WO2012157695A1 - Verre à indice de réfraction élevé - Google Patents

Verre à indice de réfraction élevé Download PDF

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Publication number
WO2012157695A1
WO2012157695A1 PCT/JP2012/062610 JP2012062610W WO2012157695A1 WO 2012157695 A1 WO2012157695 A1 WO 2012157695A1 JP 2012062610 W JP2012062610 W JP 2012062610W WO 2012157695 A1 WO2012157695 A1 WO 2012157695A1
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Prior art keywords
refractive index
less
glass
sro
content
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PCT/JP2012/062610
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English (en)
Japanese (ja)
Inventor
篤 虫明
隆 村田
智基 柳瀬
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日本電気硝子株式会社
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Application filed by 日本電気硝子株式会社 filed Critical 日本電気硝子株式会社
Priority to DE112012002137.1T priority Critical patent/DE112012002137B4/de
Priority to KR1020137025248A priority patent/KR101490828B1/ko
Priority to CN201280020313.2A priority patent/CN103492331A/zh
Publication of WO2012157695A1 publication Critical patent/WO2012157695A1/fr

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Classifications

    • 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
    • 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
    • C03C3/078—Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of zinc
    • 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
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
    • 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
    • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/85—Arrangements for extracting light from the devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays

Definitions

  • the present invention relates to a high refractive index glass, for example, an organic EL device, particularly a high refractive index glass suitable for organic EL lighting.
  • organic EL devices have a structure in which an organic light emitting element is sandwiched between substrates (glass plates) on which a transparent conductive film such as ITO or FTO is formed (see, for example, Patent Document 1).
  • a transparent conductive film such as ITO or FTO is formed
  • Patent Document 1 when a current flows through the organic light emitting device, holes and electrons in the organic light emitting device associate to emit light. The emitted light enters the glass plate through the transparent conductive film, and is emitted to the outside while being repeatedly reflected in the glass plate.
  • the refractive index nd of the organic light emitting device is 1.8 to 1.9, and the refractive index nd of the transparent electrode film is 1.9 to 2.0.
  • the refractive index nd of the glass substrate is usually about 1.5.
  • the conventional organic EL device has a problem that it has a high reflectance due to the difference in refractive index between the glass substrate and the ITO interface, and the light generated from the organic light emitting element cannot be extracted efficiently.
  • the difference in refractive index at the interface between the glass plate and the transparent electrode film can be reduced.
  • An optical glass used in an optical lens or the like is known as a high refractive index glass.
  • optical glass is used that is heat-treated again into droplet glass that has been formed into a spherical shape by a droplet molding method or the like, and press-molded into a predetermined shape.
  • this optical glass has a high refractive index nd, it has a low liquidus viscosity, so if it is not molded by a droplet molding method or the like with a high cooling rate, the glass will be devitrified during molding. Therefore, in order to solve the above problem, it is necessary to improve the devitrification resistance of the high refractive index glass.
  • the refractive index nd of the glass plate can be increased while suppressing a decrease in liquid phase viscosity to some extent.
  • a rare metal oxide has a problem that the raw material cost is high.
  • the devitrification resistance is lowered, and it becomes difficult to form a glass plate.
  • the oxidation resistance is also lowered.
  • the present invention is consistent with the refractive index nd of the organic light emitting device and the transparent electrode film despite the low content of rare metal oxides (particularly La 2 O 3 , Nb 2 O 5 , Gd 2 O 3 ). Moreover, it is a technical object to provide a high refractive index glass having good devitrification resistance.
  • the present inventors have found that the above technical problem can be solved by regulating the content range and refractive index of each component to a predetermined range, and propose as the first invention.
  • the high refractive index glass of the first invention has a glass composition of B 2 O 3 0 to 10%, SrO 0.001 to 35%, ZrO 2 + TiO 2 0.001 to 30%, La as a glass composition.
  • 2 O 3 + Nb 2 O 5 0 contained ⁇ 10%
  • the mass ratio BaO / SrO is 0 to 40
  • the mass ratio SiO 2 / SrO is 0.1 to 40
  • a refractive index nd of 1.55 to 2 .3.
  • ZrO 2 + TiO 2 refers to the total amount of ZrO 2 and TiO 2 .
  • La 2 O 3 + Nb 2 O 5 refers to the total amount of La 2 O 3 and Nb 2 O 5 .
  • the “refractive index nd” can be measured with a commercially available refractive index measuring device.
  • the high refractive index glass of the first invention preferably has a liquidus viscosity of 10 3.0 dPa ⁇ s or more.
  • liquid phase viscosity refers to a value obtained by measuring the viscosity of glass at the liquid phase temperature by a platinum ball pulling method.
  • Liquid phase temperature refers to the temperature at which crystals precipitate after passing through a standard sieve 30 mesh (500 ⁇ m), putting the glass powder remaining on 50 mesh (300 ⁇ m) into a platinum boat and holding it in a temperature gradient furnace for 24 hours. Refers to the measured value.
  • the high refractive index glass of the first invention is preferably plate-shaped.
  • “plate shape” is not interpreted in a limited way, and includes a film shape with a small plate thickness, for example, a film-shaped glass placed along a cylinder, and an uneven shape is formed on one surface. Including.
  • the high refractive index glass of the first invention is preferably formed by a float process.
  • the high refractive index glass of the first invention preferably has a temperature at 10 4 dPa ⁇ s of 1250 ° C. or lower.
  • temperature at 10 4.0 dPa ⁇ s refers to a value measured by a platinum ball pulling method.
  • the high refractive index glass of the first invention preferably has a strain point of 650 ° C. or higher.
  • the high refractive index glass of the first invention is preferably used for an illumination device.
  • the high refractive index glass of the first invention is preferably used for organic EL lighting.
  • the high refractive index glass of the first invention is preferably used for an organic EL display.
  • the high refractive index glass of the first invention is, as a glass composition, B 2 O 3 0-8%, SrO 0.001-35% ZnO 0-12%, ZrO 2 + TiO 2 0 by mass%. 0.001-30%, La 2 O 3 + Nb 2 O 5 0-5%, Li 2 O + Na 2 O + K 2 O 0-10%, mass ratio BaO / SrO 0-20, mass ratio SiO 2 / SrO Is 0.1 to 20, the mass ratio (MgO + CaO) / SrO is 0 to 20, the refractive index nd is 1.58 or more, the liquid phase viscosity is 10 3.5 dPa ⁇ s or more, and the strain point is 670 ° C. or more.
  • Li 2 O + Na 2 O + K 2 O refers to the total amount of Li 2 O, Na 2 O, and K 2 O.
  • MgO + CaO refers to the total amount of MgO and CaO.
  • the high refractive index glass of the first invention has a glass composition of 10 to 50% by weight of SiO 2 , 0 to 8% of B 2 O 3 , 0 to 10% of CaO, 0.001 of SrO as a glass composition.
  • a glass plate for a lighting device of the first invention as a glass composition, in mass%, SiO 2 0.1 ⁇ 60% , B 2 O 3 0 ⁇ 10%, SrO 0.001 ⁇ 35% BaO 0 to 40%, ZrO 2 + TiO 2 0.001 to 30%, La 2 O 3 + Nb 2 O 5 0 to 10%, and the refractive index nd is 1.55 to 2.3.
  • the glass plate for organic EL lighting of the first invention has a glass composition of SiO 2 0.1 to 60%, B 2 O 3 0 to 10%, SrO 0.001 to 35 as a glass composition. %, BaO 0 to 40%, ZrO 2 + TiO 2 0.001 to 30%, La 2 O 3 + Nb 2 O 5 0 to 10%, and the refractive index nd is 1.55 to 2.3. It is characterized by.
  • the glass plate for an organic EL display according to the first aspect of the present invention has a glass composition of SiO 2 0.1 to 60%, B 2 O 3 0 to 10%, SrO 0.001 to 35 in terms of mass%. %, BaO 0 to 40%, ZrO 2 + TiO 2 0.001 to 30%, La 2 O 3 + Nb 2 O 5 0 to 10%, and the refractive index nd is 1.55 to 2.3. It is characterized by.
  • the high refractive index glass of the first invention has a glass composition of 35% to 60% SiO 2 , Li 2 O + Na 2 O + K 2 O 0 to 1.5%, SrO 0.1 to 0.1% by mass. 35%, BaO 0 to 35%, TiO 2 0.001 to 25%, La 2 O 3 + Nb 2 O 5 + Gd 2 O 3 0 to 9%, and refractive index nd is 1.55 to 2.3 It is characterized by being.
  • “La 2 O 3 + Nb 2 O 5 + Gd 2 O 3 ” refers to the total amount of La 2 O 3 , Nb 2 O 5 , and Gd 2 O 3 .
  • the high refractive index glass of the first invention has a glass composition of 35% to 60% of SiO 2 , Li 2 O + Na 2 O + K 2 O 0 to 1.5%, SrO 0.1 to 0.1% by mass. 20%, BaO 17-35%, TiO 2 0.01-20%, La 2 O 3 + Nb 2 O 5 + Gd 2 O 3 0-9%, with a refractive index nd of 1.55 to 2.3 It is characterized by being.
  • the content of B 2 O 3 is preferably 0 to 3% by mass.
  • the high refractive index glass of the first invention preferably further has a MgO content of 0 to 3% by mass.
  • the high refractive index glass of the first invention preferably further has a ZrO 2 + TiO 2 content of 1 to 20% by mass.
  • the high refractive index glass of the first invention is preferably formed by a downdraw method.
  • the “down draw method” includes an overflow down draw method, a slot down draw method, a redraw method, and the like.
  • the present inventors have found that the above technical problem can be solved by regulating the glass composition range to a predetermined range, and propose the second invention. That is, the high refractive index glass of the second invention has a glass composition of 30% by weight of SiO 2 30-60%, B 2 O 3 0-15%, Al 2 O 3 0-15%, Li 2 O 0 as a glass composition.
  • MgO + CaO + SrO + BaO + ZnO refers to the total amount of MgO, CaO, SrO, BaO, and ZnO.
  • La 2 O 3 + Nb 2 O 5 refers to the total amount of La 2 O 3 and Nb 2 O 5 .
  • the “refractive index nd” can be measured with a refractive index measuring device.
  • a cuboid sample of 25 mm ⁇ 25 mm ⁇ about 3 mm is prepared, and then from (annealing point Ta + 30 ° C.) to (strain point Ps ⁇ 50 ° C.).
  • annealing point Ta + 30 ° C. By annealing the temperature range at a cooling rate of 0.1 ° C./min, and then penetrating an immersion liquid having a matching refractive index nd between the glasses, using a refractive index measuring device KPR-200 manufactured by Kalnew It can be measured.
  • “Slow cooling point Ta” refers to a value measured by the method described in ASTM C338-93.
  • strain point Ps refers to a value measured by the method described in ASTM C336-71.
  • the high refractive index glass of the second invention is SiO 2 30-60%, B 2 O 3 0-15%, Al 2 O 3 0-15%, MgO + CaO + SrO + BaO + ZnO 20-60%, TiO 2 0.0001-20% , ZrO 2 0 to 20%. If it does in this way, devitrification resistance can be improved, raising refractive index nd.
  • the high refractive index glass of the second invention contains La 2 O 3 + Nb 2 O 5 0 to 10%. If it does in this way, while being able to reduce raw material cost, it becomes easy to improve devitrification resistance and acid resistance.
  • the high refractive index glass of the second invention contains Li 2 O 0 to 10%, Na 2 O 0 to 10%, K 2 O 0 to 10%. If it does in this way, acid resistance will improve and it will become difficult for a glass to become cloudy by the elution of an alkaline component in the etching process by an acid.
  • the etching process with an acid is included in a manufacturing process of an organic EL display or the like, and when the acid resistance of the glass plate is low, the glass plate is eroded and becomes cloudy in this etching step. When the glass plate becomes cloudy, the transmittance of the glass plate is lowered, and it becomes difficult to increase the definition of the display.
  • the high refractive index glass of the second invention has a refractive index nd of 1.55 to 2.3. If it does in this way, it will become easy to match
  • the high refractive index glass of the second invention has a glass composition of 35% by weight of SiO 2 , 0 to 15% of B 2 O 3, 0 to 15% of Al 2 O 3 , Li 2 O 0-10%, Na 2 O 0-10%, K 2 O 0-10%, MgO + CaO + SrO + BaO + ZnO 20-60%, TiO 2 0.0001-20%, ZrO 2 0.0001-20%, La 2 O 3 + Nb 2 O 5 is preferably contained in an amount of 0 to 10%, and the refractive index nd is preferably 1.55 to 2.3.
  • the high refractive index glass of the second invention has a glass composition of 35% by weight of SiO 2 , B 2 O 3 0 to 15%, Al 2 O 3 0 to 15%, Li 2 as a glass composition.
  • “Li 2 O + Na 2 O + K 2 O” refers to the total amount of Li 2 O, Na 2 O, and K 2 O.
  • the high refractive index glass of the second invention preferably contains 1% by mass or more of B 2 O 3 .
  • the high refractive index glass of the second invention preferably contains 1% by mass or more of MgO.
  • the high refractive index glass of the second invention is preferably plate-shaped. If it does in this way, it will become easy to apply to the substrate of various devices, such as an organic EL display, organic EL lighting, and an organic thin film solar cell.
  • “plate shape” is not limitedly interpreted, and includes a film shape with a small plate thickness, such as glass in a film shape installed along a cylinder, and an uneven shape is formed on one surface. Including things.
  • the high refractive index glass of the second invention preferably has a liquidus viscosity of 10 3.0 dPa ⁇ s or more.
  • Organic EL lighting or the like has a problem that the current density at the time of current application changes due to a slight difference in the surface smoothness of the glass plate, causing unevenness in illuminance. Further, when the glass surface is polished in order to improve the surface smoothness of the glass plate, there arises a problem that the processing cost increases. Therefore, when the liquidus viscosity is in the above range, it becomes easy to form a glass plate by an overflow down draw method or the like, and as a result, it becomes easy to produce a glass plate with good surface smoothness even if not polished.
  • liquid phase viscosity refers to a value obtained by measuring the viscosity of glass at the liquid phase temperature by a platinum ball pulling method.
  • Liquid phase temperature refers to the temperature at which crystals precipitate by passing the standard sieve 30 mesh (500 ⁇ m) and putting the glass powder remaining in 50 mesh (300 ⁇ m) into a platinum boat and holding it in a temperature gradient furnace for 24 hours. Refers to the measured value.
  • the “overflow down draw method” is a method in which molten glass overflows from both sides of a heat-resistant bowl-shaped structure, and the overflowed molten glass joins at the lower end of the bowl-shaped structure and is stretched downward to form a glass plate. This is a molding method.
  • the high refractive index glass of the second invention is preferably formed by a float method or a downdraw method.
  • the “down draw method” includes an overflow down draw method, a slot down draw method, and the like.
  • the high refractive index glass of the second invention preferably has an unpolished surface on at least one surface, and the surface roughness Ra of the surface is preferably 10 mm or less.
  • surface roughness Ra refers to a value measured by a method based on JIS B0601: 2001.
  • the organic light-emitting element and the transparent electrode film are reduced while reducing the content of rare metal oxides (particularly La 2 O 3 , Nb 2 O 5 , Gd 2 O 3 ). It is possible to provide a high refractive index glass that matches the refractive index nd and has good devitrification resistance.
  • the high refractive index glass according to an embodiment of the first invention (hereinafter referred to as the first embodiment) has, as a glass composition, mass%, B 2 O 3 0 to 10%, SrO 0.001 to 35%, ZrO 2 + TiO 2 0.001 to 30%, La 2 O 3 + Nb 2 O 5 0 to 10%, the mass ratio BaO / SrO is 0 to 40, and the mass ratio SiO 2 / SrO is 0.1 to 40 is there.
  • the reason for limiting the content range of each component as described above will be described below.
  • % display represents the mass% except the case where there is particular notice.
  • the content of B 2 O 3 is preferably 0 to 10%.
  • a suitable upper limit range of B 2 O 3 is 8% or less, 5% or less, 4% or less, 3% or less, less than 2%, 1% or less, particularly less than 1%.
  • the SrO content is preferably 0.001 to 35%.
  • SrO is a component having a large effect of increasing the refractive index nd while relatively suppressing devitrification among alkaline earth metal oxides.
  • the preferable upper limit range of SrO is 30% or less, 25% or less, 20% or less, 15% or less, 12% or less, 10% or less, and particularly 8% or less.
  • a preferable lower limit range of SrO is 0.01% or more, 0.1% or more, 1% or more, 2% or more, 3% or more, 3.5% or more, particularly 4% or more.
  • the content of TiO 2 + ZrO 2 is preferably 0.001 to 30%.
  • the preferable upper limit range of TiO 2 + ZrO 2 is 25% or less, 20% or less, 18% or less, 15% or less, 14% or less, particularly 13% or less.
  • a preferable lower limit range of TiO 2 + ZrO 2 is 0.01% or more, 0.5% or more, 1% or more, 3% or more, 5% or more, 6% or more, particularly 7% or more.
  • the content of TiO 2 is preferably 0 to 30%.
  • TiO 2 is a component that increases the refractive index nd.
  • the preferable upper limit range of TiO 2 is 25% or less, 15% or less, 12% or less, and particularly 8% or less.
  • a preferable lower limit range of TiO 2 is 0.001% or more, 0.01% or more, 0.5% or more, 1% or more, and particularly 3% or more.
  • the content of ZrO 2 is preferably 0 to 30%.
  • ZrO 2 is a component that has a large effect of increasing the refractive index nd and increasing the viscosity near the liquidus temperature.
  • the preferable upper limit range of ZrO 2 is 15% or less, 10% or less, 7% or less, and particularly 6% or less.
  • a suitable lower limit range of ZrO 2 is 0.001% or more, 0.01% or more, 0.5% or more, 1% or more, 2% or more, particularly 3% or more.
  • the content of La 2 O 3 + Nb 2 O 5 is preferably 0 to 10%.
  • the refractive index nd tends to increase, but when the content exceeds 10%, the component balance of the glass composition is lacking and the devitrification resistance decreases. There is a risk that the raw material cost will rise and the glass manufacturing cost will rise. In particular, in applications such as lighting, an inexpensive glass is required, so that the raw material cost is not increased. Therefore, the preferable lower limit range of La 2 O 3 + Nb 2 O 5 is 9% or less, 8% or less, 5% or less, 3% or less, 2% or less, 1% or less, 0.5% or less, particularly 0.1%. % Or less.
  • La 2 O 3 is a component that increases the refractive index nd.
  • the content of La 2 O 3 is preferably 10% or less, 9% or less, 8% or less, 5% or less, 2% or less, 1% or less, 0.5% or less, and particularly preferably 0.1% or less.
  • Nb 2 O 5 is a component that increases the refractive index nd.
  • the content of Nb 2 O 5 is preferably 10% or less, 9% or less, 8% or less, 5% or less, 2% or less, 1% or less, 0.5% or less, and particularly preferably 0.1% or less.
  • the mass ratio (La 2 O 3 + Nb 2 O 5 ) / (ZrO 2 + TiO 2 ) is preferably 0-30.
  • As the mass ratio (La 2 O 3 + Nb 2 O 5 ) / (ZrO 2 + TiO 2 ) is larger, it is possible to increase the refractive index nd while suppressing a decrease in devitrification resistance. If too much, the balance of the components of the glass composition is lost, devitrification resistance is lowered, and the raw material cost is too high.
  • the preferable upper limit range of the mass ratio (La 2 O 3 + Nb 2 O 5 ) / (ZrO 2 + TiO 2 ) is 20 or less, 10 or less, 5 or less, 2 or less, 1 or less, 0.1 or less, especially 0. 01 or less.
  • the mass ratio BaO / SrO is 0-40. If the mass ratio BaO / SrO is too large, the devitrification resistance may decrease, or the density and the thermal expansion coefficient may become too high. On the other hand, if the mass ratio BaO / SrO is too small, the refractive index nd may be reduced, or the component balance of the glass composition may be lost, and the devitrification resistance may be reduced. Therefore, a preferable upper limit range of the mass ratio BaO / SrO is 30 or less, 20 or less, 10 or less, 8 or less, and particularly 5 or less. A preferable lower limit range of the mass ratio BaO / SrO is 0.1 or more, 0.5 or more, 1 or more, 2.5 or more, particularly 3 or more.
  • BaO is a component that increases the refractive index nd without extremely reducing the viscosity of the glass among alkaline earth metal oxides.
  • the content of BaO is preferably 0 to 40%.
  • the preferable upper limit range of BaO is 35% or less, 32% or less, 30% or less, 29.5% or less, 29% or less, and particularly preferably 28% or less.
  • the preferable lower limit range of BaO is 0.5% or more, 1% or more, 2% or more, 5% or more, 10% or more, 15% or more, 17% or more, 20% or more, 23% or more, particularly 25%. The above is preferable.
  • the mass ratio SiO 2 / SrO is 0.1-40. If the mass ratio SiO 2 / SrO is too large, the refractive index nd tends to decrease. On the other hand, if the mass ratio SiO 2 / SrO is too small, the devitrification resistance tends to decrease, and the density and the thermal expansion coefficient may become too high. Therefore, a preferable upper limit range of the mass ratio SiO 2 / SrO is 30 or less, 20 or less, 15 or less, 10 or less, 9 or less, and particularly 8 or less. A preferable lower limit range of the mass ratio SiO 2 / SrO is 0.5 or more, 1 or more, 2 or more, 2.5 or more, particularly 3 or more.
  • the content of SiO 2 is preferably 0.1 to 60%.
  • the SiO 2 content is preferably 55% or less, 53% or less, 52% or less, 50% or less, 49% or less, 48% or less, and particularly preferably 45% or less.
  • the content of SiO 2 is preferably 3% or more, 5% or more, 10% or more, 15% or more, 20% or more, 25% or more, 30% or more, 35% or more, particularly 40% or more.
  • the content of Al 2 O 3 is preferably 0 to 20%.
  • the preferable upper limit range of Al 2 O 3 is 15% or less, 10% or less, 8% or less, and particularly 6% or less.
  • the content of Al 2 O 3 is reduced, lacks component balance of the glass composition, the glass is liable to devitrify reversed. Therefore, a preferable lower limit range of Al 2 O 3 is 0.1% or more, 0.5% or more, 1% or more, particularly 3% or more.
  • the content of MgO is preferably 0 to 10%.
  • MgO is a component that increases the refractive index nd, Young's modulus, and strain point, and also decreases the high-temperature viscosity.
  • a suitable upper limit range of MgO is 5% or less, 3% or less, 2% or less, 1.5% or less, 1% or less, particularly 0.5% or less.
  • the CaO content is preferably 0 to 10%.
  • the preferable upper limit range of CaO is 9% or less, particularly 8.5% or less.
  • the preferable lower limit range of CaO is 0.5% or more, 1% or more, 2% or more, 3% or more, particularly 4% or more.
  • the mass ratio (MgO + CaO) / SrO is preferably 0-20.
  • a suitable upper limit range of the mass ratio (MgO + CaO) / SrO is 10 or less, 8 or less, 5 or less, 3 or less, 2 or less, particularly 1 or less.
  • the content of ZnO is preferably 0 to 12%.
  • the preferable upper limit range of ZnO is 8% or less, 4% or less, 2% or less, 1% or less, 0.5% or less, 0.1% or less, particularly 0.01% or less.
  • the content of La 2 O 3 + Nb 2 O 5 + Gd 2 O 3 is preferably 0 to 10%.
  • the refractive index nd tends to increase.
  • the glass composition lacks the component balance and is devitrification resistant. There is a risk that the manufacturing cost of the glass will rise due to a decrease in properties or a rise in raw material costs. In particular, in applications such as lighting, an inexpensive glass is required, so that the raw material cost is not increased.
  • a suitable lower limit range of La 2 O 3 + Nb 2 O 5 + Gd 2 O 3 is 9% or less, 8% or less, 5% or less, 3% or less, 2% or less, 1% or less, 0.5% or less, In particular, it is 0.1% or less.
  • the content of Gd 2 O 3 is preferably 0 to 10%.
  • Gd 2 O 3 is a component that increases the refractive index. However, if the content of Gd 2 O 3 increases, the density and thermal expansion coefficient become too high, the glass composition component balance is lacking, and devitrification resistance is reduced. It becomes difficult to secure a high liquid phase viscosity because the viscosity is lowered or the high temperature viscosity is excessively lowered. Therefore, the preferable upper limit range of Gd 2 O 3 is 8% or less, 4% or less, 2% or less, 1% or less, 0.5% or less, 0.1% or less, particularly 0.01% or less.
  • the content of Li 2 O + Na 2 O + K 2 O is preferably 0 to 15%.
  • Li 2 O + Na 2 O + K 2 O is a component that lowers the viscosity of the glass and adjusts the thermal expansion coefficient.
  • the preferable upper limit range of Li 2 O + Na 2 O + K 2 O is 10% or less, 5% or less, 2% or less, 1.5% or less, 1% or less, 0.5% or less, particularly 0.1% or less. is there.
  • As a fining agent 0 to 3% of one or more selected from the group of As 2 O 3 , Sb 2 O 3 , CeO 2 , SnO 2 , F, Cl, and SO 3 can be added.
  • As 2 O 3 , Sb 2 O 3 , and F, particularly As 2 O 3 and Sb 2 O 3 it is preferable to refrain from using them as much as possible from an environmental viewpoint, and each content is 0.1%. Less than is preferable.
  • SnO 2 , SO 3 , and Cl are preferable as the fining agent.
  • the SnO 2 content is preferably 0 to 1%, 0.01 to 0.5%, particularly preferably 0.05 to 0.4%.
  • SnO 2 + SO 3 + Cl The content of SnO 2 + SO 3 + Cl is preferably 0 to 1%, 0.001 to 1%, 0.01 to 0.5%, particularly preferably 0.01 to 0.3%.
  • SnO 2 + SO 3 + Cl refers to the total amount of SnO 2 , SO 3 , and Cl.
  • PbO is a component that lowers the high temperature viscosity, but it is preferable to refrain from using it as much as possible from an environmental viewpoint, and its content is preferably 0.5% or less, more preferably less than 1000 ppm (mass).
  • Bi 2 O 3 is a component that lowers the high temperature viscosity, but it is preferable to refrain from using it as much as possible from the environmental viewpoint, and its content is preferably 0.5% or less, more preferably less than 1000 ppm (mass). .
  • glass composition range by combining preferred ranges of each component, but among them, particularly preferred from the viewpoint of refractive index nd, devitrification resistance, production cost, etc.
  • the glass composition range is as follows.
  • the refractive index nd is 1.55 or more, preferably 1.58 or more, 1.6 or more, 1.63 or more, 1.65 or more, particularly 1.66 or more. is there.
  • the refractive index nd is less than 1.55, the reflectance at the ITO-glass interface increases, and light cannot be extracted efficiently.
  • the refractive index nd exceeds 2.3, the reflectance at the air-glass interface increases, and it becomes difficult to increase the light extraction efficiency even if the glass surface is roughened. Therefore, the refractive index nd is preferably 2.3 or less, 2.2 or less, 2.1 or less, 2.0 or less, 1.9 or less, particularly 1.75 or less.
  • the liquidus temperature is preferably 1200 ° C. or lower, 1150 ° C. or lower, 1130 ° C. or lower, 1110 ° C. or lower, 1090 ° C. or lower, 1070 ° C. or lower, particularly 1050 ° C. or lower.
  • the liquid phase viscosity is 10 3.0 dPa ⁇ s or more, 10 3.5 dPa ⁇ s or more, 10 3.8 dPa ⁇ s or more, 10 4.0 dPa ⁇ s or more, 10 4.1 dPa ⁇ s or more.
  • It is preferably 10 4.2 dPa ⁇ s or more, particularly preferably 10 4.3 dPa ⁇ s or more. If it does in this way, it will become difficult to devitrify glass at the time of shaping
  • the high refractive index glass of the first embodiment is preferably plate-shaped.
  • the thickness is preferably 1.5 mm or less, 1.3 mm or less, 1.1 mm or less, 0.8 mm or less, 0.6 mm or less, 0.5 mm or less, 0.3 mm or less, particularly 0.2 mm or less.
  • the smaller the plate thickness the higher the flexibility and the easier it is to improve the design of the lighting device.
  • the plate thickness is preferably 10 ⁇ m or more, particularly 30 ⁇ m or more.
  • the high refractive index glass of the first embodiment is preferably formed by a float method. In this way, it is possible to manufacture a glass plate that is unpolished and has good surface quality at a low cost and in large quantities.
  • a downdraw method (overflow downdraw method, slot downdraw method, redraw method, etc.), rollout method, or the like can be employed as a method for forming a glass plate.
  • the high refractive index glass of the first embodiment is preferably subjected to a roughening treatment on one surface by HF etching, sand blasting, or the like.
  • the surface roughness Ra of the roughened surface is preferably 10 mm or more, 20 mm or more, 30 mm or more, particularly 50 mm or more. If the roughened surface is in contact with the air such as organic EL lighting, the roughened surface has a non-reflective structure, so that the light generated in the organic light emitting layer is difficult to return to the organic light emitting layer. As a result, the light extraction efficiency can be increased. Moreover, you may give uneven
  • the surface state of one surface can be maintained, and the other surface can be uniformly roughened.
  • a gas containing F for example, SF 6 , CF 4
  • plasma containing HF gas is generated, the efficiency of the roughening treatment is improved.
  • the density is 5.0 g / cm 3 or less, 4.8 g / cm 3 or less, 4.5 g / cm 3 or less, 4.3 g / cm 3 or less, 3.7 g / cm. It is preferably 3 or less, particularly 3.5 g / cm 3 or less. If it does in this way, glass will be reduced in weight and a device can be reduced in weight.
  • the “density” can be measured by a known Archimedes method.
  • the thermal expansion coefficient is 30 ⁇ 10 ⁇ 7 to 100 ⁇ 10 ⁇ 7 / ° C., 40 ⁇ 10 ⁇ 7 to 90 ⁇ 10 ⁇ 7 / ° C., 60 ⁇ 10 ⁇ 7 to 85 ⁇ 10 ⁇ 7 / ° C., 65 ⁇ 10 ⁇ 7 to 80 ⁇ 10 ⁇ 7 / ° C., 68 ⁇ 10 ⁇ 7 to 78 ⁇ 10 ⁇ 7 / ° C., particularly 70 ⁇ 10 ⁇ 7 to 78 ⁇ 10 ⁇ 7 / ° C. preferable.
  • thermo expansion coefficient refers to an average value in a temperature range of 30 to 380 ° C., and can be measured, for example, with a dilatometer.
  • the strain point is preferably 630 ° C. or higher, 650 ° C. or higher, 670 ° C. or higher, 690 ° C. or higher, particularly 700 ° C. or higher. If it does in this way, it will become difficult to heat-shrink glass by the high temperature heat processing in the manufacturing process of a device. In particular, when an organic EL display is manufactured using an oxide TFT or the like, a heat treatment of about 600 ° C. is necessary to stabilize the quality of the oxide TFT. If the strain point is regulated as described above, In this heat treatment, the thermal shrinkage of the glass can be reduced.
  • the temperature at 10 2.5 dPa ⁇ s is preferably 1400 ° C. or lower, 1350 ° C. or lower, 1300 ° C. or lower, 1250 ° C. or lower, particularly 1200 ° C. or lower. If it does in this way, since meltability will improve, the glass excellent in foam quality will be easy to be obtained, and the manufacture efficiency of a glass plate will improve.
  • the temperature at 10 4.0 dPa ⁇ s is 1250 ° C. or lower, 1200 ° C. or lower, 1150 ° C. or lower, 1110 ° C. or lower, particularly 1060 ° C. or lower.
  • the molding temperature can be lowered in the molding by the float method.
  • low-temperature operation becomes possible, and the refractory used in the molded part has a long life, and the manufacturing cost of the glass plate is likely to decrease.
  • glass raw materials are prepared so as to have a desired glass composition, and a glass batch is produced.
  • the glass batch is melted and clarified, the obtained molten glass is formed into a desired shape.
  • an annealing process is performed to process into a desired shape.
  • the glass plate for lighting device has, as a glass composition, SiO 2 0.1 to 60%, B 2 O 3 0 to 10%, SrO 0.001 to 35 as a glass composition. %, BaO 0 to 40%, ZrO 2 + TiO 2 0.001 to 30%, La 2 O 3 + Nb 2 O 5 0 to 10%, and the refractive index nd is 1.55 to 2.3. It is characterized by.
  • the glass plate for organic EL lighting according to the embodiment of the first invention has, as a glass composition, SiO 2 0.1 to 60%, B 2 O 3 0 to 10%, SrO 0.001 to 0.001% by mass.
  • the glass plate for an organic EL display according to the embodiment of the first invention has, as a glass composition, SiO 2 0.1 to 60%, B 2 O 3 0 to 10%, SrO 0.001 to mass%. 35%, BaO 0 to 40%, ZrO 2 + TiO 2 0.001 to 30%, La 2 O 3 + Nb 2 O 5 0 to 10%, and the refractive index nd is 1.55 to 2.3. It is characterized by that. Since the technical features of the glass plate for lighting device, the glass plate for organic EL lighting, and the glass plate for organic EL display are substantially the same as those of the high refractive index glass described in the first embodiment, a detailed description is provided. Is omitted.
  • Tables 1 to 4 show examples of the first invention (sample Nos. 1 to 19).
  • the obtained glass batch was supplied to a glass melting furnace and melted at 1500 to 1600 ° C. for 4 hours.
  • the obtained molten glass was poured onto a carbon plate, formed into a plate shape, and then subjected to a predetermined annealing treatment. Finally, various characteristics of the obtained glass plate were evaluated.
  • the density is a value measured by the well-known Archimedes method.
  • the thermal expansion coefficient is a value obtained by measuring an average thermal expansion coefficient at 30 to 380 ° C. using a dilatometer.
  • a cylindrical sample having a diameter of 5 mm ⁇ 20 mm (the end surface is R-processed) was used.
  • the strain point Ps is a value measured by the method described in ASTM C336-71. In addition, heat resistance becomes high, so that the strain point Ps is high.
  • the annealing point Ta and the softening point Ts are values measured by the method described in ASTM C338-93.
  • the temperatures at high temperature viscosities of 10 4.0 dPa ⁇ s, 10 3.0 dPa ⁇ s, and 10 2.5 dPa ⁇ s are values measured by the platinum ball pulling method. In addition, it is excellent in meltability, so that these temperatures are low.
  • the liquid phase temperature TL passes through a standard sieve 30 mesh (500 ⁇ m), and the glass powder remaining in 50 mesh (300 ⁇ m) is placed in a platinum boat and held in a temperature gradient furnace for 24 hours to measure the temperature at which crystals precipitate. It is the value. Further, the liquidus viscosity log 10 ⁇ TL indicates a value obtained by measuring the viscosity of glass at the liquidus temperature by a platinum ball pulling method. The higher the liquidus viscosity and the lower the liquidus temperature, the better the devitrification resistance and moldability.
  • the refractive index nd is a 25 mm ⁇ 25 mm ⁇ about 3 mm cuboid sample, and the temperature range from (annealing point Ta + 30 ° C.) to (strain point Ps ⁇ 50 ° C.) is 0.1 ° C./min cooling rate. This is a value measured by a refractive index measuring instrument KPR-2000 manufactured by Shimadzu Corporation while an immersion liquid having a refractive index nd matching is infiltrated between the glasses.
  • the high refractive index glass according to the embodiment of the second invention has a glass composition of 30% by mass, SiO 2 30-60%, B 2 O 3 0-15%, Al, as a glass composition.
  • 2 O 3 0-15% Li 2 O 0-10%, Na 2 O 0-10%, K 2 O 0-10%, MgO + CaO + SrO + BaO + ZnO 20-60%, TiO 2 0.0001-20%, ZrO 2 0 -20%, La 2 O 3 + Nb 2 O 5 0-10%.
  • the reason for limiting the content range of each component as described above will be described below.
  • % represents the mass% unless there is particular notice.
  • the content of SiO 2 is 30 to 60%.
  • the upper limit of the content of SiO 2 is 60% or less, preferably 50% or less, 48% or less, 45% or less, and particularly 43% or less.
  • the lower limit of the content of SiO 2 is 30% or more, preferably 35% or more, 38% or more, particularly 40% or more.
  • the content of B 2 O 3 is 0 to 15%.
  • the upper limit of the content of B 2 O 3 is 15% or less, preferably 10% or less, 8% or less, and particularly 6% or less.
  • the preferable lower limit content of B 2 O 3 is 0.1% or more, 0.5% or more, 1% or more, 1.5% or more, 2% or more, 3% or more, particularly 4% or more.
  • the mass ratio B 2 O 3 / SiO 2 is preferably 0 to 1.
  • the preferable upper limit range of the mass ratio B 2 O 3 / SiO 2 is 1 or less, 0.5 or less, 0.2 or less, 0.15 or less, particularly 0.13 or less.
  • the preferable lower limit range of the mass ratio B 2 O 3 / SiO 2 is 0.01 or more, 0.02 or more, 0.03 or more, 0.04 or more, 0.05 or more, and particularly 0.10 or more.
  • the content of Al 2 O 3 is 0 to 15%.
  • the upper limit of the content of Al 2 O 3 is 15% or less, preferably 10% or less, 8% or less, and particularly 6% or less.
  • a suitable lower limit content of Al 2 O 3 is 0.5% or more, 1% or more, 2% or more, particularly 4% or more.
  • the content of Li 2 O is 0 to 10%.
  • the upper limit of the content of Li 2 O is 10% or less, preferably 8% or less, 5% or less, 4% or less, 3% or less, less than 2%, 1% or less, particularly less than 1%, It is desirable not to contain substantially.
  • substantially does not contain Li 2 O refers to a case where the content of Li 2 O in the glass composition is less than 1000 ppm (mass).
  • the content of Na 2 O is 0 to 10%.
  • the upper limit of the content of Na 2 O is 10% or less, preferably 8% or less, 5% or less, 4% or less, 3% or less, less than 2%, 1% or less, particularly less than 1%, It is desirable not to contain substantially.
  • substantially does not contain Na 2 O refers to a case where the content of Na 2 O in the glass composition is less than 1000 ppm (mass).
  • the content of K 2 O is 0 to 10%.
  • the upper limit of the content of K 2 O is 10% or less, preferably 8% or less, 5% or less, 4% or less, 3% or less, less than 2%, 1% or less, particularly less than 1%, It is desirable not to contain substantially.
  • “substantially does not contain K 2 O” refers to a case where the content of K 2 O in the glass composition is less than 1000 ppm (mass).
  • the content of Li 2 O + Na 2 O + K 2 O is preferably 0 to 10%.
  • the content of Li 2 O + Na 2 O + K 2 O increases, the liquid phase viscosity tends to decrease, and the strain point tends to decrease.
  • the glass tends to become cloudy due to the elution of alkali components in the acid etching step. Therefore, the upper limit of the content of Li 2 O + Na 2 O + K 2 O is 10% or less, 8% or less, 5% or less, 4% or less, 3% or less, 2% or less, 1% or less, particularly less than 1%, It is desirable not to contain substantially.
  • “substantially free of Li 2 O + Na 2 O + K 2 O” the content of Li 2 O + Na 2 O + K 2 O in the glass composition refers to a case of less than 1000 ppm (by weight).
  • the content of MgO is preferably 0 to 20%.
  • MgO is a component that raises the refractive index nd, Young's modulus, and strain point and lowers the high-temperature viscosity.
  • the preferable upper limit content of MgO is 20% or less, 10% or less, particularly 6% or less.
  • a suitable lower limit content of MgO is 0.1% or more, 0.5% or more, 1% or more, 1.5% or more, 2% or more, particularly 3% or more.
  • the CaO content is preferably 0 to 15%.
  • the suitable upper limit content of CaO is 15% or less, 13% or less, 11% or less, 9.5% or less, and particularly 8% or less.
  • a suitable lower limit content of CaO is 0.5% or more, 1% or more, and particularly 2% or more.
  • the SrO content is preferably 0 to 25%.
  • the preferable upper limit content of SrO is 25% or less, 18% or less, 14% or less, and particularly 12% or less.
  • the preferable lower limit content of SrO is 0.1% or more, 0.5% or more, 1% or more, 2% or more, 5% or more, 7% or more, particularly 9% or more.
  • BaO is a component that raises the refractive index nd without drastically reducing the viscosity of the glass among alkaline earth metal oxides, and its content is preferably 0.1 to 60%.
  • the preferable upper limit content of BaO is 60% or less, 53% or less, 48% or less, 44% or less, 40% or less, 39% or less, 36% or less, 35% or less, 34% or less, particularly 33% or less. It is.
  • the preferable upper limit content of BaO is 0.1% or more, 1% or more, 2% or more, 5% or more, 10% or more, 15% or more, 20% or more, 23% or more, particularly 25% or more. .
  • the content of ZnO is preferably 0 to 20%.
  • ZnO is a component that increases the refractive index nd and strain point, and is a component that lowers the high temperature viscosity.
  • the suitable upper limit content of ZnO is 20% or less, 10% or less, 5% or less, 3% or less, and particularly 1% or less.
  • the content of MgO + CaO + SrO + BaO + ZnO is 20 to 60%.
  • the upper limit of the content of MgO + CaO + SrO + BaO + ZnO is 60% or less, preferably 55% or less, 50% or less, 48% or less, and particularly 45% or less.
  • the lower limit of the content of MgO + CaO + SrO + BaO + ZnO is 20% or more, preferably 30% or more, 35% or more, particularly 40% or more.
  • TiO 2 is a component that increases the refractive index nd.
  • the content of TiO 2 is 0.0001 to 20%.
  • the upper limit of the content of TiO 2 is 20% or less, preferably 10% or less, 7% or less, particularly 5% or less.
  • the lower limit of the content of TiO 2 is 0.0001% or more, preferably 0.001% or more, 0.01% or more, 0.02% or more, 0.05% or more, 0.1% or more, 1% or more, particularly 2% or more.
  • ZrO 2 is a component that increases the refractive index nd.
  • the content of ZrO 2 is 0 to 20%.
  • the upper limit of the content of ZrO 2 is 20% or less, preferably 10% or less, 7% or less, particularly 5% or less.
  • the preferred lower limit content of ZrO 2 is 0.0001% or more, preferably 0.001% or more, 0.01% or more, 0.02% or more, 0.05% or more, 0.1% or more. 1% or more, particularly 2% or more.
  • La 2 O 3 is a component that increases the refractive index nd.
  • the content of La 2 O 3 is preferably 0 to 10%.
  • the suitable upper limit content of La 2 O 3 is 10% or less, 5% or less, 3% or less, 2.5% or less, particularly 1% or less.
  • Nb 2 O 5 is a component that increases the refractive index nd.
  • the content of Nb 2 O 5 is preferably 0 to 10%.
  • a suitable upper limit content of Nb 2 O 5 is 10% or less, 5% or less, 3% or less, particularly 1% or less.
  • the content of Gd 2 O 3 is preferably 0 to 10%.
  • Gd 2 O 3 is a component that increases the refractive index nd.
  • a suitable upper limit content of Gd 2 O 3 is 10% or less, 5% or less, 3% or less, particularly 1% or less.
  • the content of La 2 O 3 + Nb 2 O 5 is 0 to 10%.
  • the content of La 2 O 3 + Nb 2 O 5 is increased, the density and the thermal expansion coefficient are likely to be increased, the devitrification resistance is likely to be lowered, and further, it is difficult to ensure a high liquid phase viscosity. Moreover, raw material cost rises and the manufacturing cost of a glass plate tends to rise. Therefore, the upper limit of the content of La 2 O 3 + Nb 2 O 5 is 10% or less, preferably 8% or less, 5% or less, 3% or less, 1% or less, 0.5% or less, particularly 0.1%. % Or less.
  • the total content of rare metal oxides is preferably 0 to 10%.
  • the preferable upper limit content of the rare metal oxide is 10% or less, 5% or less, 3% or less, and particularly 1% or less.
  • a fining agent 0 to 3% of one or more selected from the group of As 2 O 3 , Sb 2 O 3 , CeO 2 , SnO 2 , F, Cl, and SO 3 can be added. However, it is preferable to refrain from using As 2 O 3 , Sb 2 O 3 , and F as much as possible from an environmental viewpoint, and each content is preferably less than 0.1%. Considering the above points, SnO 2 , SO 3 , Cl, and CeO 2 are preferable as the fining agent.
  • the content of SnO 2 is preferably 0 to 1%, 0.001 to 1%, particularly 0.01 to 0.5%.
  • the content of SO 3 is preferably 0 to 1%, 0 to 0.5%, 0.001 to 0.1%, 0.005 to 0.1%, 0.01 to 0.1%, especially 0. 0.01 to 0.05%.
  • a material for introducing SO 3 sodium sulfate may be used.
  • the Cl content is preferably 0 to 1%, 0.001 to 0.5%, particularly 0.01 to 0.4%.
  • SnO 2 + SO 3 + Cl The content of SnO 2 + SO 3 + Cl is preferably 0 to 1%, 0.001 to 1%, 0.01 to 0.5%, especially 0.01 to 0.3%.
  • SnO 2 + SO 3 + Cl refers to the total amount of SnO 2 , SO 3 , and Cl.
  • the CeO 2 content is preferably 0 to 6%.
  • the preferable upper limit content of CeO 2 is 6% or less, 5% or less, 3% or less, 2% or less, particularly 1% or less.
  • the preferable lower limit content of CeO 2 is 0.001% or more, 0.005% or more, 0.01% or more, 0.05% or more, particularly 0.1% or more.
  • PbO is a component that lowers the high temperature viscosity, but it is preferable to refrain from using it as much as possible from an environmental point of view.
  • the content of PbO is preferably 0.5% or less, and desirably not substantially contained.
  • substantially does not contain PbO refers to a case where the content of PbO in the glass composition is less than 1000 ppm (mass).
  • a suitable glass composition range by combining a suitable content range of each component.
  • preferred glass composition ranges are as follows. (1) By mass%, SiO 2 30-60%, B 2 O 3 0-15%, Al 2 O 3 0-15%, Li 2 O 0-10%, Na 2 O 0-10%, K 2 O 0-10%, MgO + CaO + SrO + BaO + ZnO 20-60%, TiO 2 0.1-20%, ZrO 2 0-20%, La 2 O 3 + Nb 2 O 5 0-10% contained, (2) By mass%, SiO 2 35-45%, B 2 O 3 2-8%, Al 2 O 3 4-8%, Li 2 O 1-8%, Na 2 O 0-5%, K 2 O 0-8%, MgO + CaO + SrO + BaO + Zn30-48%, TiO 2 1-7%, ZrO 2 0.1-5%, La 2 O 3 + Nb 2 O 5 0-5%.
  • the refractive index nd is 1.55 or more, preferably 1.58 or more, 1.60 or more, particularly 1.63 or more. If the refractive index nd is less than 1.55, light cannot be extracted efficiently due to reflection at the transparent conductive film-glass plate interface. On the other hand, when the refractive index nd is higher than 2.3, the reflectance at the air-glass plate interface increases, and it becomes difficult to extract light to the outside even if the glass surface is roughened. Therefore, the refractive index nd is 2.3 or less, preferably 2.2 or less, 2.1 or less, 2.0 or less, 1.9 or less, particularly 1.75 or less.
  • the density is preferably 5.0 g / cm 3 or less, 4.8 g / cm 3 or less, 4.5 g / cm 3 or less, 4.3 g / cm 3 or less. 7 g / cm 3 or less, 3.5 g / cm 3 or less, particularly 3.4 g / cm 3 or less. In this way, the device can be reduced in weight.
  • the thermal expansion coefficient at 30 to 380 ° C. is preferably 45 ⁇ 10 ⁇ 7 to 110 ⁇ 10 ⁇ 7 / ° C., 50 ⁇ 10 ⁇ 7 to 100 ⁇ 10 ⁇ 7 / ° C. 60 ⁇ 10 ⁇ 7 to 95 ⁇ 10 ⁇ 7 / ° C., 65 ⁇ 10 ⁇ 7 to 90 ⁇ 10 ⁇ 7 / ° C., 65 ⁇ 10 ⁇ 7 to 85 ⁇ 10 ⁇ 7 / ° C., especially 67 ⁇ 10 ⁇ 7 to 80 ⁇ 10 ⁇ 7 / ° C.
  • the strain point is preferably 600 ° C. or higher, particularly 630 ° C. or higher.
  • a device such as an organic thin film solar cell
  • conventional high refractive index glass has insufficient heat resistance, it has been difficult to achieve both transparency and low electrical resistance. Therefore, when the strain point is within the above range, in a device such as an organic thin film solar cell, both transparency and low electrical resistance can be achieved, and the glass is less likely to be thermally contracted by heat treatment in the device manufacturing process.
  • the temperature at 10 2.5 dPa ⁇ s is preferably 1450 ° C. or lower, 1400 ° C. or lower, 1350 ° C. or lower, 1300 ° C. or lower, 1250 ° C. or lower, particularly 1200 ° C. or lower. . If it does in this way, since meltability will improve, the manufacturing efficiency of glass will improve.
  • the liquidus temperature is preferably 1200 ° C. or lower, 1150 ° C. or lower, 1130 ° C. or lower, 1110 ° C. or lower, 1090 ° C. or lower, 1050 ° C. or lower, 1050 ° C. or lower, 1040 ° C. or lower, 1000 ° C. or lower, particularly 980 ° C. or lower.
  • the liquid phase viscosity is preferably 10 3.5 dPa ⁇ s or more, 10 3.8 dPa ⁇ s or more, 10 4.0 dPa ⁇ s or more, 10 4.2 dPa ⁇ s or more, 10 4.4 dPa or more.
  • the high refractive index glass of the second embodiment is preferably plate-shaped.
  • the thickness (in the case of a plate shape) is preferably 1.5 mm or less, 1.3 mm or less, 1.1 mm or less, 0.8 mm or less, 0.6 mm or less, 0.5 mm or less, 0.3 mm or less. 0.2 mm or less, particularly 0.1 mm or less.
  • the thickness is preferably 10 ⁇ m or more, particularly 30 ⁇ m or more.
  • the high refractive index glass of the second embodiment is plate-shaped, it is preferable that at least one surface has an unpolished surface (particularly, the entire effective surface of at least one surface is unpolished).
  • the theoretical strength of glass is inherently very high, but breakage often occurs even at a stress much lower than the theoretical strength. This is because a small defect called Griffith flow occurs on the glass surface in a post-molding process such as a polishing process. Therefore, if the glass surface is unpolished, the mechanical strength of the original glass is hardly impaired, and thus the glass is difficult to break. Further, since the polishing step can be simplified or omitted, the manufacturing cost of the glass plate can be reduced.
  • the surface roughness Ra of the unpolished surface is preferably 10 mm or less, 5 mm or less, 3 mm or less, particularly 2 mm or less.
  • the surface roughness Ra is larger than 10 mm, the quality of the transparent conductive film formed on the surface is lowered, and it becomes difficult to obtain uniform light emission.
  • the high refractive index glass of the second embodiment is preferably formed by a downdraw method, particularly an overflow downdraw method.
  • a downdraw method particularly an overflow downdraw method.
  • the surface to be the surface is not in contact with the bowl-shaped refractory and is molded in a free surface state.
  • the structure and material of the bowl-shaped structure are not particularly limited as long as desired dimensions and surface accuracy can be realized. Further, there is no particular limitation on the method for applying force to the molten glass in order to perform downward stretching.
  • a method of rotating and stretching a heat-resistant roll having a sufficiently large width in contact with the molten glass may be adopted, or a plurality of pairs of heat-resistant rolls may be used only in the vicinity of the end face of the molten glass.
  • a slot downdraw method can be employed as the downdraw method. If it does in this way, it will become easy to produce a glass plate with small board thickness.
  • the “slot down draw method” is a method of forming a glass plate by drawing and forming molten glass from a substantially rectangular gap while drawing it downward.
  • the high refractive index glass of the second embodiment is preferably formed by a float method. In this way, a large glass plate can be produced at a low cost and in large quantities.
  • a redraw method for example, a float method, a roll-out method, etc. can be employed.
  • the high refractive index glass of the second embodiment is preferably subjected to a roughening treatment on one surface by HF etching, sandblasting, or the like.
  • the surface roughness Ra of the roughened surface is preferably 10 mm or more, 20 mm or more, 30 mm or more, particularly 50 mm or more. If the roughened surface is in contact with the air such as organic EL lighting, the roughened surface has a non-reflective structure, so that the light generated in the organic light emitting layer is difficult to return to the organic light emitting layer. As a result, the light extraction efficiency can be increased. Moreover, you may give uneven
  • the surface roughening process is performed by an atmospheric pressure plasma process, the surface state of one surface can be maintained and the surface roughening process can be uniformly performed on the other surface.
  • a gas containing F for example, SF 6 , CF 4
  • plasma containing HF gas is generated, the efficiency of the roughening treatment is improved.
  • a method of forming an uneven shape on one surface during molding is also preferable. In this case, a separate roughening process becomes unnecessary, and the efficiency of the roughening process is improved.
  • glass raw materials are prepared so as to obtain a desired glass composition, and a glass batch is prepared.
  • the glass batch is melted and refined, and then formed into a desired shape. Thereafter, it is processed into a desired shape.
  • Tables 5 to 12 show examples of the second invention (sample Nos. 20 to 55) and comparative examples (sample No. 56).
  • the obtained glass batch was supplied to a glass melting furnace and melted at 1500 ° C. for 4 hours.
  • the obtained molten glass was poured onto a carbon plate, formed into a plate shape, and then subjected to a predetermined annealing treatment. Finally, various characteristics of the obtained glass plate were evaluated.
  • the refractive index nd is a 25 mm ⁇ 25 mm ⁇ about 3 mm cuboid sample, and the temperature range from (annealing point Ta + 30 ° C.) to (strain point Ps ⁇ 50 ° C.) is 0.1 ° C./min cooling rate. This is a value measured by a refractive index measuring instrument KPR-2000 manufactured by Shimadzu Corporation while an immersion liquid in which the refractive index nd matches is infiltrated between the glasses.
  • the density is a value measured by the well-known Archimedes method.
  • the thermal expansion coefficient is a value obtained by measuring an average thermal expansion coefficient at 30 to 380 ° C. using a dilatometer.
  • a cylindrical sample having a diameter of 5 mm ⁇ 20 mm (the end surface is R-processed) was used.
  • the strain point Ps is a value measured by the method described in ASTM C336-71. In addition, heat resistance becomes high, so that the strain point Ps is high.
  • the annealing point Ta and the softening point Ts are values measured by the method described in ASTM C338-93.
  • the temperatures at high temperature viscosities of 10 4.0 dPa ⁇ s, 10 3.0 dPa ⁇ s, 10 2.5 dPa ⁇ s, and 10 2.0 dPa ⁇ s are values measured by the platinum ball pulling method. In addition, it is excellent in meltability, so that these temperatures are low.
  • the liquid phase temperature TL passes through a standard sieve 30 mesh (500 ⁇ m), and the glass powder remaining in 50 mesh (300 ⁇ m) is placed in a platinum boat and held in a temperature gradient furnace for 24 hours to measure the temperature at which crystals precipitate. It is the value. Further, the liquidus viscosity log 10 ⁇ TL is a value obtained by measuring the viscosity of glass at the liquidus temperature by a platinum ball pulling method. The higher the liquidus viscosity and the lower the liquidus temperature, the better the devitrification resistance and moldability.
  • the HCl resistance was evaluated by the following method. First, after both surfaces of each glass sample were optically polished, a part thereof was masked, and then chemical treatment was performed under the following conditions. After the chemical treatment, the mask was removed, and the level difference between the mask portion and the erosion portion was measured with a surface roughness meter, and the value was taken as the erosion amount.
  • the HCl resistance (erosion amount) is evaluated as “X” when the erosion amount exceeds 20 ⁇ m, and “ ⁇ ” when the erosion amount is 20 ⁇ m or less.
  • the treatment conditions for HCl resistance are immersed in a 10% by mass HCl aqueous solution at 80 ° C. for 24 hours, and the treatment conditions for HCl resistance (appearance) are immersed in a 10% by mass HCl aqueous solution at 80 ° C. for 24 hours. It is.
  • sample No. Nos. 20 to 55 did not substantially contain an alkali component and a rare metal oxide, had a refractive index nd of 1.623 or more, and had good acid resistance.
  • Sample No. Nos. 20, 24, 27 to 37, 39, 43 to 45, and 47 to 55 had liquid phase viscosities of 10 3.4 dPa ⁇ s or more.
  • it approximates the thermal expansion coefficient of the transparent conductive film it is expected that the warpage of the glass plate can be suppressed.
  • sample No. No. 56 contained a large amount of rare metal oxide in the glass composition, so that the density was high and the acid resistance was low.
  • the high refractive index glass of the present invention has a refractive index nd of 1.55 or more and a high liquidus viscosity. And from a viewpoint of raw material cost, it is possible to remove a rare metal oxide from the glass composition, and from an environmental viewpoint, it is also possible to remove As 2 O 3 , Sb 2 O 3 and the like from the glass composition. Therefore, the high refractive index glass of the present invention is suitable for an organic EL device substrate, particularly an organic EL lighting substrate.
  • the high refractive index glass of the present invention includes a flat panel display substrate such as a liquid crystal display, a cover glass of an image sensor such as a charge coupled device (CCD) and a 1 ⁇ close proximity solid-state imaging device (CIS), and a substrate for a solar cell. Etc. can also be used.
  • a flat panel display substrate such as a liquid crystal display
  • a cover glass of an image sensor such as a charge coupled device (CCD) and a 1 ⁇ close proximity solid-state imaging device (CIS)
  • CCD charge coupled device
  • CIS 1 ⁇ close proximity solid-state imaging device

Abstract

Le verre à indice de réfraction élevé selon la présente invention est caractérisé par sa composition qui est la suivante, en termes de % en poids, 0 à 10 % de B2O3, 0,001 à 35 % de SrO, 0,001 à 30 % de ZrO2+TiO2 et 0 à 10 % de La2O3+Nb2O5, le rapport pondéral BaO/SrO variant de 0 à 40 et le rapport pondéral SiO2/SrO variant de 0,1 à 40. Ledit verre est caractérisé par un indice de réfraction nd égal à 1,55 à 2,3.
PCT/JP2012/062610 2011-05-18 2012-05-17 Verre à indice de réfraction élevé WO2012157695A1 (fr)

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TW201307238A (zh) 2013-02-16
CN103492331A (zh) 2014-01-01
DE112012002137T5 (de) 2014-03-06

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