficult to cause devitrification. Therefore, in both of physically strengthened glass and chemically strengthened glass, if the content of SrO is 0.1% or more, it is effective in preventing devitrification.
  • the content of SrO is more preferably 0.2% or more, and still more preferably 0.3% or more. If the content of SrO is 5% or less, the weight increase of the glass is not a problem.
  • the content of SrO is more preferably 3% or less, and still more preferably 1% or less.
  • BaO is a component to improve the meltability at high temperatures or to make it difficult to cause devitrification. In the case of physically tempered glass, if the content of BaO is 1% or more, energy dissipation tends to occur easily due to the mixing effect of the alkaline earth.
  • the content of BaO is more preferably 2% or more, and still more preferably 2.5% or more.
  • the content of BaO is 20% or less, the viscosity is not too high, the meltability is improved, the specific gravity is reduced, and the weight can be reduced, which is preferable. 15% or less is more preferable, 13% or less is further preferable, and 10% or less is particularly preferable.
  • the effect of enhancing DOL can be obtained by reducing the content of BaO, so 5% or less is preferable. 3% or less is more preferable, 1% or less is more preferable, and substantially no content is most preferable.
  • H B 2 O 3 (three coordination) ⁇ 0.039 + E ⁇ 0.036 + ⁇ RO ⁇ ( ⁇ 0.030) ⁇ 2.3 (8) (Wherein B 2 O 3 (three coordinates) is the three-coordinate boron content in the glass (mol% based on oxide), E is the Young's modulus (GPa) of the glass, ⁇ RO is the alkaline earth in the glass) Total content of metal oxides (mol% based on oxides) If H is 0.4 or more, the mirror constant tends to be large.
  • H is more preferably 0.45 or more, further preferably 0.50 or more, and particularly preferably 0.55 or more.
  • the upper limit of H is not particularly limited, it is preferably 2 or less, more preferably 1.5 or less, since there is a limit to the fraction of B atoms capable of taking three coordinates out of the total B 2 O 3 content. preferable.
  • J [B 2 O 3] ⁇ 0.031-0.026 ⁇ [K 2 O] (10) (Wherein [B 2 O 3 ] is the B 2 O 3 content in the glass (mol% based on oxide), [K 2 O] is the K 2 O content in the glass (mol% based on the oxide )))) If J is at least 0.45, the mirror constant tends to be large. As for J, 0.50 or more is more preferable, and 0.55 or more is further more preferable.
  • the upper limit of J is not particularly limited, but when the content of B 2 O 3 and the content of the alkali metal oxide are too large, deliquescence occurs and the surface deterioration particularly in outdoor use becomes remarkable, so 1 or less Is preferable, and 0.8 or less is more preferable.
  • the addition of the alkaline earth metal oxide RO to the glass raises the Young's modulus E of the glass.
  • the effect of raising the Young's modulus of glass is higher in alkaline earth metal oxides than in alkaline metal oxides, and among alkaline earth metal oxides, CaO is higher than other alkaline earth metal oxides.
  • the content of CaO is preferably 0.5% or more, more preferably 1.0% or more, in terms of molar percentage based on the oxide.
  • the tempered glass of the present invention preferably has ⁇ M R 2 O 2 > 30 shown by the following formula (11).
  • ⁇ M R2O > ⁇ (Mixri) / ⁇ Ri (11)
  • Mi is atomic weight of alkali metal
  • Ri is content of alkali metal oxide contained in glass (mol% on the basis of oxide)
  • ⁇ M R 2 O 2 > is correlated with atomic weight of alkali metal in glass It is a value.
  • the tempered glass of the present invention preferably contains substantially no lanthanoid.
  • substantially free of lanthanoid means that the lanthanoid is not included unless it is mixed as an unavoidable impurity.
  • substantially no lanthanoid By containing substantially no lanthanoid, the weight of the glass can be reduced. In addition, when sunlight strikes the glass, no light emission or luminescence occurs.
  • the tempered glass of this invention does not contain F substantially.
  • not containing substantially F means not containing F except when it is mixed as an unavoidable impurity. By containing substantially no F, the composition hardly changes even if the glass is heat-treated.
  • the glass plate according to the embodiment of the present invention may contain SO 3 .
  • SO 3 is mainly derived from sodium sulfate (Na 2 SO 4 ) used as a fining agent.
  • the content of SO 3 is preferably 0.001% to 0.2% in terms of mass% based on the oxide. If the content of SO 3 is 0.001% or more, the fining effect at the time of glass melting is good, and bubbles are reduced.
  • the content of SO 3 is preferably 0.003% or more, more preferably 0.01% or more, and still more preferably 0.02% or more. If the content of SO 3 is 0.2% or less, the gas component of SO 2 hardly remains in the glass as bubbles.
  • the content of SO 3 is preferably 0.1% or less, more preferably 0.05% or less, and still more preferably 0.03% or less.
  • the glass plate according to the embodiment of the present invention may contain SnO 2 .
  • SnO 2 acts as a fining agent.
  • the content of SnO 2 is preferably 0 to 1% in terms of mass% based on the oxide. If SnO 2 is contained, the fining effect at the time of glass melting is good and bubbles are reduced.
  • the content of SnO 2 may be 0.1% or more, 0.2% or more, or 0.3% or more. In addition, if the content of SnO 2 is 1% or less, the raw material cost can be suppressed, and the volatilization in the production line is small.
  • the content of SnO 2 is more preferably 0.7% or less, further preferably 0.5% or less, and particularly preferably 0.4% or less.
  • the glass plate according to the embodiment of the present invention has, for example, Fe 2 O 3 , TiO 2 , CeO 2 , CoO, Se, MnO 2 , MnO, Cr 2 O 3 , V 2 O 5 , NiO, Er 2 O as coloring components. Although 3 may be contained, it is not necessary to contain a coloring component.
  • the glass plate of the embodiment of the present invention preferably contains substantially no MnO 2 , MnO, Cr 2 O 3 , V 2 O 5 , NiO or Er 2 O 3 .
  • the tempered glass of the present invention is air-cooled and tempered glass, it is preferable to satisfy the low-temperature thermal expansion coefficient ⁇ LT and the high-temperature thermal expansion coefficient ⁇ HT described below from the viewpoint of ease of air-cooling and tempering.
  • a cooling medium is sprayed on the surface to rapidly cool the surface to give a residual stress.
  • the ease of air-cooling reinforcement in the present specification means that residual stress is easily given when the air-cooling reinforcement treatment is performed in the above-described procedure.
  • the average thermal expansion coefficient at 50 to 350 ° C. is taken as the low temperature thermal expansion coefficient ⁇ LT .
  • the tempered glass of the present invention preferably has a low temperature thermal expansion coefficient ⁇ LT of 60 ⁇ 10 ⁇ 7 ⁇ K ⁇ 1 or more from the viewpoint of imparting residual stress.
  • the tempered glass of the present invention preferably has a low temperature thermal expansion coefficient ⁇ LT of 70 ⁇ 10 ⁇ 7 ⁇ K ⁇ 1 or more, and more preferably 80 ⁇ 10 ⁇ 7 ⁇ K 1 or more.
  • a load of 10 g is applied to a sample with a diameter of 5 mm and a length of 20 mm, and a thermal expansion curve obtained by measurement at a temperature rising rate of 5 ° C./min is between the glass transition point and the deformation point
  • the local maximum value of the thermal expansion coefficient at the point is taken as the high temperature thermal expansion coefficient ⁇ HT .
  • the low temperature thermal expansion coefficient ⁇ LT and the high temperature thermal expansion coefficient ⁇ HT generally have a correlation, and when the low temperature thermal expansion coefficient ⁇ LT is large, the high temperature thermal expansion coefficient ⁇ HT tends to be large.
  • the ratio ⁇ HT / ⁇ LT of the high temperature thermal expansion coefficient ⁇ HT to the low temperature thermal expansion coefficient ⁇ LT is preferably 2 or more, more preferably 3 or more, It is more preferably 4 or more, more preferably 5 or more, still more preferably 6 or more, particularly preferably 7 or more, and most preferably 8 or more.
  • the residual stress imparted to the glass by the air-cooling tempering treatment is determined by the product ⁇ LT ⁇ E of the low temperature thermal expansion coefficient ⁇ LT of the glass and the Young's modulus E. Therefore, a glass with a larger value of ⁇ LT ⁇ E is preferable as a wind-cooled tempered glass.
  • the product ⁇ LT ⁇ E of the low temperature thermal expansion coefficient ⁇ LT and the Young's modulus E is preferably 4 ⁇ 10 5 Pa ⁇ K ⁇ 1 or more, and 5 ⁇ 10 5 Pa ⁇ K ⁇ 1 The above is more preferable, 6 ⁇ 10 5 Pa ⁇ K ⁇ 1 or more is more preferable, and 7 ⁇ 10 5 Pa ⁇ K ⁇ 1 or more is particularly preferable.
  • Examples 1-14 are examples, and examples 15-27 are comparative examples.
  • a glass raw material was appropriately prepared, heated and melted, then homogenized by defoaming, stirring and the like, and molded by a float method to obtain a glass plate (plate thickness 2.2 mm).
  • the compositions (mol% based on oxide) of the glasses used in Examples and Comparative Examples are shown in Tables 1 to 3.
  • the content of three-coordinate boron (B (three-coordinate) (mol%)) is represented by the following formulas (12) and (13) Identified.
  • I [Al 2 O 3 ] ⁇ 0.03 + ⁇ RO ⁇ 0.014 (9)
  • [Al 2 O 3 ] is the Al 2 O 3 content in the glass (mol% on oxide basis)
  • ⁇ RO is the total content of alkaline earth metal oxides in the glass (mol% on oxide basis)
  • J represented by the following formula (10) was determined.
  • the glass plate obtained by the above procedure is processed into a rectangular solid, and the lengths of the long side and the short side of the glass plate are measured by a micrometer with an error of ⁇ 0.01 mm, and the weight of the glass plate is ⁇ 0.02 g It measured and calculated
  • ⁇ Young's modulus E, Poisson's ratio >> The Young's modulus E and Poisson's ratio ⁇ of the glass plate obtained by the above procedure were measured by an ultrasonic pulse method. For Examples 1 to 6 and Examples 15 to 22 not containing B 2 O 3 , G represented by the following formula (7) was determined.
  • B 2 O 3 (three coordination) ⁇ 0.039 + E ⁇ 0.036 + ⁇ RO ⁇ ( ⁇ 0.030) ⁇ 2.3 (8)
  • B 2 O 3 (three coordinates) is the three-coordinate boron content (mol% on the basis of oxide) in the glass
  • E is the Young's modulus (GPa) of the glass
  • RORO is the alkaline earth metal in the glass Total content of oxide (mol% based on oxide).
  • a deformation point (unit: ° C.), a low temperature thermal expansion coefficient ⁇ LT (unit: ⁇ 10 -7 / ° C.), and a high temperature thermal expansion coefficient ⁇ HT (unit: ⁇ 10 -7 / ° C.) were determined.
  • Tables 1 to 3 values shown in parentheses are calculated values.
  • the fictive temperature of the glass was adjusted by adjusting the cooling rate.
  • the fictive temperature of the glass was determined as follows. In the glass of each composition, three plate-like glasses are prepared and suspended at different cooling start temperatures T (° C.) in a platinum crucible and suspended so as not to contact wall surfaces using platinum wires and ceramic rods. It was placed in a held electric furnace. Here, the cooling start temperature and the holding time are kept at Tg + 50 ° C. for 5 minutes, Tg + 30 ° C. for 20 minutes, and Tg + 10 ° C. for 2 hours, and then the glass is taken out of the electric furnace out of the furnace at room temperature about 25 ° C. The cooling was performed at a cooling rate of 1000 ° C./min or more.
  • the refractive index n d at the d-line of these glasses is measured using a refractometer (KPR 2000; manufactured by Shimadzu Device Manufacturing Co., Ltd.), and from the refractive index n d and the cooling start temperature T, in equation (4)
  • the constants a and b were determined by linear regression.
  • processing The glass plate obtained by the above-mentioned procedure was processed into a size of 40 mm ⁇ 6 mm ⁇ 3 mm, and eight glass plates were produced in which front and back surfaces and end faces in the longitudinal direction (four in total) were mirror-polished.
  • HMV-2 Vickers hardness tester
  • a diamond indenter with a facing angle of 110 ° the indenter was scratched by pressing the indenter under different loads onto eight glass plates.
  • the pressing load was set to 0.05 kgf, 0.1 kgf, 0.3 kgf, 0.5 kgf, 0.75 kgf, 1.0 kgf, 2.0 kgf, and 3.0 kgf.
  • Heat treatment was performed to remove the influence of strain caused by scratching. The heat treatment was performed by maintaining the cooling start temperature described in Tables 1 to 3 for 1 hour, and cooling to room temperature at a cooling rate described in Tables 1 to 3.
  • the span of the jig for 4-point bending was such that the load side (upper): 10 mm and the support side (lower): 30 mm.
  • CS surface compressive stress
  • DOL compressive stress layer depth
  • the number of fractures of the glass after the strengthening treatment was measured by the following procedure. Using an auto punch (automatic punch M with a carbide tip; made by Niigata Seiki Co., Ltd.) against a glass sample (10 cm square) after tempering treatment, an angle of 120 ° is located 10 mm away from one corner of the sample It was crushed by impact with an indenter. The number of broken glass fragments was taken as the number of broken glass. When the glass was not crushed, the number of crushing was set to zero. For the glasses of Examples 1, 3 and 5, the number of fractures of the glass after tempering treatment was measured by the following procedure.
  • the tempered glass of each of Examples 1 to 14 in which the Miller constant A is 2.2 MPa ⁇ m 0.5 or more has a fracture number of less than 10 and a small number of fragments.
  • the tempered glass of Examples 15 to 27 having a Miller constant A of less than 2.2 MPa ⁇ m 0.5 had a fracture number of 38 or more and a large number of fractured pieces.
  • the tempered glass of the present invention is suitably used, for example, as a window glass of a vehicle, a window glass of a building, an outer wall, a solar cell cover glass, particularly as a window glass of a building.

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Abstract

La présente invention concerne un verre renforcé dont la constante de miroir A est d'au moins 2.2MPa·m0,5, la contrainte de compression de surface (CS) est d'au moins 10 MPa, et l'épaisseur de plaque t est comprise entre 1,2 et 50 mm.
PCT/JP2018/026961 2017-07-18 2018-07-18 Verre renforcé WO2019017404A1 (fr)

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