WO2015186606A1 - Verre à phases séparées, verre à phases séparables, dispositif el organique et procédé de production de verre à phases séparées - Google Patents

Verre à phases séparées, verre à phases séparables, dispositif el organique et procédé de production de verre à phases séparées Download PDF

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WO2015186606A1
WO2015186606A1 PCT/JP2015/065449 JP2015065449W WO2015186606A1 WO 2015186606 A1 WO2015186606 A1 WO 2015186606A1 JP 2015065449 W JP2015065449 W JP 2015065449W WO 2015186606 A1 WO2015186606 A1 WO 2015186606A1
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phase
glass
less
separated
phase separation
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PCT/JP2015/065449
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English (en)
Japanese (ja)
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篤 虫明
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日本電気硝子株式会社
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Priority claimed from JP2014113865A external-priority patent/JP2015227273A/ja
Priority claimed from JP2014113864A external-priority patent/JP2015227272A/ja
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Publication of WO2015186606A1 publication Critical patent/WO2015186606A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—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
    • C03C3/089—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
    • C03C4/00—Compositions for glass with special properties
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
    • Y02P40/57—Improving the yield, e-g- reduction of reject rates

Definitions

  • the present invention relates to a phase separation glass, a phase separation glass, an organic EL device, and a method for producing a phase separation glass.
  • the light source for illumination is divided into a “directional light source” that illuminates a limited area and a “diffuse light source” that illuminates a wide area.
  • LED lighting corresponds to a “directional light source” and is being adopted as an alternative to an incandescent bulb.
  • an alternative light source for a fluorescent lamp corresponding to a “diffusion light source” is desired, and organic EL (electroluminescence) illumination is a promising candidate.
  • the organic EL element includes a glass plate, a transparent conductive film as an anode, an organic EL layer including an organic compound exhibiting electroluminescence that emits light by current injection, and a cathode, and a cathode. It is an element.
  • As the organic EL layer used in the organic EL element a low molecular dye material, a conjugated polymer material or the like is used.
  • a hole injection layer, a hole transport layer, an electron transport layer, an electron injection A laminated structure with layers and the like is formed.
  • An organic EL layer having such a laminated structure is disposed between the anode and the cathode, and by applying an electric field to the anode and the cathode, holes injected from the transparent electrode that is the anode and those injected from the cathode The electrons recombine in the light emitting layer, and the emission center is excited by the recombination energy to emit light.
  • Organic EL elements are being studied for use in mobile phones and displays, and some have already been put into practical use.
  • the organic EL element has a luminous efficiency equivalent to that of a thin television such as a liquid crystal display or a plasma display.
  • Patent Document 1 a light extraction layer in which a glass frit having a high refractive index is sintered is formed on the surface of a soda glass plate, and a scattering substance is dispersed in the light extraction layer, thereby reducing the light extraction efficiency. It is also described to increase.
  • the present invention has been made in view of the above circumstances, and its technical problem is that the light extraction efficiency of the organic EL element can be increased without forming a light extraction layer made of a sintered body, and Provide glass with excellent productivity.
  • phase separation glass having a high refractive index and restricting the total light transmittance to a predetermined range, and proposes the present invention.
  • the refractive index n d is 1.55 or more, and having a phase separation structure comprising at least a first phase and a second phase.
  • “refractive index n d ” refers to the value of the d-line measured by a refractive index measuring device.
  • a rectangular parallelepiped sample of 25 mm ⁇ 25 mm ⁇ about 3 mm is first prepared, and is slowly cooled at a cooling rate of 0.1 ° C./min in the temperature range from (annealing point Ta + 30 ° C.) to (strain point Ps ⁇ 50 ° C.).
  • the refractive index n d is aligned, it can be measured by the refractive index measuring instrument KPR-2000 of Shimadzu Corporation (hereinafter, the same).
  • the light scattering accompanying formation of a 1st phase and a 2nd phase can be confirmed visually.
  • the details of each phase can be confirmed by observing the surface of the sample after being immersed in a 1M hydrochloric acid solution for 10 minutes with a scanning electron microscope.
  • the phase-separated glass of the present invention is characterized by having a phase-separated structure including at least a first phase and a second phase.
  • a phase-separated structure including at least a first phase and a second phase.
  • the refractive index n d is 1.55 or more.
  • the refractive index n d of the transparent conductive film is 1.9 to 2.0, and the refractive index n d of the organic EL layer was 1.8-1.9.
  • the refractive index n d of the glass plate was typically about 1.50.
  • the refractive index nd is regulated as described above, so that the difference in refractive index between the glass plate and the transparent conductive film is reduced, so that light incident from the organic EL layer is reflected at the interface between the glass plate and the transparent conductive film. Light extraction efficiency can be increased.
  • the difference between the maximum value and the minimum value of the total light transmittance at a wavelength of 400 to 700 nm is preferably 40% or less.
  • phase-separated glass When phase-separated glass is used, short-wavelength light is scattered more strongly than long-wavelength light due to Rayleigh scattering, and when an organic EL element, particularly a white OLED, is produced, the viewing angle dependency of the color increases, and lighting applications There is a risk of becoming unsuitable. Therefore, the phase separation glass of the present invention regulates the total light transmittance as described above in order to eliminate such problems.
  • the difference between the maximum value and the minimum value of the total light transmittance at wavelengths of 400 to 700 nm can be reduced by regulating the particle size of the phase-separated particles within a predetermined range and causing a scattering phenomenon due to Mie scattering. it can.
  • the “total light transmittance” is a value measured in the thickness direction with a spectrophotometer (for example, UV-2500PC manufactured by Shimadzu Corporation). For example, glass whose both surfaces are mirror-polished is used as a measurement sample. be able to.
  • the phase separation glass of the present invention preferably has a diffuse transmittance of 10% or more at a wavelength of 400 to 700 nm.
  • diffuse transmittance is a value measured in the thickness direction with a spectrophotometer (for example, UV-2500PC manufactured by Shimadzu Corporation).
  • a spectrophotometer for example, UV-2500PC manufactured by Shimadzu Corporation.
  • glass whose both surfaces are mirror-polished is used as a measurement sample. Can do.
  • the phase separation glass of the present invention preferably has a wavelength having a haze value of 5% or more at a wavelength of 400 to 700 nm. If it does in this way, since it will become easy to scatter light in glass, it will become easy to take out light outside, and it will become easy to raise light extraction efficiency as a result.
  • the “haze value” is a value calculated by (diffuse transmittance) ⁇ 100 / (total light transmittance).
  • the phase separation glass of the present invention preferably has a total light transmittance of 10% or more at a wavelength of 400 to 700 nm.
  • the phase-separated glass of the present invention preferably has an average particle diameter of phase-separated particles of 100 nm or more.
  • phase-separated glass of the present invention preferably has a refractive index n d is less than 1.65.
  • the phase-separated glass of the present invention is composed of 30 to 75% of SiO 2 , 0.1 to 50% of B 2 O 3 , and Al 2 O 3 0 to 35 as a glass composition. % Is preferably contained. If it does in this way, it will become easy to raise a refractive index and it will become easy to raise productivity of a glass plate.
  • the phase-separated glass of the present invention does not substantially contain a rare metal oxide in the glass composition.
  • rare metal oxide refers to rare earth oxides such as La 2 O 3 , Nd 2 O 3 , Gd 2 O 3 , and CeO 2 , Y 2 O 3 , Nb 2 O 5 , and Ta 2 O 5 .
  • are metal oxide refers to the case where the content of the rare metal oxide in the glass composition is 0.1% by mass or less.
  • the content of SiO 2 in the first phase is preferably larger than the content of SiO 2 in the second phase. If it does in this way, the refractive index of a 1st phase and a 2nd phase will become easy to differ, and the scattering function of glass can be improved.
  • the content of the second of B 2 O 3 in the phase is preferably larger than the content of B 2 O 3 in the first phase. If it does in this way, the refractive index of a 1st phase and a 2nd phase will become easy to differ, and the scattering function of glass can be improved.
  • the phase-separated glass of the present invention preferably has a P 2 O 5 content of 0.001 to 10% by mass in the glass composition.
  • the mass ratio (Al 2 O 3 + B 2 O 3 ) / SiO 2 in the glass composition is preferably 0.3 or more.
  • the phase separation glass of the present invention preferably has a mass ratio TiO 2 / B 2 O 3 in the glass composition of 0.01 to 2.
  • the phase-separated glass of the present invention preferably has a BaO—SrO content of 1 to 12% by mass in the glass composition.
  • the phase separation glass of the present invention has a flat plate shape.
  • the phase separation glass of the present invention preferably has a thickness of 5 to 500 ⁇ m.
  • the organic EL device of the present invention is characterized by comprising the above phase separation glass.
  • the organic EL device of the present invention is preferably illumination.
  • phase-separated glass of the present invention After the refractive index n d is molded more than 1.55 min chemistry glass, by heat-treating phase separation glass obtained, at least a first phase And a phase-separated glass having a phase-separated structure including the second phase. If it does in this way, in order to obtain a phase separation glass by heat-processing a phase separation glass, it becomes easy to control a phase separation structure. In particular, if the element structure of the organic EL device is different, the optimal phase separation structure will also be different, but from the same phase separation glass, the optimum phase separation structure for the element structure of the organic EL device can be obtained simply by adjusting the heat treatment conditions. Obtainable.
  • phase-separating glass refers to glass that has not yet phase-separated but has a property of phase-separating by heat treatment at 1100 ° C. or lower.
  • the refractive index n d is molded phase separation glass of less than 1.65.
  • the method for producing a phase separation glass of the present invention preferably forms the phase separation glass into a flat plate shape.
  • the refractive index n d is not less than 1.55, and when subjected to heat treatment 800 ° C. 24 hours, the state where no phase separation, at least a first phase And the second phase.
  • Sample No. after heat treatment according to Example 2 This is data obtained by mirror-polishing both surfaces of 1 (plate thickness: 1.0 mm) and measuring the total light transmittance and diffuse transmittance in the thickness direction with a spectrophotometer.
  • Sample No. 2 according to Example 2. 1 is an image obtained by observing the obtained sample surface with a scanning electron microscope after 1 was immersed in a 1M hydrochloric acid solution for 10 minutes.
  • Sample No. after heat treatment according to Example 3 8 is an image obtained by immersing 8 in a 1M hydrochloric acid solution for 10 minutes and observing the obtained sample surface with a scanning electron microscope.
  • Example 3 8 is a data obtained by mirror-polishing both surfaces of 8 (plate thickness 1.0 mm) and measuring the total light transmittance and diffuse transmittance in the thickness direction with a spectrophotometer. It is the data which measured the total light transmittance and diffuse transmittance of the thickness direction about the composite substrate which concerns on Example 4 (plate thickness of 0.3 mm of a phase separation glass plate, total plate thickness of 2.3 mm) with the spectrophotometer. . It is the data which measured the total light transmittance and diffuse transmittance of the thickness direction about the composite substrate which concerns on Example 4 (plate thickness of the phase separation glass plate 0.1mm, total plate thickness 2.1mm) with the spectrophotometer. . Sample No.
  • Example 6 It is the image which observed the sample surface obtained by immersing 17 in 1M hydrochloric acid solution for 10 minutes with the scanning electron microscope.
  • Sample No. 6 in Example 6 20 is an image obtained by immersing 20 in a 1M hydrochloric acid solution for 10 minutes and then observing the obtained sample surface with a scanning electron microscope.
  • Sample No. 6 in Example 6 22 shows an image obtained by immersing 22 in a 1M hydrochloric acid solution for 10 minutes and then observing the obtained sample surface with a scanning electron microscope.
  • Sample No. 6 in Example 6 23 is an image obtained by observing the obtained sample surface with a scanning electron microscope after 23 was immersed in a 1M hydrochloric acid solution for 10 minutes.
  • Example 7 This is data obtained by mirror-polishing both surfaces of 20 (plate thickness 0.7 mm) and measuring the total light transmittance and diffuse transmittance in the thickness direction with a spectrophotometer.
  • Sample No. 7 in Example 7 This is data obtained by mirror-polishing both surfaces of 21 (plate thickness 0.7 mm) and measuring the total light transmittance and diffuse transmittance in the thickness direction with a spectrophotometer.
  • Sample No. 7 in Example 7 This is data obtained by mirror-polishing both surfaces of 22 (plate thickness 0.7 mm) and measuring the total light transmittance and diffuse transmittance in the thickness direction with a spectrophotometer.
  • Sample No. 7 in Example 7 This is data obtained by mirror-polishing both surfaces of 23 (plate thickness 0.7 mm) and measuring the total light transmittance and diffuse transmittance in the thickness direction with a spectrophotometer.
  • the phase separation glass of the present invention is characterized by having a phase separation structure including at least a first phase and a second phase.
  • the content of SiO 2 in the first phase is preferably larger than the content of SiO 2 in the second phase. If in the glass composition containing B 2 O 3, B 2 O 3 content in the second phase is preferably larger than the content of B 2 O 3 in the first phase. If it does in this way, the refractive index of a 1st phase and a 2nd phase will become easy to differ, and the scattering function of glass can be improved.
  • the refractive index n d is 1.55 or more, preferably 1.56 or more, 1.57 or more, 1.58 or more, 1.59 or more, 1.60 or more, 1. 61 or more and 1.62 or more, particularly preferably 1.63 or more.
  • the refractive index n d is less than 1.55, it becomes difficult to efficiently extract light by reflection at the interface, such as a glass plate and a transparent conductive film.
  • the refractive index n d is too high, since the introduction of the components to improve the devitrification resistance is limited, the liquidus viscosity becomes difficult to prepare a high glass plate.
  • the refractive index n d is preferably 2.30 or less, 2.00 or less, 1.80 or less, in particular less than 1.65.
  • the difference between the maximum value and the minimum value of the total light transmittance at a wavelength of 400 to 700 nm is preferably 40% or less, 30% or less, 20% or less, and 10% or less, particularly preferably. Is 5% or less.
  • the difference between the maximum value and the minimum value of the total light transmittance at a wavelength of 400 to 700 nm is too large, a scattering phenomenon due to Rayleigh scattering occurs. In this case, when an organic EL element, particularly a white OLED is manufactured. In addition, the viewing angle dependency of color increases.
  • the average particle size of the phase-separated particles of at least one phase is preferably 100 nm or more, 200 nm or more, 300 nm or more, 400 to 5000 nm.
  • the thickness is preferably 600 to 3000 nm. In this way, a scattering phenomenon due to Mie scattering is likely to occur, and the wavelength dependency of the total light transmittance is easily reduced.
  • the average particle size of the phase-separated particles can be adjusted by the glass composition, molding conditions, slow cooling conditions, heat treatment temperature, heat treatment time, and the like.
  • Phase-separated glass of the present invention has a glass composition, in mass%, SiO 2 30 ⁇ 75% , Al 2 O 3 0 ⁇ 35%, preferably contains 2 O 3 0.1 ⁇ 50% B .
  • % display means the mass%.
  • the content of SiO 2 is preferably 30 to 75%.
  • the content of SiO 2 is preferably 75% or less, 70% or less, 65% or less, 60% or less, 55% or less, 50% or less, 45% or less, 42% or less, 40% or less, Preferably it is less than 40%.
  • the content of SiO 2 is preferably 30% or more, 32% or more, 34% or more, and particularly preferably 36% or more.
  • the content of Al 2 O 3 is preferably 0 to 35%.
  • Al 2 O 3 is a component that enhances devitrification resistance. However, if the content of Al 2 O 3 is too large, the phase separation is liable to decrease, and the component balance of the glass composition is impaired. Conversely, devitrification resistance tends to decrease. Moreover, acid resistance tends to decrease. Therefore, the content of Al 2 O 3 is preferably 35% or less, 30% or less, 25% or less, 20% or less, 15% or less, 12% or less, 10% or less, and particularly preferably 8% or less. is there.
  • the content of Al 2 O 3 is preferably 0.1% or more, 3% or more and 4% or more, particularly preferably 5% or more.
  • the content of B 2 O 3 is preferably 0.1 to 50%.
  • B 2 O 3 is a component that enhances phase separation, but if the content of B 2 O 3 is too large, the component balance of the glass composition is impaired, and devitrification resistance is likely to decrease. The acid resistance tends to decrease. Therefore, the content of B 2 O 3 is preferably 50% or less, 40% or less, 30% or less, 25% or less, 20% or less, or 17% or less, and particularly preferably 15% or less. Further, the content of B 2 O 3 is preferably 0.1% or more, 0.5% or more, 1% or more, 4% or more, 7% or more, 9% or more, particularly preferably 10% or more. is there.
  • the mass ratio (Al 2 O 3 + B 2 O 3 ) / SiO 2 is preferably 0.3 or more, 0.33 or more, 0.35 or more, 0.37 or more, 0.39 or more, 0.4 or more, 0 .41 or more, 0.42 or more, 0.43 to 0.7, 0.44 to 0.65, and particularly preferably 0.45 to 0.6. If it does in this way, it will become easy to improve a refractive index, phase separation, and devitrification resistance simultaneously.
  • “(Al 2 O 3 + B 2 O 3 ) / SiO 2 ” is a value obtained by dividing the total amount of Al 2 O 3 and B 2 O 3 by the content of SiO 2 .
  • the content of Li 2 O is preferably 0 to 30%.
  • Li 2 O is a component that enhances phase separation. However, if the content of Li 2 O is too large, the liquid phase viscosity tends to decrease and the strain point tends to decrease. Furthermore, the alkali component is easily eluted in the acid etching step. Therefore, the content of Li 2 O is preferably 30% or less, 20% or less, 10% or less, 5% or less, less than 1%, and particularly preferably 0.5% or less.
  • the content of Na 2 O is preferably 0-30%.
  • Na 2 O is a component that enhances the phase separation.
  • the content of Na 2 O is preferably 30% or less, 20% or less, 10% or less, 5% or less, less than 1%, and particularly preferably 0.5% or less.
  • the content of K 2 O is preferably 0 to 30%.
  • K 2 O is a component that enhances phase separation. However, if the content of K 2 O is too large, the liquid phase viscosity tends to decrease and the strain point tends to decrease. Furthermore, the alkali component is easily eluted in the acid etching step. Therefore, the content of K 2 O is preferably 30% or less, 20% or less, 10% or less, 5% or less, less than 1%, and particularly preferably 0.5% or less.
  • the content of MgO is preferably 0 to 30%.
  • MgO is a component that raises the refractive index, Young's modulus, and strain point and lowers the high-temperature viscosity.
  • the content of MgO is preferably 30% or less, 20% or less, 10% or less, 8% or less, 7% or less, 6% or less, 5% or less, 4% or less, 3% or less, 2% or less. Yes, particularly preferably less than 1%.
  • the content of MgO is preferably 0.1% or more, particularly preferably 0.9% or more.
  • the CaO content is preferably 0-30%.
  • CaO is a component that lowers the high-temperature viscosity. However, when the content of CaO increases, the density tends to increase, and the balance of components of the glass composition is impaired, and devitrification resistance tends to decrease. Therefore, the CaO content is preferably 30% or less, 20% or less, 10% or less, 8% or less, 5% or less, and particularly preferably 3% or less.
  • the CaO content is preferably 0.1% or more and 0.5% or more, and particularly preferably 1% or more.
  • the SrO content is preferably 0-30%. If the SrO content is increased, the refractive index and the density are likely to be increased, and the balance of components of the glass composition is impaired, so that the devitrification resistance is likely to be lowered. Therefore, the SrO content is preferably 30% or less, 25% or less, 20% or less, or 18% or less, and particularly preferably 15% or less. The SrO content is preferably 1% or more, 3% or more, 5% or more, 7% or more, 9% or more, and particularly preferably 10% or more.
  • BaO is a component that increases the refractive index of alkaline earth metal oxides without extremely reducing the viscosity of the glass.
  • the BaO content is preferably 40% or less, 30% or less, 26% or less, 24% or less, or 22% or less, and particularly preferably 20% or less.
  • the content of BaO is preferably 1% or more, more than 5%, more than 7%, 10% or more, 12% or more, 14% or more, and particularly preferably 16% or more.
  • MgO + CaO + SrO + BaO The content of MgO + CaO + SrO + BaO is preferably 25 to 40%, 28 to 37%, particularly preferably 30 to 35%, from the viewpoint of refractive index and devitrification resistance.
  • MgO + CaO + SrO + BaO refers to the total amount of MgO, CaO, SrO and BaO.
  • the content of BaO—SrO is preferably 1 to 12%, 2 to 11%, 3 to 10%, 4 to 9%, particularly preferably 5 to 8%. If it does in this way, it will become easy to improve devitrification resistance, maintaining a high refractive index.
  • BaO—SrO refers to a value obtained by subtracting the SrO content from the BaO content.
  • the content of ZnO is preferably 0 to 20%.
  • the content of ZnO is preferably 20% or less, 10% or less, 7% or less, 5% or less, and particularly preferably 4% or less.
  • the content of ZnO is preferably 0.1% or more, 0.5% or more, 1% or more, 1.5% or more, and particularly preferably 2% or more.
  • TiO 2 is a component that increases the refractive index, and its content is preferably 0 to 20%. However, when the content of TiO 2 is increased, the component balance of the glass composition is impaired, and the devitrification resistance is easily lowered. In addition, the total light transmittance may be reduced. Therefore, the content of TiO 2 is preferably 20% or less, 15% or less, 10% or less, and particularly preferably 8% or less. The content of TiO 2 is preferably 0.001% or more, 0.01% or more, 0.1% or more, 1% or more, 2% or more, 3% or more, 4% or more, particularly preferably 5% or more.
  • TiO 2 / B 2 O 3 is preferably 0.01 to 2 , 0.1 to 1.7, 0.15 to 1.4, 0.2 to 1.2, 0.25 to 1. Particularly preferred is 0.3 to 0.8. If it does in this way, it will become easy to make high refractive index and high phase separation compatible.
  • TiO 2 / B 2 O 3 is a value obtained by dividing the content of TiO 2 by the content of B 2 O 3 .
  • ZrO 2 is a component that increases the refractive index, and its content is preferably 0 to 20%. However, when the content of ZrO 2 increases, the component balance of the glass composition is impaired, and the devitrification resistance is likely to decrease. Therefore, the content of ZrO 2 is preferably 20% or less, 10% or less, and particularly preferably 5% or less. Further, the content of ZrO 2 is preferably 0.001% or more, 0.01% or more, 0.1% or more, 1% or more, 1.5% or more, and particularly preferably 2% or more.
  • P 2 O 5 is a component that increases phase separation, and its content is preferably 0 to 10%. However, when the content of P 2 O 5 is increased, the component balance of the glass composition is impaired, and the devitrification resistance is likely to be lowered. Therefore, the content of P 2 O 5 is preferably 10% or less, 7% or less, 4% or less, 3% or less, and particularly preferably 2% or less. Further, the content of P 2 O 5 is preferably 0.001% or more, 0.01% or more, 0.1% or more, 1% or more, 1.4% or more, particularly preferably 1.6%. That's it.
  • the mass ratio P 2 O 5 / (MgO + CaO) is preferably 0.1 or more, 0.2 or more, 0.3 or more, 0.4 or more, 0.5 or more, particularly preferably more than 0.6. .
  • P 2 O 5 / (MgO + CaO) is a value obtained by dividing the content of P 2 O 5 by the total amount of MgO and CaO.
  • La 2 O 3 is a component that increases the refractive index, and its content is preferably 0 to 10%.
  • the content of La 2 O 3 is preferably 10% or less, 5% or less, 3% 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, and its content is preferably 0 to 10%.
  • the content of Nb 2 O 5 increases, the density tends to increase and the devitrification resistance tends to decrease. Furthermore, the raw material cost rises, and the manufacturing cost of the glass plate is likely to rise. Therefore, the content of Nb 2 O 5 is preferably 10% or less, 5% or less, 3% or less, 1% or less, 0.5% or less, and particularly preferably 0.1% or less.
  • Gd 2 O 3 is a component that increases the refractive index, and its content is preferably 0 to 10%.
  • the content of Gd 2 O 3 is preferably 10% or less, 5% or less, 3% or less, 1% or less, 0.5% or less, and particularly preferably 0.1% or less.
  • the total content of rare metal oxides is preferably 0 to 10%.
  • Rare metal oxide is a component that increases the refractive index, but as the content of these components increases, the density and thermal expansion coefficient tend to increase, and devitrification resistance decreases, ensuring high liquid phase viscosity. It becomes difficult to do. Furthermore, the raw material cost rises, and the manufacturing cost of the glass plate is likely to rise. Therefore, the rare metal oxide content is preferably 10% or less, 5% or less, 3% or less, 1% or less, or 0.5% or less, and particularly preferably 0.1% or less.
  • the following oxide conversion means that an oxide having a valence different from the indicated oxide is handled after being converted to the indicated oxide.
  • the content of SnO 2 is preferably 0 to 1%, 0.001 to 1%, and particularly preferably 0.01 to 0.5%.
  • the content of Fe 2 O 3 is preferably 0.05% or less, 0.04% or less, or 0.03% or less, and particularly preferably 0.02% or less. Further, the content of Fe 2 O 3 is preferably 0.001% or more.
  • the CeO 2 content is preferably 0 to 6%.
  • the content of CeO 2 is preferably 6% or less, 5% or less, 3% or less, 2% or less, 1% or less, and particularly preferably 0.1% or less.
  • the content of CeO 2 is preferably 0.001% or more, particularly preferably 0.01% 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 particularly preferably less than 0.1%.
  • other components may be introduced in a total amount, preferably up to 10% (desirably 5%).
  • the phase-separated glass of the present invention preferably has the following characteristics.
  • the density is preferably 5.0 g / cm 3 or less, 4.5 g / cm 3 or less, 4.0 g / cm 3 or less, and 3.5 g / cm 3 or less, and particularly preferably 3.2 g / cm 3 or less. is there. If it does in this way, an organic EL device can be reduced in weight.
  • the average thermal expansion coefficient at 30 to 380 ° C. is preferably 30 ⁇ 10 ⁇ 7 / ° C. to 100 ⁇ 10 ⁇ 7 / ° C., 40 ⁇ 10 ⁇ 7 / ° C. to 90 ⁇ 10 ⁇ 7 / ° C., 50 ⁇ 10 ⁇ 7 / ° C. to 80 ⁇ 10 ⁇ 7 / ° C., particularly preferably 55 ⁇ 10 ⁇ 7 / ° C. to 65 ⁇ 10 ⁇ 7 / ° C.
  • flexibility is required for a glass plate from the viewpoint of enhancing design elements. In order to increase flexibility, it is necessary to reduce the thickness of the glass plate.
  • the thermal expansion coefficients of the glass plate and the transparent conductive film such as ITO or FTO are mismatched, the glass plate warps. It becomes easy. Therefore, if the average coefficient of thermal expansion at 30 to 380 ° C. is set in the above range, such a situation can be easily prevented.
  • the “average thermal expansion coefficient at 30 to 380 ° C.” can be measured with a dilatometer or the like.
  • the strain point is preferably 450 ° C. or higher, 500 ° C. or higher, 550 ° C. or higher, and particularly preferably 600 ° C. or higher.
  • the higher the temperature of the transparent conductive film the higher the transparency and the lower the electrical resistance.
  • the conventional glass plate has insufficient heat resistance, it has been difficult to form a transparent conductive film at a high temperature. Therefore, when the strain point is within the above range, both transparency of the transparent conductive film and low electric resistance can be achieved, and furthermore, in the manufacturing process of the organic device, the glass plate is hardly thermally contracted by heat treatment.
  • 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, and particularly preferably 1200 ° C. or lower. If it does in this way, since a meltability will improve, productivity of a glass plate will improve.
  • Liquid phase temperature becomes like this. Preferably it is 1300 degrees C or less, 1250 degrees C or less, 1200 degrees C or less, Most preferably, it is 1150 degrees C or less.
  • the liquid phase viscosity is preferably 10 2.5 dPa ⁇ s or more, 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 or more.
  • the “liquid phase temperature” passed through 30 mesh (500 ⁇ m sieve opening), and the glass powder remaining in 50 mesh (300 ⁇ m sieve opening) was placed in a platinum boat and held in a temperature gradient furnace for 24 hours. Later, it refers to a value obtained by measuring the temperature at which crystals are deposited. “Liquid phase viscosity” refers to the viscosity of the glass at the liquidus temperature.
  • the phase separation temperature is preferably 900 ° C. or lower, and particularly preferably 850 ° C. or lower.
  • the phase separation viscosity is preferably 10 4.0 dPa ⁇ s or more, and particularly preferably 10 5.0 to 10 8.0 dPa ⁇ s. In this way, the heat treatment temperature can be lowered. As a result, the heat treatment cost can be reduced.
  • the “phase separation temperature” indicates that clear turbidity is observed when glass is placed in a platinum boat and remelted at 1400 ° C., then the platinum boat is transferred to a temperature gradient furnace and held in the temperature gradient furnace for 30 minutes. Refers to temperature.
  • Phase separation viscosity refers to a value obtained by measuring the viscosity of glass at the phase separation temperature by the platinum pulling method.
  • the phase-separated glass of the present invention is based on the premise that the glass does not phase-separate in the molding step and the slow cooling (cooling) step, but phase-separates in the subsequent heat treatment step, but the molding step and / or the slow cooling step.
  • the glass may be phase-separated.
  • the phase separation temperature is preferably 700 ° C. or higher, 750 ° C. or higher, and particularly preferably 780 ° C. or higher.
  • the phase separation viscosity is preferably 10 9.0 dPa ⁇ s or less, and particularly preferably 10 5.0 to 10 8.0 dPa ⁇ s.
  • a glass plate which has a phase separation structure by a float process or an overflow down draw method.
  • a separate heat treatment step becomes unnecessary, and the manufacturing cost of the glass plate can be easily reduced.
  • a phase separation phenomenon may occur in the bowl-shaped structure, or a phase separation phenomenon may occur during stretch molding or slow cooling. If it does in this way, the number of manufacturing processes of glass will decrease and glass productivity can be raised.
  • the phase separation phenomenon can be controlled by the glass composition, molding conditions, slow cooling conditions, and the like.
  • the glass may be phase-separated in the melting step, for example, other than the forming step and the slow cooling (cooling) step.
  • the total light transmittance at a wavelength of 400 to 700 nm is preferably 20% or more, 30% or more, 40% or more, and particularly preferably 50% or more. If the total light transmittance is too low, it becomes difficult to extract the light in the glass into the air.
  • the diffuse transmittance at a wavelength of 400 to 700 nm is preferably 10% or more, 20% or more, 30% or more, 40% or more, and particularly preferably 50% or more. If the diffuse transmittance is too low, it becomes difficult to extract the light in the glass into the air.
  • the haze value at a wavelength of 400 to 700 nm is preferably 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, Preferably it is 90% or more. If the haze value is too low, the desire for light scattering becomes insufficient, and it becomes difficult to extract the light in the glass into the air.
  • the phase-separated glass of the present invention preferably has a flat plate shape, that is, a glass plate. If it does in this way, it will become easy to apply to an organic EL device.
  • a flat plate shape it is preferable to have an unpolished surface on at least one surface (in particular, the entire effective surface of at least one surface is an unpolished surface).
  • the theoretical strength of glass is 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 surface of the glass plate in a post-molding process such as a polishing process. Therefore, if the surface of the glass plate is unpolished, the original mechanical strength is hardly lost, and thus the glass plate 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 thickness (in the case of a flat plate) is preferably 5 to 500 ⁇ m. If the thickness is too large, if the light scattering function is excessive, the total light transmittance becomes low, and it becomes difficult to extract the light in the phase separation glass into the air. Therefore, the thickness is preferably 500 ⁇ m or less, 400 ⁇ m or less, 300 ⁇ m or less, 200 ⁇ m or less, 100 ⁇ m or less, and particularly preferably 50 ⁇ m or less. On the other hand, if the thickness is too small, the light scattering function tends to be lowered, and it becomes difficult to take out the light in the phase separation glass into the air. Therefore, the thickness is preferably 5 ⁇ m or more, 10 ⁇ m or more, 20 ⁇ m or more, and particularly preferably 30 ⁇ m or more.
  • the surface roughness Ra of at least one surface is preferably 0.01 to 1 ⁇ m.
  • the surface roughness Ra is preferably 1 ⁇ m or less, 0.8 ⁇ m or less, 0.5 ⁇ m or less, 0.3 ⁇ m or less, 0.1 ⁇ m or less, 0.07 ⁇ m or less, 0.05 ⁇ m or less, 0.03 ⁇ m or less, particularly preferably Is 10 nm or less.
  • the phase-separated glass (or phase-separated glass) of the present invention is preferably formed by a downdraw method, particularly an overflow downdraw method.
  • a downdraw method particularly an overflow downdraw method.
  • the overflow down draw method the surface to be the surface is not in contact with the bowl-shaped refractory and is molded in a free surface state.
  • a slot downdraw method can be employed. If it does in this way, it will become easy to produce a thin glass plate.
  • a redraw method for example, a float method, a roll-out method, etc.
  • the float process can efficiently produce a large glass plate.
  • the phase-separated glass of the present invention is preferably subjected to a heat treatment step. This makes it easy to control the scattering phenomenon of the phase separation glass (especially the scattering phenomenon due to Mie scattering), and to easily reduce the difference between the maximum value and the minimum value of the total light transmittance at wavelengths of 400 to 700 nm.
  • the heat treatment temperature is preferably 610 ° C. or higher, 710 ° C. or higher, 760 ° C. or higher, 800 ° C., particularly preferably 810 ° C. or higher. This makes it easier to control the scattering phenomenon (particularly the scattering phenomenon due to Mie scattering) of the phase separation glass.
  • the heat treatment temperature is preferably 1100 ° C. or lower and 1000 ° C. or lower, particularly preferably 900 ° C. or lower. If the heat treatment temperature is too high, in addition to an increase in heat treatment cost, the scattering intensity becomes too strong, and the linear transmittance, total light transmittance, and the like may decrease.
  • the heat treatment time is preferably 1 minute or longer, particularly 5 minutes or longer. This makes it easier to control the scattering phenomenon (particularly the scattering phenomenon due to Mie scattering) of the phase separation glass.
  • the heat treatment temperature is preferably 72 hours or less, 48 hours or less, 24 hours or less, and particularly preferably 60 minutes or less. If the heat treatment time is too long, in addition to an increase in the heat treatment cost, the scattering intensity becomes too strong, and the linear transmittance, total light transmittance, and the like may decrease.
  • At least one surface may be a roughened surface. If the roughened surface is arranged on the side in contact with air such as organic EL lighting, in addition to the scattering effect of the glass plate, the non-reflective structure of the roughened surface allows light emitted from the organic EL layer to be within the organic EL layer. As a result, the light extraction efficiency can be increased.
  • the surface roughness Ra of the roughened surface is preferably 10 mm or more, 20 mm or more, 30 mm or more, and particularly preferably 50 mm or more.
  • the roughened surface can be formed by HF etching, sandblasting, or the like.
  • the roughened surface can be formed by an atmospheric pressure plasma process. In this way, it is possible to uniformly roughen the other surface while maintaining the surface state of one surface of the glass plate. Moreover, it is preferable to use a gas containing F (for example, SF 6 , CF 4 ) as a source of the atmospheric pressure plasma process. In this way, since plasma containing HF gas is generated, the roughened surface can be formed efficiently.
  • a gas containing F for example, SF 6 , CF 4
  • a roughened surface can be formed on at least one surface during molding of the glass plate. This eliminates the need for a separate roughening process and improves the efficiency of the roughening process.
  • the uneven surface roughness Ra is preferably 10 mm or more, 20 mm or more, 30 mm or more, and particularly preferably 50 mm or more.
  • Phase-separated glass of the present invention when incorporated into the organic EL element, the current efficiency of the organic EL element becomes is preferably higher than that incorporating the glass having a refractive index n d is not phase separation of the same extent.
  • the current efficiency at 20 mA / cm 2 compared with a case incorporating a glass having a refractive index n d is not phase separation of comparable, more than 5%, 8% or more, 10% or more, particularly 12% or more It is preferable to be high. In this way, the brightness of the organic EL device can be increased. In particular, even if the existing glass composition is not significantly changed, the luminance of the organic EL device can be increased only by introducing a component that induces phase separation in the glass composition.
  • phase-separated glass of the present invention is a plate-shaped phase-separated glass plate, it can be bonded to a substrate to constitute a composite substrate.
  • the phase separation glass plate functions as a light scattering plate, it is possible to increase the light extraction efficiency of the organic EL element only by combining with the substrate.
  • the phase separation glass plate and the substrate are joined and the phase separation glass plate is disposed on the side in contact with air, the scratch resistance of the composite substrate can be improved.
  • a resin substrate As the substrate, various materials can be used.
  • a metal substrate, or a glass substrate can be used.
  • a glass substrate is preferable from the viewpoints of permeability, weather resistance, and heat resistance.
  • Various materials can be used as the glass substrate.
  • a soda lime glass substrate, an aluminosilicate glass substrate, and an alkali-free glass substrate can be used.
  • the thickness of the glass substrate is preferably from 0.3 to 3.0 mm, from 0.4 to 2.0 mm, particularly preferably from more than 0.5 to 1.8 mm, from the viewpoint of maintaining strength.
  • Refractive index n d of the glass substrate is preferably 1.50 greater, 1.51 or more, 1.52 or more, 1.53 or more, 1.54 or more, 1.55 or more, 1.56 or more, 1.60 or more And particularly preferably 1.63 or more. If the refractive index of the glass substrate is too low, it becomes difficult to efficiently extract light by reflection at the interface of the glass substrate and the transparent conductive film. On the other hand, if the refractive index nd is too high, the reflectance at the interface between the glass substrate and the phase separation glass plate becomes high, and it becomes difficult to extract the light in the glass substrate into the air through the phase separation glass plate. Therefore, the refractive index n d is preferably 2.30 or less, 2.20 or less, 2.10 or less, 2.00 or less, 1.90 or less, 1.80 or less, particularly preferably 1.75 or less is there.
  • the surface roughness Ra of at least one surface (particularly the unpolished surface) of the glass substrate is preferably 0.01 to 1 ⁇ m. If the surface roughness Ra is too large, it becomes difficult to produce a composite substrate by optical contact. In addition, when a transparent conductive film or the like is formed on the surface, the quality of the transparent conductive film is lowered and uniform. It becomes difficult to obtain luminescence. Therefore, the surface roughness Ra of at least one surface is preferably 1 ⁇ m or less, 0.8 ⁇ m or less, 0.5 ⁇ m or less, 0.3 ⁇ m or less, 0.1 ⁇ m or less, 0.07 ⁇ m or less, 0.05 ⁇ m or less, 0. It is 03 ⁇ m or less, particularly preferably 10 nm or less.
  • a method of joining with an adhesive tape, an adhesive sheet, an adhesive, a curing agent, or the like, or a method of joining with an optical contact can be used.
  • a method of bonding with an ultraviolet curable resin is preferable from the viewpoint of bonding reliability
  • a method of bonding with an optical contact is preferable from the viewpoint of increasing the transmittance of the composite substrate.
  • the organic EL device of the present invention includes the above-described phase separation glass.
  • Examples of the organic EL device include organic EL lighting.
  • this organic EL device it is preferable to incorporate phase separation glass in the state of the composite substrate.
  • Method of manufacturing a phase-separated glass of the present invention after the refractive index n d is molded more than 1.55 min chemistry glass, by heat-treating phase separation glass obtained, at least a first phase and a second phase A phase separation glass having a phase separation structure containing is obtained.
  • the phase-separated glass is phase-separated by heat treatment at 1100 ° C. or lower to become the above-described phase-separated glass.
  • the phase-separable glass has a property of phase separation from at least a first phase and a second phase from a state where the phase separation is not performed when heat treatment is performed at 800 ° C. for 24 hours.
  • various characteristics such as the refractive index of the phase-separated glass plate are the same as those of the above-described phase-separated glass except that the phase-separated glass plate is not phase-separated, detailed description is omitted.
  • the heat treatment means a heat treatment step separately performed after the molding step and the slow cooling step. Since the heat treatment temperature and the heat treatment time are as described above, detailed description thereof is omitted.
  • Table 1 shows sample No. 1 to 7 are shown.
  • the obtained glass batch was supplied to the glass melting furnace, and it melted at 1400 degreeC for 7 hours.
  • a simple slow cooling treatment was performed from the strain point to room temperature over 10 hours.
  • the obtained glass plate was processed as necessary to evaluate various properties.
  • the density ⁇ is a value measured by the well-known Archimedes method.
  • the average thermal expansion coefficient ⁇ is a value measured with a dilatometer in a temperature range of 30 to 380 ° C.
  • a ⁇ 5 mm ⁇ 20 mm cylindrical sample (the end surface is R-processed) was used as a measurement sample.
  • 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 a meltability, so that high temperature viscosity is low.
  • the liquid phase temperature TL passes through 30 mesh (a sieve opening of 500 ⁇ m), puts the glass powder remaining in a 50 mesh (a sieve opening of 300 ⁇ m) into a platinum boat, and holds it in a temperature gradient furnace for 24 hours. It is the value which measured the temperature which precipitates.
  • the liquid phase viscosity log ⁇ TL is a value obtained by measuring the viscosity of the glass at the liquid phase temperature by a platinum ball pulling method.
  • the phase separation temperature TP is measured at a temperature at which white turbidity is clearly recognized when each glass is put in a platinum boat, remelted at 1400 ° C., then transferred to a temperature gradient furnace, and held in the temperature gradient furnace for 30 minutes. It is a thing.
  • the phase separation viscosity log ⁇ TP is obtained by measuring the viscosity of each glass at the phase separation temperature by the platinum ball pulling method.
  • phase separation after molding was transparent when the molded sample after the above-mentioned slow cooling treatment was visually observed as “ ⁇ ” when white turbidity due to phase separation was observed, and without white turbidity due to phase separation. Things were evaluated as “x”.
  • the phase separation after the heat treatment is the one in which white turbidity due to the phase separation was observed when the molded sample after the slow cooling treatment was heat-treated at 800 ° C. for 24 hours and the obtained heat-treated sample was visually observed. “ ⁇ ” was evaluated as “ ⁇ ” when the sample was transparent without white turbidity due to phase separation.
  • Refractive index n d is the value of the d-line as determined by the refractive index measuring instrument KPR-2000 manufactured by Shimadzu Corporation. Specifically, first, a rectangular parallelepiped sample of 25 mm ⁇ 25 mm ⁇ about 3 mm is prepared, and the temperature range from (annealing point Ta + 30 ° C.) to (strain point Ps ⁇ 50 ° C.) is set at a cooling rate of 0.1 ° C./min. It is a value measured by infiltrating an immersion liquid having a matching refractive index n d after annealing.
  • Specimen No. after the above slow cooling treatment 1 was put into a platinum boat having a size of about 15 mm ⁇ 130 mm, and then the platinum boat was put into an electric furnace and remelted at 1400 ° C.
  • the remelted glass in the platinum boat had a thickness of about 3 to 5 mm.
  • the platinum boat was taken out of the electric furnace and allowed to cool in the air.
  • the obtained phase separation glass it heat-processed on the conditions for 24 hours at 800 degreeC, and was made to phase-separate.
  • Each of the heat-treated samples 1 had a wavelength at which the haze value was 5% or more at a wavelength of 400 to 700 nm, and had a light scattering function.
  • the obtained glass batch was supplied to the glass melting furnace, and it melted at 1400 degreeC for 7 hours.
  • a simple slow cooling treatment was performed from the strain point to room temperature over 10 hours.
  • the obtained glass plate was processed as necessary to evaluate various properties.
  • the measuring method of various characteristics is as described in the first embodiment.
  • the molded glass plate (Sample No. 8) was put into a platinum boat having a size of about 15 mm ⁇ 130 mm, and the platinum boat was put into an electric furnace and remelted at 1400 ° C.
  • the remelted glass in the platinum boat had a thickness of about 3 to 5 mm.
  • the platinum boat was taken out of the electric furnace and allowed to cool in the air.
  • the obtained glass it heat-processed on condition of 850 degreeC for 24 hours, and phase-separated. Further, it was immersed in a 1M hydrochloric acid solution for 10 minutes, and after carbon deposition, the surface of the sample was observed with a field emission scanning electron microscope (S-4300SE manufactured by Hitachi High-Technologies Corporation).
  • Sample No. 8 subjected to heat treatment has a phase separation structure having phase separation particles of about 300 to 400 nm, and a phase rich in B 2 O 3 (second phase: layer poor in SiO 2 ) is a hydrochloric acid solution.
  • a phase rich in B 2 O 3 (second phase: layer poor in SiO 2 ) is a hydrochloric acid solution.
  • the phase rich in B 2 O 3 is eluted by the hydrochloric acid solution, and the phase rich in SiO 2 is not eluted in the hydrochloric acid solution.
  • phase-separated glass after the heat treatment is processed into a glass plate having a thickness of about 10 mm ⁇ 30 mm ⁇ 1.0 mm, both surfaces are mirror-polished, and the spectrophotometer (Spectrophotometer UV-2500PC, manufactured by Shimadzu Corporation) The total light transmittance and diffuse transmittance of were measured. The result is shown in FIG.
  • the difference between the maximum value and the minimum value of the total light transmittance at a wavelength of 400 to 700 nm is within 20%, the total light transmittance at a wavelength of 400 to 700 nm is 20% or more, The diffuse transmittance at a wavelength of 400 to 700 nm was 20% or more.
  • phase-separated glass after the heat treatment was processed into a glass plate having a thickness of about 10 mm ⁇ 30 mm ⁇ 1.0 mm to obtain a phase-separated glass plate.
  • a glass substrate (OA-10L manufactured by Nippon Electric Glass Co., Ltd .: refractive index n d 1.52) having a thickness of about 10 mm ⁇ 30 mm ⁇ 2.0 mm was prepared.
  • an ultraviolet curable resin Optoclave UT20 manufactured by MS Ardel Co., Ltd.
  • a composite substrate having a total thickness of 2.3 mm was obtained.
  • the total light transmittance and diffuse transmittance in the thickness direction were measured with a spectrophotometer (Spectrophotometer UV-2500PC manufactured by Shimadzu Corporation). The result is shown in FIG.
  • phase-separated glass after the heat treatment was processed into a glass plate having a thickness of about 10 mm ⁇ 30 mm ⁇ 1.0 mm to obtain a phase-separated glass plate.
  • a glass substrate (OA-10L manufactured by Nippon Electric Glass Co., Ltd .: refractive index n d 1.52) having a thickness of about 10 mm ⁇ 30 mm ⁇ 2.0 mm was prepared.
  • an ultraviolet curable resin Optoclave UT20 manufactured by MS Ardel Co., Ltd.
  • a composite substrate having a total thickness of 2.1 mm was obtained.
  • the total light transmittance and diffuse transmittance in the thickness direction were measured with a spectrophotometer (Spectrophotometer UV-2500PC manufactured by Shimadzu Corporation). The result is shown in FIG.
  • the difference between the maximum value and the minimum value of the total light transmittance at a wavelength of 400 to 700 nm is within 20%, and the total light transmittance at a wavelength of 400 to 700 nm is low.
  • the diffuse transmittance at a wavelength of 400 to 700 nm was 20% or more.
  • Example 3 sample no. No. 8 was used for the experiment.
  • Regarding 9 to 14 it is considered that the same tendency can be obtained by the same experiment.
  • Tables 4 and 5 show the sample numbers. 15 to 46 are shown.
  • the obtained glass batch was supplied to the glass melting furnace, and it melted at 1400 degreeC for 7 hours.
  • a slow cooling treatment was performed from the strain point to room temperature over 10 hours.
  • the obtained glass plate was processed as necessary to evaluate various properties.
  • the measuring method of various characteristics is as described in the first embodiment.
  • FIGS. 7 to 10 show sample Nos. Images obtained by observing the sample surfaces of 17, 20, 22, and 23 with a field emission scanning electron microscope are shown.
  • FIGS. 17,20,22,23 has a phase separation structure, phase rich in B 2 O 3 (second phase: poor SiO 2 layer) were eluted by hydrochloric acid solution.
  • the phase rich in B 2 O 3 is eluted by the hydrochloric acid solution, and the phase rich in SiO 2 is not eluted in the hydrochloric acid solution.
  • Sample No. in Table 4 23 (plate thickness 0.7 mm: not heat-treated after forming) was produced, and ITO (thickness 100 nm) was deposited on the glass plate surface as a transparent electrode layer using a mask. Subsequently, 6% by mass of polymer PEDOT-PSS (thickness 40 nm) as a hole injection layer, ⁇ -NPD (thickness 50 nm) as a hole transport layer, and Ir (ppy) 3 as an organic light emitting layer were doped on ITO.
  • PEDOT-PSS thickness 40 nm
  • ⁇ -NPD thickness 50 nm
  • Ir (ppy) 3 as an organic light emitting layer
  • the glass plate according to the comparative example as a glass composition, in mass%, SiO 2 36.0%, Al 2 O 3 5.1%, B 2 O 3 14.1%, CaO 7.0%, SrO 11.2%, BaO 17.9%, ZnO 3.1%, ZrO 2 2.0%, and contains TiO 2 3.6%, a refractive index n d is 1.63.
  • Sample No. in Table 4 A glass plate (thickness 0.7 mm: not heat-treated after molding) according to No. 21 was prepared, and ITO (thickness 100 nm) was deposited on the glass plate surface as a transparent electrode layer using a mask. Subsequently, 6% by mass of polymer PEDOT-PSS (thickness 40 nm) as a hole injection layer, ⁇ -NPD (thickness 50 nm) as a hole transport layer, and Ir (ppy) 3 as an organic light emitting layer were doped on ITO.
  • PEDOT-PSS thickness 40 nm
  • ⁇ -NPD thickness 50 nm
  • Ir (ppy) 3 an organic light emitting layer

Abstract

　Verre à phases séparées ayant un indice de réfraction nd de 1,55 ou plus, et ayant une structure à phases séparées comprenant au moins une première phase et une seconde phase.
PCT/JP2015/065449 2014-06-02 2015-05-28 Verre à phases séparées, verre à phases séparables, dispositif el organique et procédé de production de verre à phases séparées WO2015186606A1 (fr)

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JP2015202970A (ja) * 2014-04-11 2015-11-16 日本電気硝子株式会社 ガラスフィルム及びこれを用いた複合基板
WO2016117406A1 (fr) * 2015-01-21 2016-07-28 日本電気硝子株式会社 Verre à phases séparées
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Publication number Priority date Publication date Assignee Title
JP2015202971A (ja) * 2014-04-11 2015-11-16 日本電気硝子株式会社 分相ガラス及びこれを用いた複合基板
JP2015202970A (ja) * 2014-04-11 2015-11-16 日本電気硝子株式会社 ガラスフィルム及びこれを用いた複合基板
WO2016117406A1 (fr) * 2015-01-21 2016-07-28 日本電気硝子株式会社 Verre à phases séparées
US11787731B2 (en) 2020-10-29 2023-10-17 Corning Incorporated Phase separable glass compositions having improved mechanical durability

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