WO2015186606A1 - Phase-separated glass, phase-separable glass, organic el device, and method for producing phase-separated glass - Google Patents

Abstract

　Phase-separated glass having a refractive index n_d of 1.55 or higher, and having a phase-separated structure including at least a first phase and a second phase.

Description

Phase separation glass, phase separation glass, organic EL device, and method for producing phase separation glass

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.

In recent years, the energy consumed in living spaces such as homes has increased due to the widespread use, increase in size, and multifunctionality of home appliances. In particular, the energy consumption of lighting equipment is increasing. For this reason, highly efficient illumination is actively studied.

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. On the other hand, 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. When forming a light emitting layer, 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. In addition, 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.

However, in order to apply the organic EL element to the light source for illumination, the luminance has not yet reached the practical level, and further improvement of the luminous efficiency is necessary.

One reason for the decrease in luminance is that light is confined in the glass plate due to the difference in refractive index between the glass plate and air. For example, when a glass plate having a refractive index n _{d of} 1.50 is used, since the refractive index n _{d of} air is 1.0, the critical angle is calculated to be 42 ° from Snell's law. Therefore, light having an incident angle greater than the critical angle causes total reflection, is confined in the glass plate, and is not extracted into the air.

JP 2012-25634 A

In order to solve the above problems, it has been studied to form a light extraction layer between a transparent conductive film or the like and a glass plate. For example, in 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.

However, in order to form the light extraction layer on the surface of the glass plate, a printing step of applying a glass paste to the surface of the glass plate is required, and this step causes an increase in production cost. Further, when the scattering particles are dispersed in the glass frit, the transmittance of the light extraction layer is lowered due to the absorption of the scattering particles themselves.

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.

As a result of intensive studies, the inventor has found that the above technical problem can be solved by using a phase separation glass having a high refractive index and restricting the total light transmittance to a predetermined range, and proposes the present invention. To do. That is, phase-separated glass of 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. Here, “refractive index n _d ” refers to the value of the d-line measured by a refractive index measuring device. For example, 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.). after, while penetration of immersion 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). Moreover, the light scattering accompanying formation of a 1st phase and a 2nd phase can be confirmed visually. Furthermore, 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. In this way, when applied to an organic EL device, the light incident on the glass plate from the organic EL layer is scattered at the interface between the first phase and the second phase, so that the light can be easily taken out to the outside. As a result, the light extraction efficiency can be increased without forming a light extraction layer made of a sintered body. The “organic EL device” includes not only organic EL lighting but also an organic EL display.

Phase-separated glass of the present invention, the refractive index _{n d} is 1.55 or more. In conventional organic EL devices such as organic EL lighting, the light incident from the organic EL layer is reflected at the interface between the glass plate and the transparent conductive film due to the large difference in refractive index between the glass plate and the transparent conductive film. However, there is also a problem that the light extraction efficiency is lowered. Specifically, 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. In contrast, the refractive index _{n d} of the glass plate was typically about 1.50. Therefore, if the refractive index _nd is regulated as described above, 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.

Secondly, in the phase-separated glass of the present invention, 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. 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. Note that 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. Here, 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.

Third, 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. Here, “diffuse 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. Can do.

Fourth, 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. Here, the “haze value” is a value calculated by (diffuse transmittance) × 100 / (total light transmittance).

Fifth, 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.

Sixth, the phase-separated glass of the present invention preferably has an average particle diameter of phase-separated particles of 100 nm or more.

Seventh, phase-separated glass of the present invention preferably has a refractive index n _d is less than 1.65.

Eighth, in the phase-separated glass of the present invention, the phase-separated glass 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.

Ninth, it is preferable that the phase-separated glass of the present invention does not substantially contain a rare metal oxide in the glass composition. Here, “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 . “Rare 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.

Tenth, in the phase-separated glass of the present invention, 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.

Eleventh, phase-separated glass of the present invention, 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.

Twelfth, 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.

Thirteenth, in the phase-separated glass of the present invention, the mass ratio (Al ₂ O ₃ + B ₂ O ₃ ) / SiO _{2 in} the glass composition is preferably 0.3 or more.

Fourteenth, 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.

Fifteenth, the phase-separated glass of the present invention preferably has a BaO—SrO content of 1 to 12% by mass in the glass composition.

Sixteenth, it is preferable that the phase separation glass of the present invention has a flat plate shape.

Seventeenth, the phase separation glass of the present invention preferably has a thickness of 5 to 500 μm.

Eighteenth, the organic EL device of the present invention is characterized by comprising the above phase separation glass.

Nineteenth, the organic EL device of the present invention is preferably illumination.

To a twenty-producing method of the 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. Furthermore, if the glass is phase-separated at the time of molding, there is a problem that the glass is easily devitrified. However, after the phase-separation at the time of molding is suppressed, heat treatment is performed after molding to phase-separate the glass. Such a problem can be avoided accurately. The phase separation phenomenon can be controlled not only by heat treatment conditions (heat treatment temperature, heat treatment time) but also by glass composition, molding conditions, annealing conditions, and the like. Here, “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 twenty-first method of manufacturing a phase-separated glass of the present invention, it is preferable that the refractive index n _d is molded phase separation glass of less than 1.65.

Twenty-second, the method for producing a phase separation glass of the present invention preferably forms the phase separation glass into a flat plate shape.

Twenty-third, in the method for producing a phase separation glass of the present invention, it is preferable to form the phase separation glass by an overflow down draw method.

The twenty-fourth, phase separation glass of the present invention, 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. Sample No. after heat treatment according to 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. 6 in 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. Sample No. 7 in 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.

Phase-separated glass of the present invention, 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. When 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. On the other hand, if 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. Further, the reflectance at the interface between the glass plate and the air becomes high, and it becomes difficult to extract light to the outside. Therefore, 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.

In the phase separation glass of the present invention, 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. When 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.

In the phase-separated glass of the present invention, the average particle size of the phase-separated particles of at least one phase (first phase and / or second phase) is preferably 100 nm or more, 200 nm or more, 300 nm or more, 400 to 5000 nm. In particular, 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 . Hereinafter, the reason why each component is limited as described above will be described. In addition, in description of the containing range of each component,% display means the mass%.

The content of SiO ₂ is preferably 30 to 75%. When the content of SiO ₂ increases, the meltability and moldability tend to decrease, and the refractive index tends to decrease. Therefore, 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%. On the other hand, when the content of SiO ₂ decreases, it becomes difficult to form a glass network structure, and vitrification becomes difficult. Further, the viscosity of the glass is excessively lowered, and it becomes difficult to ensure a high liquid phase viscosity. Therefore, 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 .

In addition to the above components, for example, the following components can be introduced.

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. However, when the content of Na 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 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. However, when MgO is contained in a large amount, the liquidus temperature rises and devitrification resistance decreases. Or the density may become too high. Therefore, 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%. When MgO is introduced, 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. When the content of BaO increases, the refractive index and density tend to increase. When the content of BaO is too large, the component balance of the glass composition is impaired and devitrification resistance tends to decrease. Therefore, 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. Further, 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.

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. Here, “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%. When the ZnO content is increased, the refractive index and density are likely to be increased, the balance of the components of the glass composition is impaired, and devitrification resistance is likely to be reduced. Therefore, 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.

The mass ratio 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. . In this way, phase separation can be improved while maintaining a high strain point. Here, “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%. When the content of La ₂ O ₃ increases, the density tends to increase, and the devitrification resistance and acid resistance easily decrease. Furthermore, the raw material cost rises, and the manufacturing cost of the glass plate is likely to rise. Therefore, 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%. When 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%. When the content of Gd ₂ O ₃ is increased, the density becomes too high, the component balance of the glass composition is lacking, the devitrification resistance is lowered, the high temperature viscosity is lowered too much, and a high liquid phase viscosity is secured. It becomes difficult to do. Therefore, 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.

As a refining agent, one or two or more selected from the group of As ₂ O ₃ , Sb ₂ O ₃ , SnO ₂ , Fe ₂ O ₃ , F, Cl, SO ₃ , and CeO ₂ are converted into the following oxides. Up to 3% can be introduced. In particular, SnO ₂ , Fe ₂ O ₃ and CeO ₂ are preferable as the fining agent. On the other hand, it is preferable to refrain from using As ₂ O ₃ and Sb ₂ O ₃ as much as possible from the environmental viewpoint, and the content of each is preferably less than 0.3%, particularly preferably less than 0.1%. is there. Here, “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%. When the content of CeO ₂ is increased, the devitrification resistance is likely to be lowered. Therefore, 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. On the other hand, when CeO ₂ is introduced, 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%.

In addition to the above components, 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. In recent years, in an organic EL device, there is a case where 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. In this case, if 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. However, since 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. · S or more, 10 ^4.4 dPa · s or more, particularly preferably 10 ^4.6 dPa · s or more. If it does in this way, it will become difficult to devitrify glass at the time of shaping | molding, for example, it will become easy to shape | mold a glass plate by the float method or the overflow downdraw method. Here, the “liquid phase temperature” passed through 30 mesh (500 μm sieve opening), and the glass powder remaining in 50 mesh (300 μm 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. Here, 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. When glass is subjected to phase separation in the forming step and / or the slow cooling step, the phase separation temperature is preferably 700 ° C. or higher, 750 ° C. or higher, and particularly preferably 780 ° C. or higher. In addition, 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. If it does in this way, it will become easy to phase-separate glass at a formation process and / or a slow cooling process, and it will become easy to shape a glass plate which has a phase separation structure by a float process or an overflow down draw method. As a result, after forming the glass plate, a separate heat treatment step becomes unnecessary, and the manufacturing cost of the glass plate can be easily reduced. When a glass plate is formed by the overflow downdraw method, 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. In addition, 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. When it has 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 μm. 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 μm or less, 400 μm or less, 300 μm or less, 200 μm or less, 100 μm or less, and particularly preferably 50 μm 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 μm or more, 10 μm or more, 20 μm or more, and particularly preferably 30 μm or more.

When it has a flat plate shape, the surface roughness Ra of at least one surface (especially an unpolished surface) is preferably 0.01 to 1 μm. When surface roughness Ra is large, when forming a transparent conductive film etc. on the surface, the quality of a transparent conductive film falls and it becomes difficult to obtain uniform light emission. The surface roughness Ra is preferably 1 μm or less, 0.8 μm or less, 0.5 μm or less, 0.3 μm or less, 0.1 μm or less, 0.07 μm or less, 0.05 μm or less, 0.03 μm 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. In this way, it is possible to produce a glass plate that is unpolished and has good surface quality. The reason is that, in the case of 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. In addition to the overflow downdraw method, a slot downdraw method can be employed. If it does in this way, it will become easy to produce a thin glass plate.

Other than the above molding method, for example, a redraw method, a float method, a roll-out method, etc. can be employed. In particular, 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. On the other hand, 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. On the other hand, 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.

When the phase separation glass of the present invention has a flat plate shape, 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. Moreover, you may form an uneven | corrugated shape in the surface of a glass plate by heat processing, such as a repress. In this way, an accurate non-reflective structure can be formed on the glass surface. Uneven shape, taking into account the refractive index n _d, may be adjusted the spacing and depth.

Further, 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.

Furthermore, 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.

In addition, you may affix the resin film which has a predetermined uneven | corrugated shape on the surface of a glass plate, without forming a roughening surface in a glass plate. 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. For example, 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.

When the 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. In this way, since 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. Furthermore, if 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.

As the substrate, various materials can be used. For example, a resin substrate, a metal substrate, or a glass substrate can be used. Among these, a glass substrate is preferable from the viewpoints of permeability, weather resistance, and heat resistance. Various materials can be used as the glass substrate. For example, 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 μm. 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 μm or less, 0.8 μm or less, 0.5 μm or less, 0.3 μm or less, 0.1 μm or less, 0.07 μm or less, 0.05 μm or less, 0. It is 03 μm or less, particularly preferably 10 nm or less.

Various methods can be used as a method of joining the phase separation glass plate and the substrate. For example, 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. Among them, a method of bonding with an ultraviolet curable resin is preferable from the viewpoint of bonding reliability, and 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. In 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. Specifically, it is preferable that 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. Here, since 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.

Here, 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.

Hereinafter, the present invention will be described in detail based on examples. The following examples are merely illustrative. The present invention is not limited to the following examples.

Table 1 shows sample No. 1 to 7 are shown.

First, after preparing a glass raw material so that it might become a glass composition of Table 1, the obtained glass batch was supplied to the glass melting furnace, and it melted at 1400 degreeC for 7 hours. Next, after the obtained molten glass was poured onto a carbon plate and formed into a flat plate shape, a simple slow cooling treatment was performed from the strain point to room temperature over 10 hours. Finally, the obtained glass plate was processed as necessary to evaluate various properties.

The density ρ is a value measured by the well-known Archimedes method.

The average thermal expansion coefficient α is a value measured with a dilatometer in a temperature range of 30 to 380 ° C. In addition, a φ5 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 μm), puts the glass powder remaining in a 50 mesh (a sieve opening of 300 μm) 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 ηTL 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 ηTP is obtained by measuring the viscosity of each glass at the phase separation temperature by the platinum ball pulling method.

The 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. After remelting, the platinum boat was taken out of the electric furnace and allowed to cool in the air. About the obtained phase separation glass, it heat-processed on the conditions for 24 hours at 800 degreeC, and was made to phase-separate. Further, after the heat-treated sample was processed into a glass plate having a thickness of about 10 mm × 30 mm × 1.0 mm, both surfaces were mirror-polished, and a spectrophotometer (spectrum photometer UV-2500PC manufactured by Shimadzu Corporation) was used for wavelengths of 300 to 800 nm. Thus, the total light transmittance and diffuse transmittance in the thickness direction were measured. The result is shown in FIG. Further, the heat-treated sample was immersed in a 1M hydrochloric acid solution for 10 minutes, and then carbon deposited, and the surface of the sample was observed with a field emission scanning electron microscope (S-4300SE manufactured by Hitachi High-Technologies Corporation). The result is shown in FIG.

As shown in FIG. 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.

Table 2 shows sample No. 8 is shown.

First, after preparing a glass raw material so that it might become a glass composition of Table 2, the obtained glass batch was supplied to the glass melting furnace, and it melted at 1400 degreeC for 7 hours. Next, after the obtained molten glass was poured onto a carbon plate and formed into a flat plate shape, a simple slow cooling treatment was performed from the strain point to room temperature over 10 hours. Finally, 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. After remelting, the platinum boat was taken out of the electric furnace and allowed to cool in the air. About 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). The result is shown in FIG. 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. Was eluted. Note that 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.

The 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.

As shown in FIG. 4, 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.

The 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. Moreover, 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. Next, after joining the phase-separated glass plate and the glass substrate using an ultraviolet curable resin (Optoclave UT20 manufactured by MS Ardel Co., Ltd.), the surface of the phase-separated glass plate is processed to a thickness of 0.3 mm by polishing. A composite substrate having a total thickness of 2.3 mm was obtained. With respect to this composite substrate, 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.

Furthermore, the 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. Moreover, 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. Next, after joining the phase-separated glass plate and the glass substrate using an ultraviolet curable resin (Optoclave UT20 manufactured by MS Ardel Co., Ltd.), the surface of the phase-separated glass plate is processed to a thickness of 0.1 mm by polishing. A composite substrate having a total thickness of 2.1 mm was obtained. With respect to this composite substrate, 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.

As shown in FIGS. 5 and 6, in the composite substrate, 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.

In Example 3 and Example 4, 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.

First, after preparing a glass raw material so that it might become a glass composition as described in a table | surface, the obtained glass batch was supplied to the glass melting furnace, and it melted at 1400 degreeC for 7 hours. Next, after the obtained molten glass was poured on a carbon plate and formed into a flat plate shape, a slow cooling treatment was performed from the strain point to room temperature over 10 hours. Finally, 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.

Sample No. above. After immersing 17, 20, 22, and 23 in a 1M hydrochloric acid solution for 10 minutes, carbon was deposited, and the surface of the sample was observed with a field emission scanning electron microscope (S-4300SE, manufactured by Hitachi High-Technologies Corporation). The results are shown in 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. As can be seen from 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. In the phase-separated glass, 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.

Specimen No. so that the plate thickness is 0.7 mm. After processing 20 to 23 and further mirror-polishing both surfaces, the total light transmittance and diffuse transmittance in the thickness direction were measured at a wavelength of 300 to 800 nm using a spectrophotometer (Spectrophotometer UV-2500PC manufactured by Shimadzu Corporation). Was measured. The results are shown in FIGS. As can be seen from FIGS. Nos. 20 to 23 each had a wavelength with a haze value of 5% or more at a wavelength of 400 to 700 nm, and had a light scattering function.

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, α-NPD (thickness 50 nm) as a hole transport layer, and Ir (ppy) ₃ as an organic light emitting layer were doped on ITO. After forming CBP (thickness 30 nm), hole blocking layer BAlq (thickness 10 nm), electron transporting layer Alq (thickness 30 nm), LiF (thickness 0.8 nm) as an electron injection layer, and Al (thickness 150 nm) as a counter electrode, The inside was sealed and the organic EL element was produced. With respect to the obtained organic EL element, a luminance meter (BM-9 manufactured by Topcon Co., Ltd.) was arranged in a direction perpendicular to the light emitting surface, front luminance was measured, and current efficiency was evaluated. As a comparative example, Sample No. In the case where an organic EL element was fabricated by incorporating a non-phase-divided glass plate (plate thickness 0.7 mm) having the same refractive index _nd as 23, the front luminance was measured in the same manner, and the current efficiency was evaluated. As a result, sample no. When the glass according to No. 23 was incorporated, the current efficiency at 20 mA / cm ² was improved by 14% as compared with the case where the glass plate according to the comparative example was incorporated. 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, α-NPD (thickness 50 nm) as a hole transport layer, and Ir (ppy) ₃ as an organic light emitting layer were doped on ITO. After forming CBP (thickness 30 nm), hole blocking layer BAlq (thickness 10 nm), electron transporting layer Alq (thickness 30 nm), LiF (thickness 0.8 nm) as an electron injection layer, and Al (thickness 150 nm) as a counter electrode, The inside was sealed and the organic EL element was produced. With respect to the obtained organic EL element, a luminance meter (BM-9 manufactured by Topcon Co., Ltd.) was arranged in a direction perpendicular to the light emitting surface, front luminance was measured, and current efficiency was evaluated. As a comparative example, when the organic EL element was fabricated by incorporating the same glass plate (plate thickness 0.7 mm) as that used in Example 8, the front luminance was measured in the same manner to evaluate the current efficiency. As a result, sample no. When incorporating the glass plate according to 21, the current efficiency at 20 mA / cm ² was improved by 9% than incorporating a glass plate according to a comparative example.

Claims (24)

1. Refractive index n _d is not less than 1.55, phase-separated glass, characterized in that it comprises a phase-separated structure including at least a first phase and a second phase.
2. 2. The phase separation glass according to claim 1, wherein the difference between the maximum value and the minimum value of the total light transmittance at a wavelength of 400 to 700 nm is 40% or less.
3. 3. The phase separation glass according to claim 1 or 2, wherein the diffuse transmittance at a wavelength of 400 to 700 nm is 10% or more.
4. The phase-separated glass according to any one of claims 1 to 3, wherein a haze value at a wavelength of 400 to 700 nm has a wavelength of 5% or more.
5. The phase separation glass according to any one of claims 1 to 4, wherein the total light transmittance at a wavelength of 400 to 700 nm is 10% or more.
6. 6. The phase separation glass according to claim 1, wherein the average particle size of the phase separation particles is 100 nm or more.
7. Phase-separated glass according to any one of claims 1 to 6, the refractive index n _d is equal to or less than 1.65.
8. The phase-separated glass contains, by mass%, SiO ₂ 30 to 75%, B ₂ O ₃ 0.1 to 50%, and Al ₂ O ₃ 0 to 35% as a glass composition. 8. The phase separation glass according to any one of 1 to 7.
9. The phase-separated glass according to any one of claims 1 to 8, wherein the glass composition does not substantially contain a rare metal oxide.
10. The content of SiO ₂ in the first phase, phase-separated glass according to any one of claims 1 to 9, characterized in that more than the content of SiO ₂ in the second phase.
11. Second content of B ₂ O ₃ in phases, divided according to any one of claims 1 to 10, characterized in that more than the content of B ₂ O ₃ in the first phase Phase glass.
12. The phase-separated glass according to any one of claims 1 to 11, wherein the content of P ₂ O ₅ in the glass composition is 0.001 to 10 mass%.
13. The phase-separated glass according to any one of claims 1 to 12, wherein a mass ratio (Al ₂ O ₃ + B ₂ O ₃ ) / SiO ₂ in the glass composition is 0.3 or more.
14. The phase-separated glass according to any one of claims 1 to 13, wherein a mass ratio TiO ₂ / B ₂ O ₃ in the glass composition is 0.01 to 2.
15. The phase-separated glass according to any one of claims 1 to 14, wherein the content of BaO-SrO in the glass composition is 1 to 12 mass%.
16. The phase-separated glass according to any one of claims 1 to 15, which has a flat plate shape.
17. The phase-separated glass according to any one of claims 1 to 16, wherein the thickness is 5 to 500 µm.
18. An organic EL device comprising the phase-separated glass according to any one of claims 1 to 17.
19. The organic EL device according to claim 18, wherein the organic EL device is illumination.
20. After the refractive index n _d is molded more than 1.55 min chemistry glass, by heat-treating phase separation glass obtained, the phase-separated glass with a phase separation structure comprising at least a first phase and a second phase A method for producing phase-separated glass, characterized in that it is obtained.
21. Method of manufacturing a phase-separated glass of claim 20 having a refractive index n _d is characterized by shaping the phase separation of glass of less than 1.65.
22. The method for producing a phase separation glass according to claim 21, wherein the phase separation glass is formed into a flat plate shape.
23. The method for producing a phase separation glass according to claim 21 or 22, wherein the phase separation glass is formed by an overflow downdraw method.
24. 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, that it has the property of phase separation into at least a first phase and a second phase Characteristic phase separation glass.
    
    

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