WO2025070525A1 - Verre et procédé de production de verre - Google Patents

Verre et procédé de production de verre Download PDF

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Publication number
WO2025070525A1
WO2025070525A1 PCT/JP2024/034246 JP2024034246W WO2025070525A1 WO 2025070525 A1 WO2025070525 A1 WO 2025070525A1 JP 2024034246 W JP2024034246 W JP 2024034246W WO 2025070525 A1 WO2025070525 A1 WO 2025070525A1
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WIPO (PCT)
Prior art keywords
glass
less
content
mass
raw material
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PCT/JP2024/034246
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English (en)
Japanese (ja)
Inventor
晃治 清水
直樹 菅野
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AGC Inc
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Asahi Glass Co Ltd
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Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Publication of WO2025070525A1 publication Critical patent/WO2025070525A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B3/00—Charging the melting furnaces
    • C03B3/02—Charging the melting furnaces combined with preheating, premelting or pretreating the glass-making ingredients, pellets or cullet
    • 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
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements

Definitions

  • the present invention relates to glass and a method for manufacturing glass.
  • Patent Document 1 describes an optical glass that contains La 2 O 3 and B 2 O 3 and contains sulfur S in an amount of 1 ppm or more and less than 300 ppm. Patent Document 1 describes that degassing can be promoted by containing sulfur S.
  • the present invention aims to provide glass and a method for manufacturing glass that can suppress the inclusion of air bubbles while suppressing a decrease in transmittance.
  • the glass according to the present disclosure contains La 2 O 3 and B 2 O 3 and has, by mass ratio, an S content of 100 ppm or more, an internal transmittance for light with a wavelength of 440 nm of 70% or more, and ⁇ OH of 0.1 mm -1 or more and 1.0 mm -1 or less.
  • the method for producing glass according to the present disclosure includes mixing a raw material containing La, a raw material containing B, a raw material containing SO3 , and a raw material containing H2O , heating and melting the mixed raw materials, and cooling the melted raw materials to obtain glass, wherein the raw material containing H2O is mixed so that the ratio of the amount of H2O added to the total mass of the glass based on oxides is 0.5 wt% or more and 20 wt% or less.
  • the present invention makes it possible to suppress the inclusion of air bubbles while also suppressing the decrease in transmittance.
  • FIG. 1 is a schematic diagram of the glass according to this embodiment.
  • FIG. 2 is a cross-sectional view of the glass according to this embodiment when made into a glass plate.
  • FIG. 1 is a schematic diagram of the glass according to the present embodiment.
  • the glass 10 according to the present embodiment is a plate-shaped glass plate, but the shape of the glass 10 is not limited to a plate shape and may be any shape.
  • the glass 10 is used as a light guide plate. More specifically, the glass 10 is used as a light guide plate for a head-mounted display.
  • a head-mounted display is a display device (wearable device) that is worn on a person's head.
  • the use of the glass 10 is arbitrary, and is not limited to being used as a light guide plate, and is not limited to being used in a head-mounted display.
  • composition The composition of the glass 10 will be described below.
  • the glass 10 contains La 2 O 3 and B 2 O 3.
  • La 2 O 3 and B 2 O 3 By containing La 2 O 3 and B 2 O 3 , a high refractive index and high transmittance can be appropriately achieved.
  • the presence or absence of La 2 O 3 and B 2 O 3 can be measured by ICP mass spectrometry.
  • Agilent 8800 manufactured by Agilent Technologies can be used as a measuring device.
  • (S) Glass 10 has a S content relative to the total mass of glass 10 (S content/total mass of glass) in terms of mass ratio of 60 ppm or more, preferably 80 ppm or more, 100 ppm or more, preferably 120 ppm or more, more preferably 140 ppm or more, even more preferably 160 ppm or more, preferably 500 ppm or less, more preferably 400 ppm or less, even more preferably 350 ppm or less, preferably 300 ppm or less, more preferably 250 ppm or less, and even more preferably 200 ppm or less.
  • the content of S relative to the total mass of glass 10 is preferably 100 ppm to 500 ppm, more preferably 100 ppm to 300 ppm, more preferably 120 ppm to 250 ppm, more preferably 140 ppm to 200 ppm, and even more preferably 160 ppm to 200 ppm.
  • the S content can be measured by ion chromatography.
  • the total mass of glass 10 refers to the total mass of glass 10 based on oxides.
  • the oxide basis refers to assuming that all raw materials containing metal atoms other than S, which are components of glass 10, are decomposed and converted to metal oxides during melting, and the sum of the masses of these metal oxides is the total mass of glass 10 (100 wt %).
  • the ⁇ OH of the glass 10 is 0.1 mm -1 or more, preferably 0.2 mm -1 or more, more preferably 0.3 mm -1 or more, and even more preferably 0.4 mm -1 or more.
  • the ⁇ OH of the glass 10 is 1.0 mm -1 or less, preferably 0.8 mm -1 or less, more preferably 0.6 mm -1 or less, and even more preferably 0.5 mm -1 or less.
  • the ⁇ OH of the glass 10 is 0.1 mm -1 or more and 1.0 mm -1 or less, preferably 0.2 mm -1 or more and 0.8 mm -1 or less, more preferably 0.3 mm -1 or more and 0.6 mm -1 or less, and even more preferably 0.4 mm -1 or more and 0.5 mm -1 or less.
  • ⁇ OH is an index indicating the amount of water in the glass, and a larger ⁇ OH value means a larger amount of water in the glass.
  • the degree of water content based on the amount of ⁇ OH and the amount of H 2 O contained in the raw materials. Furthermore, by setting the upper limit of ⁇ OH in the glass 10 within this range, it is possible to suppress the generation of bubbles before molding. It is generally known that water contained in glass dissolved in a Pt container generates O2 bubbles due to H permeation through the Pt container. In order to suppress O2 bubbles, it is preferable to suppress the amount of water before the molding process.
  • the ⁇ OH of the glass 10 is calculated by the following formula (1).
  • ⁇ OH indicates the value of ⁇ OH (mm ⁇ 1 ) of the glass 10
  • D indicates the thickness (mm) of the glass 10
  • ⁇ 1 indicates the transmittance (%) of the glass 10 at a reference wave number of 4000 (cm ⁇ 1 )
  • ⁇ 2 indicates the minimum transmittance (%) of the glass 10 at a reference wave number of 3450 (cm ⁇ 1 ).
  • FT-IR Fourier transform infrared spectrophotometer
  • the glass 10 preferably contains SiO 2.
  • the glass 10 preferably has a SiO 2 content of 2.5% or more, more preferably 3.0% or more, and even more preferably 3.5% or more, expressed in mass% based on oxide.
  • the glass 10 preferably has a SiO 2 content of 7.0% or less, more preferably 6.0% or less, and even more preferably 5.0% or less, expressed in mass% based on oxide.
  • the glass 10 preferably has a SiO 2 content of 2.5% or more and 7.0% or less, more preferably 3.0% or more and 6.0% or less, and even more preferably 3.5% or more and 5.0% or less, expressed in mass% based on oxide.
  • the upper limit of the SiO 2 content is in this range, good melting properties can be realized.
  • the lower limit of the SiO 2 content is in this range, good devitrification resistance can be realized.
  • the glass 10 contains B 2 O 3.
  • the content of B 2 O 3 is preferably 6% or more, more preferably 7% or more, even more preferably 7.5% or more, and most preferably 8% or more, expressed in mass% based on oxide.
  • the content of B 2 O 3 is preferably 12% or less, more preferably 10% or less, even more preferably 9.5% or less, and most preferably 9% or less, expressed in mass% based on oxide.
  • the content of B 2 O 3 is preferably 6% or more and 12% or less, more preferably 7% or more and 10% or less, even more preferably 7.5% or more and 9.5% or less, and most preferably 8% or more and 9% or less, expressed in mass% based on oxide.
  • the upper limit of the content of B 2 O 3 is in this range, good melting property can be realized.
  • the lower limit of the content of B 2 O 3 is in the above range, good devitrification resistance can be realized.
  • the glass 10 may contain P 2 O 5 or may not contain P 2 O 5.
  • the glass 10 may have a P 2 O 5 content of 0% or more, 0.3% or more, or 0.5% or more, expressed in mass% based on oxide.
  • the glass 10 has a P 2 O 5 content of 3% or less, more preferably 2% or less, and even more preferably 1% or less, expressed in mass% based on oxide.
  • the glass 10 has a P 2 O 5 content of 0% or more and 3% or less, 0.3% or more and 2% or less, or 0.5% or more and 1% or less, expressed in mass% based on oxide.
  • the P 2 O 5 content is within this range, devitrification resistance can be appropriately achieved. In order to appropriately maintain devitrification resistance, it is more preferable not to contain P 2 O 5 .
  • the glass 10 may contain CaO or may not contain CaO.
  • the glass 10 has a CaO content of 0% or more, more preferably 1% or more, and even more preferably 2% or more, expressed in mass% on an oxide basis.
  • the glass 10 has a CaO content of 5% or less, more preferably 4% or less, and even more preferably 3% or less, expressed in mass% on an oxide basis.
  • the glass 10 has a CaO content of 0% or more and 5% or less, more preferably 1% or more and 4% or less, and even more preferably 2% or more and 3% or less, expressed in mass% on an oxide basis.
  • the glass 10 may contain SrO or may not contain SrO.
  • the glass 10 has an SrO content of 0% or more, more preferably 1% or more, and even more preferably 2% or more, expressed in mass% on an oxide basis.
  • the glass 10 has an SrO content of 5% or less, more preferably 4% or less, and even more preferably 3% or less, expressed in mass% on an oxide basis.
  • the glass 10 has an SrO content of 0% or more and 5% or less, more preferably 1% or more and 4% or less, and even more preferably 2% or more and 3% or less, expressed in mass% on an oxide basis. When the SrO content is within this range, devitrification resistance, high refractive index, and high transmittance can be appropriately realized.
  • the glass 10 may contain BaO or may not contain BaO.
  • the glass 10 has a BaO content of 0% or more, more preferably 1% or more, and even more preferably 2% or more, expressed in mass% on an oxide basis.
  • the glass 10 has a BaO content of 5% or less, more preferably 4% or less, and even more preferably 3% or less, expressed in mass% on an oxide basis.
  • the glass 10 has a BaO content of 0% or more and 5% or less, more preferably 1% or more and 4% or less, and even more preferably 2% or more and 3% or less, expressed in mass% on an oxide basis.
  • the glass 10 may contain Li 2 O to improve melting properties, or may not contain Li 2 O.
  • the glass 10 may have a Li 2 O content of 0% or more, 0.1% or more, or 0.3% or more, expressed in mass% based on oxide.
  • the glass 10 has a Li 2 O content of 3% or less, more preferably 2% or less, and even more preferably 1% or less, expressed in mass% based on oxide.
  • the glass 10 has a Li 2 O content of 0% or more and 3% or less, 0.1% or more and 2% or less, or 0.3% or more and 1% or less, expressed in mass% based on oxide.
  • the Li 2 O content is within this range, devitrification resistance, high refractive index, and high transmittance can be appropriately realized. In order to appropriately maintain devitrification resistance, it is more preferable not to contain Li 2 O.
  • the glass 10 may contain Na 2 O or may not contain Na 2 O.
  • the glass 10 may have a Na 2 O content of 0% or more, 0.1% or more, or 0.3% to 1% in mass% on an oxide basis.
  • the glass 10 has a Na 2 O content of 3% or less, more preferably 2% or less, and even more preferably 1% or less, in mass% on an oxide basis.
  • the glass 10 has a Na 2 O content of 0% or more and 3% or less, 0.1% or more and 2% or less, or 0.3% or more and 1% or less, in mass% on an oxide basis.
  • the Na 2 O content is within this range, devitrification resistance, high refractive index, and high transmittance can be appropriately realized. In order to appropriately maintain devitrification resistance, it is more preferable not to contain Na 2 O.
  • the glass 10 may contain K 2 O or may not contain K 2 O.
  • the glass 10 may have a K 2 O content of 0% or more, 0.1% or more, or 0.3% or more, expressed in mass% based on oxide.
  • the glass 10 has a K 2 O content of 3% or less, more preferably 2% or less, and even more preferably 1% or less, expressed in mass% based on oxide.
  • the glass 10 has a K 2 O content of 0% or more and 3% or less, 0.1% or more and 2% or less, or 0.3% or more and 1% or less, expressed in mass% based on oxide.
  • the K 2 O content is within this range, devitrification resistance, high refractive index, and high transmittance can be appropriately realized. In order to appropriately maintain devitrification resistance, it is preferable not to contain K 2 O.
  • the glass 10 may contain ZnO or may not contain ZnO.
  • the glass 10 has a ZnO content of 0% or more, more preferably 1% or more, and even more preferably 2% or more, expressed in mass% on an oxide basis.
  • the glass 10 has a ZnO content of 5% or less, more preferably 4% or less, and even more preferably 3% or less, expressed in mass% on an oxide basis.
  • the glass 10 has a ZnO content of 0% or more and 5% or less, more preferably 1% or more and 4% or less, and even more preferably 2% or more and 3% or less, expressed in mass% on an oxide basis.
  • the glass 10 preferably contains TiO 2.
  • the glass 10 preferably has a TiO 2 content of 14% or more, more preferably 15% or more, and even more preferably 16% or more, expressed in mass% based on oxide.
  • the glass 10 preferably has a TiO 2 content of 20% or less, more preferably 18% or less, and even more preferably 17% or less, expressed in mass% based on oxide.
  • the glass 10 preferably has a TiO 2 content of 14% or more and 20% or less, more preferably 15% or more and 18% or less, and even more preferably 16% or more and 17% or less, expressed in mass% based on oxide.
  • the glass 10 preferably contains Nb 2 O 5.
  • the content of Nb 2 O 5 in the glass 10 is preferably 8% or more, more preferably 8.5% or more, and even more preferably 9% or more, expressed in mass% on an oxide basis.
  • the content of Nb 2 O 5 in the glass 10 is preferably 13% or less, more preferably 12% or less, preferably 11% or less, and even more preferably 10% or less, expressed in mass% on an oxide basis.
  • the content of Nb 2 O 5 in the glass 10 is preferably 8% or more and 13% or less, more preferably 8.5% or more and 12% or less, more preferably 9% or more and 12% or less, more preferably 9% or more and 11% or less, and even more preferably 9% or more and 10% or less, expressed in mass% on an oxide basis.
  • the upper limit of the content of Nb 2 O 5 is within this range, devitrification resistance can be appropriately achieved.
  • the lower limit of the Nb 2 O 5 content falls within this range, a high refractive index can be appropriately achieved.
  • the glass 10 may contain Ta 2 O 5 or may not contain Ta 2 O 5.
  • the glass 10 has a Ta 2 O 5 content of 0% or more, more preferably 0.3% or more, and even more preferably 0.5% or more, expressed in mass% based on oxide.
  • the glass 10 has a Ta 2 O 5 content of 5% or less, more preferably 3% or less, and even more preferably 1% or less, expressed in mass% based on oxide.
  • the glass 10 has a Ta 2 O 5 content of 0% or more and 5% or less, more preferably 0.3% or more and 3% or less, and even more preferably 0.5% or more and 1% or less, expressed in mass% based on oxide.
  • the glass 10 preferably contains WO3 .
  • the content of WO3 is preferably 0% or more, more preferably 0.1% or more, more preferably 0.2% or more, and even more preferably 0.3% or more, expressed in mass% based on oxide.
  • the content of WO3 is preferably 5% or less, more preferably 3% or less, more preferably 2% or less, even more preferably 1% or less, and even more preferably 0.5% or less, expressed in mass% based on oxide.
  • the content of WO3 is preferably 0% or more and 5% or less, more preferably 0.1% or more and 3% or less, more preferably 0.2% or more and 2% or less, and even more preferably 0.3% or more and 1% or less, expressed in mass% based on oxide.
  • the content of WO3 is within this range, meltability, resistance to devitrification, and a high refractive index can be appropriately realized.
  • La2O3 Glass 10 contains La 2 O 3.
  • the content of La 2 O 3 is preferably 38% or more, more preferably 40% or more, and even more preferably 41% or more, expressed in mass% based on oxide.
  • the content of La 2 O 3 is preferably 47% or less, more preferably 45% or less, and even more preferably 44% or less, expressed in mass% based on oxide.
  • the content of La 2 O 3 is preferably 38% or more and 47% or less, more preferably 40% or more and 45% or less, and even more preferably 41% or more and 44% or less, expressed in mass% based on oxide.
  • specific gravity and devitrification resistance can be appropriately realized.
  • the lower limit of the content of La 2 O 3 is within this range, both a high refractive index and a high transmittance can be appropriately realized.
  • the glass 10 preferably contains Gd 2 O 3.
  • the content of Gd 2 O 3 in the glass 10 is preferably 6% or more, more preferably 7% or more, more preferably 8% or more, and even more preferably 9% or more, expressed in mass% based on the oxide.
  • the content of Gd 2 O 3 in the glass 10 is preferably 12% or less, more preferably 11% or less, more preferably 10% or less, and even more preferably 9.5% or less, expressed in mass% based on the oxide.
  • the content of Gd 2 O 3 in the glass 10 is preferably 6% or more and 12% or less, more preferably 7% or more and 11% or less, more preferably 8% or more and 11% or less, more preferably 8% or more and 10% or less, and even more preferably 9% or more and 9.5% or less, expressed in mass% based on the oxide.
  • the upper limit of the content of Gd 2 O 3 is within this range, the specific gravity and devitrification resistance can be appropriately realized.
  • the lower limit of the Gd 2 O 3 content falls within this range, a high refractive index and high transmittance can be appropriately achieved.
  • the glass 10 preferably contains Y 2 O 3.
  • the glass 10 preferably has a Y 2 O 3 content of 0% or more, more preferably 1% or more, and even more preferably 2% or more, expressed in mass% based on oxide.
  • the glass 10 preferably has a Y 2 O 3 content of 5% or less, more preferably 4.0% or less, and even more preferably 3.5% or less, expressed in mass% based on oxide.
  • the glass 10 preferably has a Y 2 O 3 content of 0% or more and 5% or less, more preferably 1% or more and 4.0% or less, and even more preferably 2% or more and 3.5% or less, expressed in mass% based on oxide.
  • the specific gravity and devitrification resistance can be appropriately realized.
  • the lower limit of the Y 2 O 3 content within this range, a high refractive index and high transmittance can be appropriately realized.
  • the total content of SiO 2 and B 2 O 3 is preferably 9% or more, more preferably 10% or more, and even more preferably 11% or more, in terms of mass% based on oxides.
  • the total content of SiO 2 and B 2 O 3 is preferably 14% or less, and more preferably 13% or less, in terms of mass% based on oxides.
  • the total content of SiO 2 and B 2 O 3 is preferably 9% or more, more preferably 10% or more and 14% or less, and even more preferably 11% or more and 13% or less, in terms of mass% based on oxides.
  • the ratio ( TiO2 / B2O3 ) of the content of TiO2 to the content of B2O3 contained in the glass 10 is preferably 3.00 or less, more preferably 2.50 or less, even more preferably 2.20 or less, even more preferably 2.00 or less, even more preferably 1.95 or less, even more preferably 1.90 or less, and even more preferably 1.70 or less.
  • the ratio ( TiO2 / B2O3 ) is preferably 0.50 or more, more preferably 0.80 or more, even more preferably 1.00 or more, even more preferably 1.20 or more, even more preferably 1.30 or more, and even more preferably 1.50 or more.
  • the ratio ( TiO2 / B2O3 ), in terms of mass ratio, is preferably 0.50 or more and 3.00 or less, more preferably 0.80 or more and 2.50 or less, even more preferably 1.00 or more and 2.20 or less, even more preferably 1.20 or more and 2.00 or less, even more preferably 1.30 or more and 1.95 or less, even more preferably 1.50 or more and 1.90 or less, and even more preferably 1.50 or more and 1.70 or less.
  • the total content of Pt and Fe in the glass 10, in terms of mass ratio, is preferably 10 ppm or less, more preferably 9 ppm or less, even more preferably 8 ppm or less, and even more preferably 7 ppm or less, relative to the entirety of the glass 10.
  • the total content of Pt and Fe in the glass 10, in terms of mass ratio is preferably 0 ppm or more and 10 ppm or less, more preferably 0.1 ppm or more and 9 ppm or less, even more preferably 0.3 ppm or more and 8 ppm or less, and even more preferably 0.5 ppm or more and 7 ppm or less, relative to the entirety of the glass 10.
  • the Pt and Fe contents can be measured by ICP mass spectrometry, using, for example, an Agilent 8800 manufactured by Agilent Technologies.
  • the glass 10 preferably does not contain Sb. By not containing Sb, high transmittance can be appropriately achieved. Note that not containing Sb means that the glass 10 is allowed to contain Sb as an unavoidable impurity.
  • the presence or absence of Sb can be measured by ICP mass spectrometry.
  • a measuring device for example, Agilent 8800 manufactured by Agilent Technologies can be used.
  • Glass characteristics The properties of the glass 10 are described below.
  • the internal transmittance ⁇ 440 of the glass 10 is 70% or more, preferably 85% or more, more preferably 88% or more, and more preferably 92% or more.
  • the transmittance ⁇ 440 of the glass 10 may be 99.9% or less, may be 99.8% or less, may be 99% or less, or may be 98% or less.
  • the transmittance ⁇ 440 of the glass 10 is 70% or more, preferably 85% or more and 99% or less, more preferably 88% or more and 98% or less, and more preferably 92% or more and 98% or less.
  • the transmittance ⁇ 440 refers to the internal transmittance for light with a wavelength of 440 nm. More specifically, the internal transmittance ⁇ 440 is the internal transmittance for light with a wavelength of 440 nm when converted to a thickness of 10 mm.
  • the internal transmittance can be calculated from the measured values of the external transmittances of two different plate thicknesses and the following formula (2).
  • the external transmittance means the transmittance including the surface reflection loss.
  • ⁇ is the internal transmittance of the glass when converted to a thickness of 10 mm
  • T1 and T2 are the external transmittances
  • ⁇ d is the difference in thickness of the sample.
  • the external transmittance can be measured using a spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation) for a sample that has been mirror-polished on both sides to a plate thickness of 10 mm.
  • the refractive index n d of the glass 10 is preferably 1.95 or more, more preferably 1.98 or more, more preferably 2.03 or more, and even more preferably 2.04 or more.
  • the refractive index n d of the glass 10 is preferably 2.06 or less, and more preferably 2.05 or less.
  • the refractive index n d of the glass 10 is more preferably 1.98 or more and 2.06 or less, and even more preferably 2.03 or more and 2.05 or less.
  • the refractive index n d refers to the refractive index at the helium d line (wavelength 587.6 nm) and can be measured by the V - block method.
  • the Abbe number v d of the glass 10 is preferably 24 or more, more preferably 25 or more, and even more preferably 26 or more.
  • the Abbe number v d of the glass 10 is preferably 30 or less, more preferably 28 or less, and even more preferably 27 or less.
  • the Abbe number v d of the glass 10 is preferably 24 or more and 30 or less, more preferably 25 or more and 28 or less, and even more preferably 26 or more and 27 or less.
  • the Abbe number v d represents the ratio of the refractive index (n d -1) to the dispersion (n F -n C ).
  • the refractive index n F refers to the refractive index at the F line of hydrogen (wavelength 486.1 nm)
  • the refractive index n C refers to the refractive index at the C line of hydrogen (wavelength 656.3 nm).
  • the glass transition temperature Tg of the glass 10 is preferably 680° C. or higher, more preferably 700° C. or higher, and even more preferably 710° C. or higher.
  • the glass transition temperature Tg of the glass 10 is preferably 760° C. or lower, more preferably 750° C. or lower, even more preferably 740° C. or lower, and even more preferably 730° C. or lower.
  • the glass transition temperature Tg of the glass 10 is preferably 680° C. or higher and 760° C. or lower, more preferably 700° C. or higher and 750° C. or lower, and even more preferably 710° C. or higher and 740° C. or lower.
  • the glass transition temperature can be measured according to the method specified in JIS R3103-3:2001 "Viscosity and Viscosity Fixed Points of Glass-Part 3: Transition Temperature Measurement Method by Thermal Expansion Method".
  • the devitrification temperature of glass 10 is preferably less than 1290° C., more preferably equal to or lower than 1270° C., and even more preferably equal to or lower than 1250° C. When the devitrification temperature is within this range, the temperature at which the raw materials are melted during the production of glass 10 can be relatively low, and Pt contained in the melting equipment can be prevented from being dissolved and mixed into the glass, thereby appropriately suppressing a decrease in transmittance.
  • the devitrification temperature can be measured by the following method. A sample glass was crushed to obtain glass particles that passed through a 4 mm sieve and remained on a 2 mm sieve. The glass particles were immersed in ethanol, ultrasonically cleaned, and then dried in a dryer.
  • the linear thermal expansion coefficient ⁇ of the glass 10 is preferably 94 ⁇ 10 ⁇ 7 /° C. or less, more preferably 93 ⁇ 10 ⁇ 7 /° C. or less, even more preferably 92 ⁇ 10 ⁇ 7 /° C. or less, and even more preferably 91 ⁇ 10 ⁇ 7 /° C. or less.
  • the linear thermal expansion coefficient ⁇ of the glass 10 is more preferably 86 ⁇ 10 ⁇ 7 /° C. or more, and even more preferably 87 ⁇ 10 ⁇ 7 /° C. or more.
  • the linear thermal expansion coefficient ⁇ of the glass 10 is more preferably 86 ⁇ 10 ⁇ 7 /° C. or more and 93 ⁇ 10 ⁇ 7 /° C.
  • the linear thermal expansion coefficient ⁇ is the average thermal expansion coefficient in the range of 100°C to 300°C, and is a value measured in accordance with DIN-51045-1 as a standard for thermal expansion measurement.
  • thermal expansion meter DIL 402 Expedis Supreme manufactured by NETZSCH is used as a measuring device to measure in the range of 30°C to 400°C, and the average thermal expansion coefficient in the range of 100°C to 300°C may be used as the linear thermal expansion coefficient.
  • the Young's modulus E of the glass 10 is preferably 125 GPa or more, more preferably 127 GPa or more, and even more preferably 130 GPa or more.
  • the Young's modulus E of the glass 10 is preferably 145 GPa or less, more preferably 142 GPa or less, and even more preferably 140 GPa or less.
  • the Young's modulus E of the glass 10 is preferably 125 GPa or more and 145 GPa or less, more preferably 127 GPa or more and 142 GPa or less, and even more preferably 130 GPa or more and 140 GPa or less.
  • Such a high Young's modulus can appropriately suppress breakage of the glass 10.
  • the Young's modulus can be measured based on the propagation of ultrasonic waves using 38DL PLUS manufactured by OLYMPUS Corporation.
  • the specific gravity d of the glass 10 is preferably 5.5 g/ cm3 or less, more preferably 5.4 g/ cm3 or less, preferably 5.3 g/ cm3 or less, and even more preferably 5.2 g/ cm3 or less. Such a low specific gravity makes it easy to handle the glass 10.
  • the specific gravity d can be measured by the Archimedes method.
  • the glass 10 according to the present embodiment is preferably an optical glass, and is preferably a glass plate having a thickness of 0.01 mm or more and 2.0 mm or less. If the thickness is 0.01 mm or more, breakage during handling or processing of the glass 10 can be suppressed. In addition, deflection due to the weight of the glass 10 can be suppressed. This thickness is more preferably 0.1 mm or more, even more preferably 0.2 mm or more, and even more preferably 0.3 mm or more. On the other hand, if the thickness is 2.0 mm or less, the optical element using the glass 10 can be made lightweight. This thickness is more preferably 1.5 mm or less, even more preferably 1.0 mm or less, and even more preferably 0.8 mm or less.
  • the area of the main surface is preferably 8 cm 2 or more. If this area is 8 cm 2 or more, a large number of optical elements can be arranged, and productivity is improved. This area is more preferably 30 cm 2 or more, even more preferably 170 cm 2 or more, even more preferably 300 cm 2 or more, and particularly preferably 1000 cm 2 or more. On the other hand, if the area is 6500 cm 2 or less, the glass plate becomes easy to handle, and breakage during handling or processing of the glass plate can be suppressed. This area is more preferably 4500 cm 2 or less, even more preferably 4000 cm 2 or less, even more preferably 3000 cm 2 or less, and particularly preferably 2000 cm 2 or less.
  • the LTV (Local Thickness Variation) in 25 cm2 of the main surface is preferably 2 ⁇ m or less.
  • a nanostructure of a desired shape can be formed on the main surface using imprint technology or the like, and the desired light guide characteristics can be obtained.
  • ghost phenomena and distortions due to differences in optical path length can be prevented in the light guide.
  • This LTV is more preferably 1.5 ⁇ m or less, even more preferably 1.0 ⁇ m or less, and particularly preferably 0.5 ⁇ m or less.
  • the warp is preferably 50 ⁇ m or less. If the warp of this glass 10 is 50 ⁇ m or less, a nanostructure of the desired shape can be formed on the main surface using imprinting technology or the like, and the desired light guiding characteristics can be obtained. When multiple light guiding bodies are to be obtained, they can be obtained with stable quality.
  • the warp of this glass 10 is more preferably 40 ⁇ m or less, even more preferably 30 ⁇ m or less, and particularly preferably 20 ⁇ m or less.
  • the warp is preferably 30 ⁇ m or less. If the warp of this glass 10 is 30 ⁇ m or less, a nanostructure of the desired shape can be formed on the main surface using imprint technology or the like, and the desired light guiding characteristics can be obtained. When multiple light guiding bodies are to be obtained, they can be obtained with stable quality.
  • the warp of this glass 10 is more preferably 20 ⁇ m or less, even more preferably 15 ⁇ m or less, and particularly preferably 10 ⁇ m or less.
  • the warp is preferably 100 ⁇ m or less. If the warp of this glass 10 is 100 ⁇ m or less, a nanostructure of the desired shape can be formed on the main surface using imprinting technology or the like, and the desired light guiding characteristics can be obtained. When multiple light guiding bodies are to be obtained, they can be obtained with stable quality.
  • the warp of this glass 10 is more preferably 70 ⁇ m or less, even more preferably 50 ⁇ m or less, even more preferably 35 ⁇ m or less, and particularly preferably 20 ⁇ m or less.
  • Figure 2 is a cross-sectional view of the glass according to this embodiment when it is used as a glass plate.
  • "Warping" refers to the difference C between the maximum value B and minimum value A of the perpendicular distance between the reference line G1D of the glass plate G1 and the center line G1C of the glass plate G1 in any cross section that passes through the center of the main surface G1F of the glass plate G1 and is perpendicular to the main surface G1F of the glass plate G1 when the glass 10 according to this embodiment is used as the glass plate G1.
  • the intersection line between any of the orthogonal cross sections and the main surface G1F of the glass sheet G1 is the base line G1A.
  • the intersection line between any of the orthogonal cross sections and the other main surface G1G of the glass sheet G1 is the top line G1B.
  • the center line G1C is a line connecting the center of the glass sheet G1 in the thickness direction. The center line G1C is calculated by finding the midpoint between the base line G1A and the top line G1B in the direction of laser irradiation described below.
  • the reference line G1D is found as follows. First, the base line G1A is calculated based on a measurement method that cancels the effects of the weight. A straight line is found from the base line G1A using the least squares method. The straight line found is the reference line G1D. A known method is used as the measurement method that cancels the effects of the weight.
  • the main surface G1F of the glass plate G1 is supported at three points, a laser is irradiated onto the glass plate G1 using a laser displacement meter, and the height of the main surface G1F and the other main surface G1G of the glass plate G1 from an arbitrary reference plane is measured.
  • the glass plate G1 is inverted, and three points on the other main surface G1G opposite to the three points on which the one main surface G1F is supported are supported, and the heights of the main surface G1F and the other main surface G1G of the glass plate G1 from an arbitrary reference plane are measured.
  • the influence of the weight is cancelled.
  • the height of the main surface G1F is measured as described above. After inverting the glass sheet G1, the height of the other main surface G1G is measured at a position corresponding to the measurement point of the main surface G1F. Similarly, before inversion, the height of the other main surface G1G is measured. After inverting the glass sheet G1, the height of the main surface G1F is measured at a position corresponding to the measurement point of the other main surface G1G.
  • the warpage is measured, for example, by a laser displacement meter.
  • the surface roughness Ra of the main surface is preferably 2 nm or less.
  • an Ra in this range a nanostructure of a desired shape can be formed on the main surface using imprinting technology or the like, and the desired light guiding characteristics can be obtained.
  • diffuse reflection at the interface can be suppressed, preventing ghosting and distortion.
  • This Ra is more preferably 1.7 nm or less, even more preferably 1.4 nm or less, even more preferably 1.2 nm or less, and particularly preferably 1 nm or less.
  • the surface roughness Ra is the arithmetic mean roughness defined in JIS B0601 (2001). In this specification, it is a value measured over an area of 10 ⁇ m x 10 ⁇ m using an atomic force microscope (AFM).
  • the method for producing the glass 10 according to the present embodiment is not particularly limited, but a preferred method for producing the glass 10 will be described below.
  • the process includes a mixing step for mixing the raw materials for glass 10, a melting step for melting the raw materials, and a cooling step for cooling the molten raw materials to obtain glass 10.
  • a mixing step for mixing the raw materials for glass 10 a melting step for melting the raw materials
  • existing methods for manufacturing flat glass can be used.
  • known methods such as the float method, fusion method, and roll-out method can be used.
  • the raw materials of glass 10 are selected according to the composition of glass 10 to be obtained, and are mixed in a compounding ratio according to the composition of glass 10 to be obtained.
  • at least a raw material containing La, a raw material containing B, a raw material containing SO3 , and a raw material containing H2O are prepared as the raw materials of glass 10, and these raw materials are mixed.
  • the raw material containing La, the raw material containing B, the raw material containing SO 3 , and the raw material containing H 2 O are not limited to being different raw materials, and at least two of them may be the same raw material.
  • one kind of raw material containing B and H 2 O may be used as the raw material containing B and the raw material containing H 2 O.
  • the raw materials of glass 10 are not limited to the raw materials containing La, the raw materials containing B, the raw materials containing SO 3 , and the raw materials containing H 2 O, and other raw materials may be used according to the composition of glass 10 to be obtained.
  • the raw material containing La is a simple substance of La or a compound of La, and is preferably a compound of La.
  • the raw material containing La for example, La2O3 is preferably used.
  • the raw material containing B is a simple substance of B or a compound of B, and is preferably a compound of B.
  • the raw material containing B for example, at least one of B 2 O 3 and H 3 BO 3 is preferably used, and in a glass composition containing 7 wt % or more of B 2 O 3 , it is more preferable to use H 3 BO 3 in order to realize a higher transmittance.
  • the raw material containing SO 3 is preferably a compound containing SO 3 (containing at least one S and three O), and more preferably a sulfate.
  • the raw material containing SO 3 for example, at least one of La 2 (SO 4 ) 3.9H 2 O and Zr (SO 4 ) 2.4H 2 O is preferably used.
  • a raw material containing H2O is a compound that generates H2O upon combustion, in other words, a compound that contains at least two H and one O.
  • a raw material containing H2O it is preferable to use at least one of H3BO3 , a hydrate, and an organic material.
  • a sulfate hydrate such as La2 ( SO4 ) 3.9H2O and a nitrate hydrate such as La( NO3 ) 3.4H2O , which have good melting properties, are preferable.
  • the organic substance a sugar such as glucose C6H12O6 is preferable.
  • H3BO3 a glass composition containing 7 wt% or more of B2O3 .
  • H2O Addition Ratio the ratio of the amount of H2O added (amount of H2O added/total mass of glass) based on the oxides in the mass ratio is defined as the H2O addition ratio.
  • the amount of H2O added refers to the mass of the H2O component in the raw material containing H2O added in the mixing process, in other words, the mass of the components excluding the components other than H2O from the raw material containing H2O .
  • the mass of the components excluding B2O3 from H3BO3 is the mass of H2O ( 3H2O ) in the raw material containing H2O .
  • the ratio of the amount of H 3 BO 3 (a raw material containing H 2 O) added to the total mass of glass 10 based on oxides is 18.66 wt %
  • the ratio of H 2 O added, excluding B 2 O 3 is 8.16 wt %.
  • the H 2 O addition ratio is preferably 5 wt% or more, more preferably 6 wt% or more, and even more preferably 7 wt% or more.
  • the H 2 O addition ratio is preferably 20 wt% or less, more preferably 15 wt% or less, and even more preferably 10 wt% or less.
  • the H 2 O addition ratio is preferably 5 wt% or more and 20 wt% or less, more preferably 6 wt% or more and 15 wt% or less, and even more preferably 7 wt% or more and 10 wt% or less.
  • ⁇ OH evaluated in a glass state is an index of the amount of water remaining in the molding process, and in order to evaluate the moisture itself during the glass melting in the fining process where Pt dissolution progresses most, it is more preferable to take into account the H 2 O addition ratio.
  • the SO3 addition ratio the ratio of the amount of SO3 added (amount of SO3 added/total mass of glass) to the total mass of glass 10 based on oxides in mass ratio is defined as the SO3 addition ratio.
  • the amount of SO3 added refers to the mass of the SO3 component in the raw material containing SO3 mixed in the mixing process, in other words, the mass of the components excluding components other than SO3 from the raw material containing SO3 .
  • the SO 3 addition ratio is preferably 0.3 wt% or more, more preferably 0.5 wt% or more, and even more preferably 0.7 wt% or more.
  • the SO 3 addition ratio is preferably 2.5 wt% or less, more preferably 2.2 wt% or less, more preferably 2.0 wt% or less, more preferably 1.5 wt% or less, and even more preferably 1.0 wt% or less.
  • the SO 3 addition ratio is preferably 0.3 wt% or more and 2.0 wt% or less, more preferably 0.5 wt% or more and 1.5 wt% or less, more preferably 0.7 wt% or more and 1.3 wt% or less, and even more preferably 0.7 wt% or more and 1.0 wt% or less.
  • the raw materials are placed in a container such as a crucible, and the raw materials placed in the container are heated to melt the raw materials.
  • the container may be made of any material, but in this embodiment, a container containing Pt is used.
  • the heating temperature when melting the raw material is preferably 1350° C. or less, more preferably 1330° C. or less, and even more preferably 1300° C. or less.
  • the heating temperature when melting the raw material is preferably 1250° C. or more, and more preferably 1270° C. or more.
  • the heating temperature when melting the raw material is preferably 1350° C. or less, more preferably 1250° C. or more and 1330° C. or less, and even more preferably 1270° C.
  • the heating temperature in this range, there are no defects such as foreign matter and bubbles, and furthermore, dissolution of Pt contained in the container is suppressed, and the decrease in transmittance can be appropriately suppressed.
  • glass 10 according to the first aspect of the present disclosure contains La 2 O 3 and B 2 O 3 and, by mass ratio, has an S content of 100 ppm or more, an internal transmittance of 70% or more for light with a wavelength of 440 nm, and ⁇ OH of 0.1 mm -1 or more and 1.0 mm -1 or less.
  • Glass 10 according to the present disclosure can suppress the inclusion of bubbles by containing S in the above range.
  • the present inventor also found a problem that when a fining agent (a raw material containing SO 3 ) is added to suppress bubbles when manufacturing glass containing La 2 O 3 and B 2 O 3 , in other words, when S is contained in the glass, the transmittance decreases.
  • glass 10 according to the present disclosure can suppress the decrease in transmittance by appropriately containing water while suppressing the generation of bubbles by containing ⁇ OH in the above range.
  • Glass 10 according to the second aspect of the present disclosure is glass 10 according to the first aspect, and preferably has a refractive index n d of 1.95 or greater. Due to its high refractive index, glass 10 of the present disclosure can be appropriately used as an optical component.
  • Glass 10 according to the third aspect of the present disclosure is glass 10 according to the first or second aspect, and preferably has a ratio of the content of tetravalent Ti to the content of trivalent B of 3 or less. With such a composition, glass 10 according to the present disclosure can appropriately achieve a high refractive index and high transmittance.
  • Glass 10 according to a fourth aspect of the present disclosure is glass 10 according to any one of the first to third aspects, and preferably has a combined content of SiO 2 and B 2 O 3 of 10% or more, expressed as a mass ratio based on oxides. With such a composition, glass 10 of the present disclosure can appropriately achieve a high refractive index and high transmittance.
  • Glass 10 according to a fifth aspect of the present disclosure is glass 10 according to any of the first to fourth aspects, and preferably has a specific gravity of 5.30 g/cm 3 or less. Such a low specific gravity makes glass 10 easy to handle.
  • Glass 10 according to the sixth aspect of the present disclosure is glass 10 according to any one of the first to fifth aspects, and preferably has a devitrification temperature of 1270°C or less. Since glass 10 according to the present disclosure has a devitrification temperature of 1270°C or less, the temperature at which the raw materials are melted during the manufacture of glass 10 can be kept relatively low, and a decrease in transmittance can be suppressed.
  • the glass 10 according to the seventh aspect of the present disclosure is the glass 10 according to any one of the first to sixth aspects, and preferably does not contain Sb. This allows a high refractive index and high transmittance to be appropriately achieved.
  • the glass 10 according to the eighth aspect of the present disclosure is the glass 10 according to any one of the first to seventh aspects, and is preferably used as a light guide plate.
  • the glass 10 according to the present disclosure can be suitably used as a light guide plate.
  • a method for producing glass 10 according to a ninth aspect of the present disclosure includes mixing a raw material containing La, a raw material containing B, a raw material containing SO3 , and a raw material containing H2O , heating and melting the mixed raw materials, and cooling the melted raw materials to obtain glass, wherein the raw materials containing H2O are mixed such that the ratio of the amount of H2O added to the total mass of glass 10 based on oxides is 5 wt% or more and 20 wt% or less. According to the present disclosure, it is possible to suppress a decrease in transmittance by appropriately incorporating moisture while suppressing the time required for production.
  • a method for producing glass 10 according to a tenth aspect of the present disclosure is the method for producing glass 10 according to the ninth aspect, in which the raw material containing H 2 O is preferably at least one of boric acid (H 3 BO 3 ), a hydrate, and an organic substance.
  • the raw material containing H 2 O is preferably at least one of boric acid (H 3 BO 3 ), a hydrate, and an organic substance.
  • a method for producing glass 10 according to an eleventh aspect of the present disclosure is a method for producing glass 10 according to the ninth or tenth aspect, and preferably comprises mixing raw materials containing H 2 O such that the ratio of the amount of H 2 O added to the total mass of glass 10 based on oxides is 7 wt % or more.
  • the amount of H 2 O added within this range, moisture can be appropriately contained in glass 10, and a decrease in transmittance can be suppressed.
  • the method for producing glass 10 according to the twelfth aspect of the present disclosure is a method for producing glass 10 according to any one of the ninth to eleventh aspects, and preferably heats the mixed raw materials at 1350°C or less. By setting the heating temperature within this range, it is possible to appropriately suppress the decrease in transmittance.
  • Tables 1 to 11 show glasses of the respective examples. Note that the embodiment may be modified as long as the effects of the invention are achieved.
  • Example 1 glasses having thicknesses of 10 mm and 1 mm were manufactured with the composition shown in Table 1. Specifically, raw materials having the composition shown in Table 1 were uniformly mixed. In addition to the raw materials having the composition shown in Table 1, H 3 BO 3 as a raw material containing H 2 O and La 2 (SO 4 ) 3.9H 2 O, which is a raw material containing H 2 O and also a raw material containing SO 3 (also a raw material containing La ) , were also added as raw materials. The amount of raw material containing H 2 O added was adjusted so that the H 2 O addition ratio was the value shown in Table 1, and the amount of raw material containing SO 3 added was adjusted so that the SO 3 addition ratio was the value shown in Table 1.
  • the H 2 O addition ratio I in Table 1 is the H 2 O addition ratio of raw material I containing H 2 O
  • the H 2 O addition ratio II in Table 1 is the H 2 O addition ratio of raw material II containing H 2 O
  • the H 2 O addition ratio III in Table 1 is the H 2 O addition ratio of raw material III containing H 2 O
  • the H 2 O addition ratio (total) in Table 1 is the H 2 O addition ratio for the total of each raw material containing H 2 O.
  • the mixed raw materials were melted in a platinum crucible at 1330°C for 2 hours to obtain a uniform molten glass.
  • the molten glass was poured into a carbon mold having a length x width x height of 60 mm x width x height of 50 mm.
  • the mold was held at 740°C for 1 hour, and then cooled to room temperature at a temperature drop rate of about 1°C/min to obtain a glass block.
  • the glass block was cut into a length x width of 30 mm x width of 30 mm using a cutting machine (a small cutting machine manufactured by Marutoh Co., Ltd.), and the plate thickness was adjusted and the surface was polished using a grinding machine (SGM-6301 manufactured by Hidewa Kogyo Co., Ltd.) and a single-sided polishing machine (EJ-380IN manufactured by Engis Japan Co., Ltd.), to produce glass having a length x width of 30 mm x width of 10 mm and 1 mm in thickness.
  • a cutting machine a small cutting machine manufactured by Marutoh Co., Ltd.
  • the plate thickness was adjusted and the surface was polished using a grinding machine (SGM-6301 manufactured by Hidewa Kogyo Co., Ltd.) and a single-sided polishing machine (EJ-380IN manufactured
  • the S content (S concentration) of the glass of Example 1 was measured.
  • the measurement method was the same as that described in the above embodiment.
  • the ⁇ OH was calculated for the glass of Example 1.
  • the calculation method was the same as that described in the above embodiment.
  • the glass of Example 1 was measured for glass transition temperature Tg, coefficient of linear thermal expansion ⁇ in the range of 100° C. to 300° C., specific gravity d, refractive index n d , Abbe number v d , internal transmittance (transmittance ⁇ 440 ), and devitrification temperature.
  • the measurement methods used were the same as those described in the above embodiment. The results of each measurement are shown in Table 1.
  • Examples 2 to 51 glasses were produced in the same manner as in Example 1, except that the production conditions and compositions were as shown in Tables 1 to 11. The measurement results of the glasses of each Example are shown in Tables 1 to 11. In Examples 2 to 51, the internal transmittance columns left blank had an internal transmittance of 70% or more.
  • the glass of each example was evaluated for air bubbles and transparency.
  • bubbles a case where the number of bubbles larger than 30 ⁇ m in 100 ml of molten glass was less than 50 was rated as "good”, and a case where the number was 50 or more was rated as "bad”.
  • transmittance a case where the glass was transparent when visually observed under a fluorescent lamp was rated as "good”, and a case where the glass was cloudy was rated as "bad”.

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Abstract

La présente invention supprime une diminution de la transmittance, tout en supprimant l'inclusion de bulles d'air. Ce verre (10) contient La2O3 et B2O3, et a une teneur en S de 100 ppm ou plus en termes de rapport massique, une transmittance interne de 85% ou plus par rapport à la lumière ayant une longueur d'onde de 440 nm, et un βOH de 0,1 mm -1 à 1,0 mm -1 inclus.
PCT/JP2024/034246 2023-09-28 2024-09-25 Verre et procédé de production de verre Pending WO2025070525A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007111079A1 (fr) * 2006-03-27 2007-10-04 Asahi Glass Company, Limited Procede de fabrication de verre
JP2011042556A (ja) * 2009-07-24 2011-03-03 Nippon Electric Glass Co Ltd 光学ガラスの製造方法
JP2015117169A (ja) * 2013-12-19 2015-06-25 Hoya株式会社 ガラスの製造方法および光学素子の製造方法
JP2016052971A (ja) * 2014-09-04 2016-04-14 株式会社オハラ ガラスの製造方法およびガラス
JP2016074558A (ja) * 2014-10-06 2016-05-12 株式会社オハラ 光学ガラス及び光学素子
JP2016113311A (ja) * 2014-12-11 2016-06-23 株式会社オハラ 光学ガラス及び光学素子の製造方法
WO2019017205A1 (fr) * 2017-07-20 2019-01-24 Hoya株式会社 Verre optique, et élément optique

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007111079A1 (fr) * 2006-03-27 2007-10-04 Asahi Glass Company, Limited Procede de fabrication de verre
JP2011042556A (ja) * 2009-07-24 2011-03-03 Nippon Electric Glass Co Ltd 光学ガラスの製造方法
JP2015117169A (ja) * 2013-12-19 2015-06-25 Hoya株式会社 ガラスの製造方法および光学素子の製造方法
JP2016052971A (ja) * 2014-09-04 2016-04-14 株式会社オハラ ガラスの製造方法およびガラス
JP2016074558A (ja) * 2014-10-06 2016-05-12 株式会社オハラ 光学ガラス及び光学素子
JP2016113311A (ja) * 2014-12-11 2016-06-23 株式会社オハラ 光学ガラス及び光学素子の製造方法
WO2019017205A1 (fr) * 2017-07-20 2019-01-24 Hoya株式会社 Verre optique, et élément optique

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