WO2015186584A1

WO2015186584A1 - Phase-separated glass, method for producing phase-separated glass and composite substrate using phase-separated glass

Info

Publication number: WO2015186584A1
Application number: PCT/JP2015/065267
Authority: WO
Inventors: 篤虫明
Original assignee: 日本電気硝子株式会社
Priority date: 2014-06-02
Filing date: 2015-05-27
Publication date: 2015-12-10

Abstract

This method for producing phase-separated glass is characterized in that phase-separated glass which comprises at least a first phase and a second phase is obtained by forming phase-separable glass having a refractive index (n_d) of 1.65 or more and subsequently subjecting the obtained phase-separable glass to a heat treatment. This phase-separated glass has a refractive index (n_d) of 1.65 or more and a phase-separated structure comprising at least a first phase and a second phase, and may have a difference of 40% or less between the maximum value and the minimum value of the total light transmittance at a wavelength of 400-700 nm. In addition, this phase-separated glass has a refractive index (n_d) of 1.65 or more and a phase-separated structure comprising at least a first phase and a second phase, and may be configured such that the SiO₂ content in the first phase is higher than the SiO₂ content in the second phase.

Description

Phase separation glass, method for producing phase separation glass, and composite substrate using phase separation glass

The present invention relates to phase-separated glass, and specifically relates to phase-separated glass having a light scattering function, a method for producing the same, and a composite substrate using the same.

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, if the refractive index n _d a glass plate 1.5, since the refractive index n _d of the air is 1.0, the critical angle is calculated to be 42 ° from the 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 The idea is to create a glass manufacturing method with excellent productivity.

As a result of intensive studies, the present inventors have found that the above technical problem can be solved by heat-treating a phase separation glass having a high refractive index to obtain the phase separation glass, and propose this as the first invention. Is. That is, the manufacturing method of the phase-separated glass according to the first invention, after the refractive index n _d was molded 1.65 or more phase separation glass by heat-treating phase separation glass obtained, at least a first A phase-separated glass containing a phase and a second phase is obtained. 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 are aligned, it can be measured by the refractive index measuring instrument KPR-2000 manufactured by Shimadzu Corporation. 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. “Phase-separating glass” refers to glass that has not yet phase-separated but has a property of phase separation by heat treatment at 1100 ° C. or lower.

In the manufacturing method of the phase-separated glass according to the first invention, a refractive index n _d is molded 1.65 or more phase separation glass. 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 usually about 1.5. Therefore, if regulating the refractive index n _d of the above as phase separation of glass (phase-separated glass), the refractive index difference between such a glass plate and a transparent conductive film is reduced, the glass plate is incident light from the organic EL layer It becomes difficult to reflect at the interface between the transparent conductive film and the like, and the light extraction efficiency can be increased.

In the method for producing a phase separation glass according to the first present invention, the phase separation glass is heat-treated to obtain the phase separation glass. This makes it easy to control the 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.

In the method for producing a phase separation glass according to the first aspect of the present invention, a phase separation glass containing at least a first phase and a second phase is obtained. 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.

Secondly, the production method of the phase-separated glass according to the first aspect 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.

Thirdly, in the method for producing a phase separation glass according to the first aspect of the present invention, the phase separation glass has a glass composition of 30% by mass, SiO ₂ 30 to 75%, Al ₂ O ₃ 0 to 35%, BaO 10 as a glass composition. Preferably it contains ˜50%. If it does in this way, it will become easy to raise refractive index _nd to 1.65 or more, and it will become easy to raise productivity of a glass plate.

Fourthly, in the method for producing a phase separation glass according to the first aspect of the present invention, the phase separation glass is preferably formed into a flat plate shape.

Fifth, in the method for producing a phase separation glass according to the first aspect of the present invention, the phase separation glass is preferably used for an organic EL device, particularly for organic EL illumination.

Sixth, it is preferable that the phase-separated glass according to the first aspect of the present invention is produced by the method for producing a phase-separated glass described above.

Seventh, the phase separation glass according to the first aspect of the present invention preferably has 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). “Diffusion 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 can be used as a measurement sample. “Total light transmittance” is a value measured in the thickness direction with a spectrophotometer (eg, UV-2500PC manufactured by Shimadzu Corporation). For example, glass whose both surfaces are mirror-polished can be used as a measurement sample. .

Eighth, phase separation glass according to the first invention, a refractive index n _d is not less than 1.65, and when subjected to heat treatment for 24 hours at 900 ° C., from the state where no phase separation, at least a It has the property of phase separation into one phase and a second phase.

Furthermore, as a result of intensive studies, the inventor has found that the above technical problem can be solved by using a high refractive index phase-separated glass and regulating its total light transmittance to a predetermined range. This is proposed as the present invention. That is, phase-separated glass according to a second aspect of the present invention, the refractive index n _d is not less than 1.65, a phase separation structure comprising at least a first phase and a second phase, at a wavelength of 400 ~ 700 nm The difference between the maximum value and the minimum value of the total light transmittance is 40% or less. 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 are aligned, it can be measured by the refractive index measuring instrument KPR-2000 manufactured by Shimadzu Corporation. 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. “Total light transmittance” is a value measured in the thickness direction with a spectrophotometer (eg, UV-2500PC manufactured by Shimadzu Corporation). For example, glass whose both surfaces are mirror-polished can be used as a measurement sample. .

The phase-separated glass according to the second invention has 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 according to a second aspect of the present invention, the refractive index n _d is 1.65 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.

On the other hand, when using phase-separated glass, 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. There is a risk of becoming unsuitable for lighting applications. Therefore, the phase separation glass of the present invention regulates the difference between the maximum value and the minimum value of the total light transmittance at a wavelength of 400 to 700 nm to 40% or less. Thereby, it becomes possible to eliminate the above-mentioned problem. 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.

Second, the phase separation glass according to the second aspect of the present invention preferably has a phase separation particle size of 100 nm or more.

Thirdly, the phase separation glass according to the second invention preferably has a diffuse transmittance of 10% or more at a wavelength of 400 to 700 nm. “Diffusion 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 can be used as a measurement sample.

Fourth, the phase-separated glass according to the second aspect of the present invention is that the phase-separated glass contains, as a glass composition, 30% to 75% SiO2, 0 to 35% Al ₂ O ₃ , and 10 to 50% BaO. It is preferable to contain. 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.

Fifth, the phase separation glass according to the second aspect of the present invention preferably has a thickness of 5 to 500 μm.

Sixth, the phase separation glass according to the second aspect of the present invention is preferably used for organic EL devices, particularly organic EL lighting.

Seventh, the composite substrate according to the second aspect of the present invention is a composite substrate obtained by bonding a phase separation glass plate and a substrate, and the phase separation glass plate preferably includes the phase separation glass described above.

Eighth, the composite substrate according to the second aspect of the present invention is preferably a glass substrate.

Ninth, a composite substrate according to the second invention, it is preferable that the refractive index n _d of the substrate is 1.50 greater.

Tenth, in the composite substrate according to the second aspect of the present invention, it is preferable that the phase separation glass plate and the substrate are joined by optical contact.

Eleventh, the composite substrate according to the second aspect of the present invention is preferably used for organic EL devices, particularly organic EL lighting.

In addition, as a result of intensive studies, the present inventor has found that the above technical problem can be solved by using a phase separation glass having a high refractive index, and proposes it as a third invention. That is, phase-separated glass according to the third invention, the refractive index n _d is not less than 1.65, and has a phase separation structure comprising at least a first phase and a second phase, the first phase in the the content of SiO _2, characterized in that more than the content of SiO ₂ in the 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 are aligned, it can be measured by the refractive index measuring instrument KPR-2000 manufactured by Shimadzu Corporation. 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 separation glass according to the third aspect of the present invention has a phase separation structure including at least a first phase and a second phase, and the content of SiO ₂ in the first phase is in the second phase. More than the content of SiO ₂ . 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 according to the third invention, the refractive index n _d is 1.65 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 usually about 1.5. 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.

Second, the phase separation glass according to the third aspect of the present invention contains, as a glass composition, 30% to 75% SiO ₂ , 0 to 35% Al ₂ O ₃ , and 10 to 50% BaO by mass%. preferable. 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.

Third, the phase-separated glass according to the third aspect of the present invention preferably has an Al ₂ O ₃ content of less than 7% by mass in the glass composition.

Fourth, the phase-separated glass according to the third aspect of the present invention preferably has a B ₂ O ₃ content of 20% by mass or less in the glass composition.

Fifth, the phase-separated glass according to the third aspect of the present invention preferably has a P ₂ O ₅ content of 0.001 to 10% by mass in the glass composition.

Sixth, the phase-separated glass according to the third aspect of the present invention preferably has a La ₂ O ₃ content of 0.001 to 15% by mass in the glass composition.

Seventh, in the phase-separated glass according to the third aspect of the present invention, the Nb ₂ O ₅ content in the glass composition is preferably 0.001 to 20% by mass.

Eighth, the phase separation glass according to the third aspect 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). “Diffusion 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 can be used as a measurement sample. “Total light transmittance” is a value measured in the thickness direction with a spectrophotometer (eg, UV-2500PC manufactured by Shimadzu Corporation). For example, glass whose both surfaces are mirror-polished can be used as a measurement sample. .

Ninth, the phase separation glass according to the third aspect of the present invention preferably has a total light transmittance of 10% or more at a wavelength of 400 to 700 nm.

Tenth, the phase separation glass according to the third aspect of the present invention preferably has a flat plate shape.

Eleventh, the phase separation glass according to the third aspect of the present invention is preferably not subjected to a separate heat treatment step, phase separation is performed in the molding step, or phase separation is performed in the slow cooling (cooling) step immediately after molding. It is preferable. If it does in this way, the number of manufacturing processes of glass will decrease and glass productivity can be raised.

Twelfth, phase-separated glass according to the third invention, when incorporated into the organic EL element, the current efficiency of the organic EL elements, incorporating a glass having a refractive index n _d is not phase separation of comparable It is preferable to be higher than the case. Here, “current efficiency” is calculated by preparing a luminance meter in a direction perpendicular to the thickness direction of the glass after measuring the organic EL element using glass and measuring the front luminance of the glass. Can do. “The refractive index _nd is about the same” means that the refractive index _nd is within a range of ± 0.05.

Thirteenth, the phase separation glass according to the third aspect of the present invention is preferably used for an organic EL device, particularly for organic EL lighting.

14thly, it is preferable that the organic EL device according to the third aspect of the present invention comprises the above phase separation glass.

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] 2 (plate thickness: 1.0 mm) both surfaces were mirror-polished, and the total light transmittance and diffuse transmittance in the thickness direction were measured with a spectrophotometer. Sample No. 3 related to [Example 3]. 2 is an image obtained by immersing 2 in a 1 M hydrochloric acid solution for 10 minutes and then observing the obtained sample surface with a scanning electron microscope. Sample No. after heat treatment according to [Example 4] 3 is an image obtained by immersing 3 in a 1M hydrochloric acid solution for 10 minutes and then observing the obtained sample surface with a scanning electron microscope. Sample No. after heat treatment according to [Example 4] 3 (plate thickness: 1.0 mm) both surfaces were mirror-polished, and the total light transmittance and diffuse transmittance in the thickness direction were measured with a spectrophotometer. Data obtained by measuring the total light transmittance and diffuse transmittance in the thickness direction with a spectrophotometer for the composite substrate according to [Example 5] (plate thickness of the phase separation glass plate: 0.1 mm, total plate thickness: 2.1 mm) It is. Sample No. 6 related to [Example 6]. 5 is an image obtained by immersing 5 in a 1M hydrochloric acid solution for 10 minutes and then observing the obtained sample surface with a scanning electron microscope. Sample No. 6 related to [Example 6]. 7 is an image obtained by immersing 7 in a 1M hydrochloric acid solution for 10 minutes and then observing the obtained sample surface with a scanning electron microscope. Sample No. 6 related to [Example 6]. 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. 6 related to [Example 6]. 9 shows an image obtained by immersing 9 in a 1M hydrochloric acid solution for 10 minutes and then observing the obtained sample surface with a scanning electron microscope. In sample No. 7 according to [Example 7]. 7 is a data obtained by mirror-polishing both surfaces of 7 (plate thickness 0.7 mm) and measuring the total light transmittance and diffuse transmittance in the thickness direction with a spectrophotometer. In sample No. 7 according to [Example 7]. This is data obtained by mirror-polishing both surfaces of 8 (plate thickness 0.7 mm) and measuring the total light transmittance and diffuse transmittance in the thickness direction with a spectrophotometer. In sample No. 7 according to [Example 7]. This is data obtained by mirror-polishing both surfaces of 9 (plate thickness 0.7 mm) and measuring the total light transmittance and diffuse transmittance in the thickness direction with a spectrophotometer.

First, the phase separation glass and the manufacturing method thereof according to the first embodiment of the present invention will be described.

In the manufacturing method of the phase-separated glass according to the first embodiment of the present invention, the refractive index n _d is molded 1.65 or more phase separation glass. Refractive index _{n d} of the phase separation property glass is preferably 1.66 or more, 1.67 or more, 1.68 or more, 1.69 or more, particularly 1.70 or more. When the refractive index n _d is less than 1.65, 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, when the refractive index _nd is too high, 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, 2.20 or less, 2.10 or less, 2.00 or less, 1.90 or less or 1.80 or less, particularly preferably 1.75 or less.

In the method for producing phase-separated glass according to the first embodiment of the present invention, the thickness (in the case of a flat plate) is 1.5 mm or less, 1.3 mm or less, 1.1 mm or less, 0.8 mm or less, 0.8 mm or less. It is preferable to mold a phase separation glass of 7 mm or less, 0.5 mm or less, 0.3 mm or less, or 0.2 mm or less, and it is particularly preferable to mold a phase separation glass of 0.1 mm or less. The smaller the thickness, the higher the flexibility and the easier it is to improve the design of organic EL lighting. However, when the thickness is extremely small, the glass tends to break. Therefore, the thickness is preferably 10 μm or more, particularly preferably 30 μm or more.

In the method for producing phase-separated glass according to the first embodiment of the present invention, it is preferably molded into a flat plate shape, that is, preferably molded into a glass plate. If it does in this way, it will become easy to apply to an organic EL device. When forming into a glass plate, it is preferable to make at least one surface into an unpolished surface (especially the whole 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.

When forming into a glass plate, it is preferable to form so that the surface roughness Ra of at least one surface (especially an unpolished surface) is 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. Suitable upper limit ranges of the surface roughness Ra are 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, or 0.03 μm or less, particularly suitable The upper limit range is 10 nm or less.

In the method for producing a phase separation glass according to the first embodiment of the present invention, it is preferable to form the phase separation glass 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, the phase separation glass can be formed by a slot downdraw method. 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.

In the method for producing a phase separation glass according to the first embodiment of the present invention, a phase separation glass including at least a first phase and a second phase is obtained by heat treatment, and the phase separation glass is contained in the first phase. the content of SiO ₂ is, it is preferably greater than the content of SiO ₂ in the second phase, and if containing _B 2 _{O 3} in the glass composition, of _B 2 _{O 3} in the second phase The content 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 light-scattering function of glass can be improved.

In the method for producing phase-separated glass according to the first embodiment of the present invention, the average particle size of phase-separated particles of at least one phase (first phase and / or second phase) is 0.01 to 5 μm, particularly It is preferable to heat treat the phase separation glass so that the thickness becomes 0.05 to 0.5 μm. If the average particle size of the phase-separated particles is small, the light emitted from the organic EL layer is difficult to scatter at the interface between the first phase and the second phase. On the other hand, if the average particle size of the phase-separated particles is large, the scattering intensity becomes too strong and the total light transmittance may be lowered.

In the method for producing a phase separation glass according to the first embodiment of the present invention, the heat treatment temperature is preferably 700 ° C. or higher, 800 ° C. or higher, or 850 ° C. or higher, particularly preferably 900 ° C. or higher. This makes it easy to obtain a phase separation structure. On the other hand, the heat treatment temperature is preferably 1100 ° C. or less, particularly preferably 1000 ° C. or less. 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 (holding time at the heat treatment temperature) is preferably 1 minute or longer, particularly 5 minutes or longer. This makes it easy to obtain a phase separation structure. On the other hand, the heat treatment temperature is preferably 72 hours or less, 48 hours or less or 24 hours or less, 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.

The phase separation glass (or phase separation glass) according to the first embodiment of the present invention has, as a glass composition, 30% to 75% SiO ₂ , 0 to 35% Al ₂ O ₃ , and 10 to 50% BaO by mass%. It is preferable to contain. 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 preferable upper limit range of SiO ₂ is 75% or less, 70% or less, 65% or less, 60% or less, 55% or less, 50% or less, 45% or less, or 40% or less, and the particularly preferable upper limit range is 40%. Is less than. 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 preferable lower limit range of SiO ₂ is 30% or more, 32% or more, or 34% or more, and the particularly preferable lower limit range is 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, and acid resistance tends to decrease. Therefore, the preferable upper limit range of Al ₂ O ₃ is 35% or less, 30% or less, 25% or less, 20% or less, 15% or less, 10% or less, less than 7%, 5% or less, particularly 3% or less. The preferred lower limit range is 0.1% or more, 0.5% or more, particularly 1% or more.

The content of BaO is preferably 10 to 50%. 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 preferred upper limit range of BaO is 40% or less, 30% or less, particularly 26% or less, and the preferred lower limit range is more than 10%, 14% or more, 20% or more, 22% or more, particularly 24% or more. is there.

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

The content of B ₂ O ₃ is preferably 0 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 preferable upper limit range of B ₂ O ₃ is 50% or less, 40% or less, 30% or less, 20% or less, 10% or less, 5% or less, particularly 2% or less. 1% or more, 0.3% or more, particularly 0.5% or more.

The content of Li ₂ O is preferably 0 to 30%. Li ₂ O is a component that enhances phase separation, but if the content of Li ₂ O is too large, the liquid phase viscosity tends to decrease, the strain point tends to decrease, and further, an etching step using an acid. In this case, the alkali component is easily eluted. Therefore, a suitable upper limit range of Li ₂ O is 30% or less, 20% or less, 10% or less, 5% or less, less than 1%, particularly 0.5% or less.

The content of Na ₂ O is preferably 0-30%. Na ₂ O is a component that improves phase separation. However, if the content of Na ₂ O is too large, the liquid phase viscosity tends to decrease, the strain point tends to decrease, and further, an etching step using an acid. In this case, the alkali component is easily eluted. Therefore, a preferable upper limit range of Na ₂ O is 30% or less, 20% or less, 10% or less, 5% or less, less than 1%, particularly 0.5% or less.

The content of K ₂ O is preferably 0 to 30%. K ₂ O is a component that improves phase separation. However, if the content of K ₂ O is too large, the liquid phase viscosity tends to decrease, the strain point tends to decrease, and further, an etching step using an acid. In this case, the alkali component is easily eluted. Therefore, a preferable upper limit range of K ₂ O is 30% or less, 20% or less, 10% or less, 5% or less, less than 1%, particularly 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 preferable upper limit range of MgO is 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, Less than 1%. In addition, when introducing MgO, a suitable lower limit range is 0.1% or more, especially 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 preferable upper limit range of CaO is 30% or less, 20% or less, 10% or less, 8% or less, particularly 6% or less, and the preferable lower limit range is 0.1% or more, 1% or more, 2% or more. In particular, it is 4% 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, a preferable upper limit range of SrO is 30% or less, 20% or less, 10% or less, 8% or less, particularly 5% or less, and a preferable lower limit range is 1% or more, 3% or more, particularly 4% or more. is there.

The content of ZnO is preferably 0 to 30%. 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, a suitable upper limit range of ZnO is 20% or less, 10% or less, 5% or less, 4% or less, 3% or less, 2% or less, particularly less than 1%. In addition, when introducing ZnO, a suitable lower limit range is 0.1% or more, especially 0.9% 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 preferable upper limit range of TiO ₂ is 20% or less, 15% or less, 10% or less, particularly 8% or less, and the preferable lower limit range is 0.001% or more, 0.01% or more, 0.1%. Above, 1% or more, 2% or more, especially 3% or more.

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 preferable upper limit range of ZrO ₂ is 20% or less, 10% or less, particularly 5% or less, and the preferable lower limit range is 0.001% or more, 0.01% or more, 0.1% or more, 1%. Above, 1.5% or more, especially 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 preferable upper limit range of P ₂ O ₅ is 10% or less, 7% or less, 4% or less, 3% or less, particularly 2% or less, and the preferable lower limit range is 0.001% or more and 0.01%. These are 0.1% or more, 1% or more, 1.4% or more, particularly 1.6% or more.

The mass ratio P ₂ O ₅ / Al ₂ O ₃ is preferably 0.1 or more, 0.3 or more, 0.5 or more, 0.6 or more, 0.7 or more, 0.8 or more, 0.9 or more, One or more, especially more than one. In this way, the phase separation can be effectively enhanced. Here, “P ₂ O ₅ / Al ₂ O ₃ ” is a value obtained by dividing the content of P ₂ O _{5 by} the content of Al ₂ O ₃ .

The mass ratio P ₂ O ₅ / B ₂ O ₃ is preferably 0.1 or more, 0.3 or more, 0.5 or more, 0.6 or more, 0.7 or more, 0.8 or more, 0.9 or more, One or more, especially more than one. If it does in this way, phase separation property can be improved, ensuring acid resistance. Here, “P ₂ O ₅ / B ₂ O ₃ ” is a value obtained by dividing the content of P ₂ O _{5 by} the content of B ₂ O ₃ .

The mass ratio P ₂ O ₅ / (Li ₂ O + Na ₂ O + K ₂ O) is preferably 0.1 or more, 0.3 or more, 0.5 or more, 0.6 or more, 0.7 or more, 0.8 or more, 0.9 or more, 1 or more, particularly more than 1. In this way, phase separation can be improved while maintaining a high strain point. Here, “Li ₂ O + Na ₂ O + K ₂ O” is the total amount of Li ₂ O, Na ₂ O and K ₂ O. “P ₂ O ₅ / (Li ₂ O + Na ₂ O + K ₂ O)” is a value obtained by dividing the content of P ₂ O _{5 by} the content of Li ₂ O + Na ₂ O + K ₂ O.

La ₂ O ₃ is a component that increases the refractive index, and its content is preferably 0 to 15%. If the content of La ₂ O ₃ increases, the density tends to increase, the devitrification resistance and acid resistance easily decrease, the raw material cost increases, and the production cost of the glass plate easily increases. . Therefore, the suitable upper limit range of La ₂ O ₃ is 15% or less, 10% or less, 6% or less, particularly 4% or less, and the preferred lower limit range is 0.001% or more, 0.01% or more, 0. 5% or more, 1% or more, 2% or more, particularly 3% or more.

Nb ₂ O ₅ is a component that increases the refractive index, and its content is preferably 0 to 20%. When the content of Nb ₂ O ₅ increases, the density tends to increase, the devitrification resistance tends to decrease, the raw material cost increases, and the glass plate manufacturing cost easily increases. Therefore, a preferable upper limit range of Nb ₂ O ₅ is 20% or less, 16% or less, 14% or less, 12% or less, particularly 10% or less, and a preferable lower limit range is 0.001% or more and 0.01%. These are 1% or more, 4% or more, 6% or more, particularly 8% or more.

La ₂ O ₃ and Nb ₂ O ₅ are components that increase the refractive index. However, if the content of these components increases, the density and thermal expansion coefficient tend to increase, and the devitrification resistance decreases, resulting in a high level. It becomes difficult to ensure the liquid phase viscosity, and further, the raw material cost increases, and the manufacturing cost of the glass plate is likely to increase. Therefore, the preferred upper limit range of La ₂ O ₃ + Nb ₂ O ₅ is 35% or less, 30% or less, 25% or less, 20% or less, particularly 15% or less, and the preferred lower limit range is 0.001% or more, 1% or more, 2% or more, 4% or more, 6% or more, 8% or more, particularly 10% or more. Here, “La ₂ O ₃ + Nb ₂ O ₅ ” refers to the total amount of La ₂ O ₃ and Nb ₂ O ₅ .

The mass ratio (La ₂ O ₃ + Nb ₂ O ₅ ) / (SiO ₂ + Al ₂ O ₃ + B ₂ O ₃ ) is preferably 0.1 or more, 0.15 or more, 0.2 or more, 0.25 or more, 0 .28 or more, 0.29 or more, 0.3 or more, 0.31 or more, or 0.32 or more, particularly preferably 0.33 or more. This makes it easy to increase the refractive index nd to 1.65 or more. Here, “SiO ₂ + Al ₂ O ₃ + B ₂ O ₃ ” is the total amount of SiO ₂ , Al ₂ O ₃ and B ₂ O ₃ . “(La ₂ O ₃ + Nb ₂ O ₅ ) / (SiO ₂ + Al ₂ O ₃ + B ₂ O ₃ )” indicates that the content of La ₂ O ₃ + Nb ₂ O ₅ is SiO ₂ + Al ₂ O ₃ + B ₂ O ₃ . The value divided by the content.

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, a suitable upper limit range of Gd ₂ O ₃ is 10% or less, 5% or less, 3% or less, 2.5% or less, 1% or less, particularly 0.1% or less.

The total content of rare metal oxides is preferably 0 to 35%. 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. In addition, the raw material cost is increased, and the manufacturing cost of the glass plate is likely to increase. Therefore, the preferable upper limit range of the rare metal oxide is 35% or less, 30% or less, 25% or less, 20% or less, particularly 15% or less, and the preferable lower limit range is 0.001% or more, 1% or more, 2 % Or more, 4% or more, 6% or more, 8% or more, particularly 10% or more. The “rare metal oxide” as used in the present invention is a rare earth oxide such as La ₂ O ₃ , Nd ₂ O ₃ , Gd ₂ O ₃ , CeO ₂ , Y ₂ O ₃ , Nb ₂ O ₅ , Ta ₂ O _5. Point to.

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 an environmental viewpoint, and the content of each is preferably less than 0.3%, particularly preferably less than 0.1%. 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%, particularly 0.01 to 0.5%.

Fe ₂ O _{3 has} a preferred upper limit range of 0.05% or less, 0.04% or less, 0.03% or less, particularly 0.02% or less, and a preferred lower limit range of 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 preferable upper limit range of CeO ₂ is 6% or less, 5% or less, 3% or less, 2% or less, 1% or less, particularly 0.1% or less. On the other hand, when CeO ₂ is introduced, a suitable lower limit range of CeO ₂ is 0.001% or more, particularly 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 is desirably substantially free. Here, “substantially does not contain PbO” refers to a case where the content of PbO in the glass composition is 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 separation glass (or phase separation glass) according to the first embodiment 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, particularly 3.6 g / cm ³ or less. 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 to 100 × 10 ⁻⁷ / ° C., 40 × 10 ⁻⁷ to 90 × 10 ⁻⁷ / ° C., 50 × 10 ⁻⁷ to 85 × 10 ⁻⁷ / ° C., in particular 60 × 10 ⁻⁷ to 75 × 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, 600 ° C or higher, particularly 650 ° 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 1600 ° C. or lower, 1560 ° C. or lower, 1500 ° C. or lower, particularly 1450 ° C. or lower. If it does in this way, since a meltability will improve, productivity of a glass plate will improve.

The liquidus temperature is preferably 1300 ° C. or lower, 1250 ° C. or lower, 1200 ° C. or lower, particularly 1150 ° C. or lower. 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 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 1000 ° C. or lower, particularly 950 ° C. or lower. The phase separation viscosity is preferably 10 ^4.0 dPa · s or more, particularly 10 ^5.0 to 10 ^8.0 dPa · s. In this way, the heat treatment temperature can be lowered. As a result, it becomes easy to reduce the heat treatment cost. Furthermore, if the heat treatment temperature can be lowered, it becomes easy to suppress softening deformation of the glass plate due to the heat treatment. 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. “Phase separation viscosity” refers to a value obtained by measuring the viscosity of glass at the phase separation temperature by the platinum pulling method. In addition, although it is preferable that the phase separation glass of this invention does not phase-separate at a shaping | molding process and / or a slow cooling process, glass may phase-separate at these processes.

Wavelengths having a haze value of 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, particularly 90% or more at a wavelength of 400 to 700 nm It is preferable to have. If there is no wavelength having a haze value equal to or greater than a predetermined value, the light scattering function becomes insufficient, and it becomes difficult to extract the light in the glass into the air. The “haze value” is a value calculated by (diffuse transmittance) × 100 / (total light transmittance).

The total light transmittance at a wavelength of 400 to 700 nm is preferably 10% or more, 20% or more, 30% or more, 40% or more, particularly 50% or more. If the total light transmittance is too low, it becomes difficult to extract the light in the glass into the air.

It is preferable that the diffuse transmittance has a wavelength of 10% or more, 20% or more, particularly 30% or more at a wavelength of 400 to 700 nm. If there is no wavelength having a diffuse transmittance equal to or greater than a predetermined value, it is difficult to extract light in the glass into the air.

In the method for producing phase-separated glass according to the first embodiment of the present invention, when it has a flat plate shape, it is preferable to provide a roughening step for forming a roughened surface on at least one 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, particularly 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, particularly 50 mm or more.

Phase separation glass of the present invention, the refractive index n _d is not less than 1.65, and when subjected to heat treatment for 24 hours at 900 ° C., from the state where no phase separation, at least a first phase and a second phase It has the property of phase separation. In addition, the technical characteristics (a suitable structure and effect) of the phase separation glass of this invention are already described in the description column of the manufacturing method of the phase separation glass of this invention, and detailed description is abbreviate | omitted here.

Next, a phase separation glass and a composite substrate using the same according to a second embodiment of the present invention will be described.

The phase separation glass according to the second embodiment of the present invention has a phase separation structure including at least a first phase and a second phase, and the content of SiO ₂ in the first phase is It is preferable that the content of SiO ₂ in the second phase is larger, and when B ₂ O ₃ is contained in the glass composition, the content of B ₂ O _{3 in} the _second phase is it is preferably larger than the content of _B 2 _{O 3.} If it does in this way, the refractive index of a 1st phase and a 2nd phase will become easy to differ, and the light-scattering function of glass can be improved.

Phase-separated glass according to a second embodiment of the present invention, the refractive index _{n d} is 1.65 or more, preferably 1.66 or more, 1.67 or more, 1.68 or more, 1.69 or more, particularly 1.70 or more. When the refractive index n _d is less than 1.65, 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, when the refractive index _nd is too high, 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, 2.20 or less, 2.10 or less, 2.00 or less, 1.90 or less, 1.80 or less, particularly 1.75 or less.

In the phase separation glass according to the second embodiment 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, 10%. Hereinafter, it is especially 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 separation glass according to the second embodiment of the present invention, the particle size of the phase separation 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, particularly 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 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.

The phase-separated glass according to the second embodiment of the present invention preferably contains, as a glass composition, 30 to 75% of SiO ₂ , 0 to 35% of Al ₂ O _{3 and} 10 to 50% of BaO by mass%. In addition, in description of the containing range of each component,% display means the mass%.

The reason why each component is limited as described above is the same as that already described for the phase-separated glass according to the first embodiment of the present invention described above, and therefore the description thereof is omitted here.

The components that can be introduced in addition to the above components are the same as those already described for the phase-separated glass according to the first embodiment of the present invention, and therefore the description thereof is omitted here.

The characteristics of the phase-separated glass according to the second embodiment of the present invention are as described above for the phase-separated glass according to the first embodiment of the present invention described above with respect to the following (1) to (9). Since they are the same, the description thereof will be omitted, and other items will be described below. (1) density, (2) average thermal expansion coefficient at 30 to 380 ° C., (3) strain point, (4) temperature at 10 ^2.5 dPa · s, (5) liquidus temperature and liquidus viscosity, (6 ) Phase separation temperature and phase separation viscosity, (7) Total light transmittance, (8) Diffuse transmittance, (9) Haze value.

The phase-separated glass according to the second embodiment 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, particularly 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, particularly 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. Suitable upper limit ranges of the surface roughness Ra are 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 10 nm. It is as follows.

The phase-separated glass according to the second embodiment of the present invention is preferably formed by a down draw method, particularly an overflow down draw 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.

The phase-separated glass according to the second embodiment 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, 810 ° C or higher, particularly 910 ° 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 1200 ° C. or lower, 1100 ° C. or lower, particularly 1000 ° 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, particularly 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 according to the second embodiment 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, particularly 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.

The composite substrate according to the second embodiment of the present invention is a composite substrate in which a phase separation glass plate and a substrate are joined, and the phase separation glass plate includes the above phase separation glass. 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 0.3 to 3.0 mm, 0.4 to 2.0 mm, particularly more than 0.5 to 1.8 mm from the viewpoint of maintaining strength.

Refractive index _{n d} of the glass substrate is preferably 1.65 or more, more preferably 1.66 or more, 1.67 or more, 1.68 or more, 1.69 or more, particularly preferably at least 1.70 . 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 1.75 or less.

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 preferable upper limit range of the surface roughness Ra of at least one surface is 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 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.

Next, the phase separation glass according to the third embodiment of the present invention will be described.

Phase-separated glass according to a third embodiment of the present invention, the refractive index _{n d} is 1.65 or more, preferably 1.66 or more, 1.67 or more, 1.68 or more, 1.69 or more, particularly 1.70 or more. When the refractive index n _d is less than 1.65, 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, when the refractive index _nd is too high, 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, 2.20 or less, 2.10 or less, 2.00 or less, 1.90 or less, 1.80 or less, particularly 1.75 or less.

The phase separation glass according to the third embodiment of the present invention has a phase separation structure including at least a first phase and a second phase, and the content of SiO ₂ in the first phase is the second phase. more than the content of SiO ₂ in, and if containing _B 2 _{O 3} in the glass composition, the content of the second of _B 2 _{O 3} in the phase, of _B 2 _{O 3} in the first phase It is preferable that the content is larger than the content. If it does in this way, the refractive index of a 1st phase and a 2nd phase will become easy to differ, and the light-scattering function of glass can be improved.

In the phase-separated glass according to the third embodiment 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 0.01 to 5 μm. If the average particle size of the phase-separated particles is small, the light emitted from the organic EL layer is difficult to scatter at the interface between the first phase and the second phase. On the other hand, if the average particle size of the phase-separated particles is large, the scattering intensity becomes too strong and the total light transmittance may be lowered.

The phase-separated glass according to the third embodiment of the present invention preferably contains, as a glass composition, 30 to 75% of SiO ₂ , 0 to 35% of Al ₂ O _{3 and} 10 to 50% of BaO by mass%. In addition, in description of the containing range of each component,% display means the mass%.

The components that can be introduced in addition to the above components are mostly the same as those already described for the phase-separated glass according to the first embodiment of the present invention, and the differences are only the items described below. is there. That is, when MgO is introduced, the preferred lower limit range is 0.1% or more, 1% or more, 3% or more, or 4% or more, and the particularly preferred range is 5% or more. In the case of introducing ZnO, the preferable lower limit range is 0.1% or more, particularly 1% or more.

The characteristics of the phase-separated glass according to the third embodiment of the present invention are as described above for the phase-separated glass according to the first embodiment of the present invention described above with respect to the following (1) to (5). Since they are the same, the description thereof will be omitted, and other items will be described below. (1) Density, (2) Average thermal expansion coefficient at 30-380 ° C., (3) Strain point, (4) Temperature at 10 ^2.5 dPa · s, (5) Liquidus temperature and liquidus viscosity.

The phase separation temperature is preferably 700 ° C. or higher, 800 ° C. or higher, particularly 900 ° C. or higher. Further, the phase separation viscosity is preferably 10 ^9.0 dPa · s or less, particularly 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. 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 according to the third embodiment of the present invention is preferably phase-separated in the molding step and / or the slow cooling step, but the glass is phase-separated in the melting step, for example, other than these steps. May be.

Wavelengths having a haze value of 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, particularly 90% or more at a wavelength of 400 to 700 nm It is preferable to have. If there is no wavelength having a haze value equal to or greater than a predetermined value, the light scattering function becomes insufficient, and it becomes difficult to extract the light in the glass into the air.

The thickness (in the case of a flat plate) is preferably 1.5 mm or less, 1.3 mm or less, 1.1 mm or less, 0.8 mm or less, 0.7 mm or less, 0.5 mm or less, 0.3 mm or less, 0 .2 mm or less, particularly 0.1 mm or less. The smaller the thickness, the higher the flexibility and the easier it is to improve the design of organic EL lighting. However, when the thickness is extremely small, the glass tends to break. Therefore, the thickness is preferably 10 μm or more, particularly 30 μm or more.

The phase-separated glass according to the third embodiment 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 phase-separated glass according to the third embodiment of the present invention is preferably formed by a down draw method, particularly an overflow down draw 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.

The phase-separated glass according to the third embodiment of the present invention is preferably not subjected to a separate heat treatment step, and is phase-separated in the molding step or phase-separated in the slow cooling (cooling) step immediately after molding. It is preferable. In particular, 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.

When the phase separation glass according to the third embodiment 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 the air such as organic EL lighting, the light emitted from the organic EL layer is reflected by the non-reflective structure of the roughened surface in addition to the light scattering effect of the glass plate. 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, particularly 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.

Phase-separated glass according to a third embodiment of the present invention, when incorporated into the organic EL element, the current efficiency of the organic EL element, than when incorporating the glass having a refractive index n _d is not phase separation of comparable It is preferable to be high. 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%, 10% or more, 15% or more, preferably 20% 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.

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 and 2 are shown. This sample No. The experiments and experimental results for 1 and 2 correspond to the phase-separated glass and the manufacturing method thereof according to the first embodiment of the present invention described above.

Table 2 shows sample No. 3 and 4 are shown. This sample No. The experiments and experimental results for 3 and 4 correspond to the above-described phase separation glass and the composite substrate using the same according to the second embodiment of the present invention.

Table 3 shows sample No. 5 to 9 are shown. This sample No. The experiments and experimental results for 5 to 9 correspond to the phase-separated glass and the method for manufacturing the same according to the third embodiment of the present invention described above.

First, glass raw materials were prepared so as to have the glass compositions shown in Tables 1 to 3, and the obtained glass batch was supplied to a glass melting furnace and melted at 1400 ° C. 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 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 900 ° 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.

[Sample No. About 1]
Sample No. after the above slow cooling treatment. 1 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 phase separation glass, it heat-processed on the conditions for 24 hours at 900 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.

[Sample No. About 2]
Sample No. after the above slow cooling treatment. 2 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. The obtained phase separation glass was subjected to heat treatment at 950 ° C. for 24 hours to cause phase separation. 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 FIGS. The heat-treated samples 1 and 2 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. About 3, 4]
The glass plate (sample No. 3) after the slow cooling treatment 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 1000 degreeC on the conditions 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. 3 subjected to heat treatment had a phase separation structure having phase separation particles of about 300 to 400 nm.

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. 6, 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 0.1 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 FIG. 7, 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 40%. In addition, the diffuse transmittance at a wavelength of 400 to 700 nm was 20% or more.

In [Example 4] and [Example 5], sample No. No. 3 was used for the experiment. It is considered that the same tendency can be obtained for 4 by the same experiment.

[Sample No. About 5, 7-9]
Sample No. after the above slow cooling treatment (not heat-treated). 5, 7 to 9 were immersed in a 1M hydrochloric acid solution for 10 minutes, carbon was deposited, and the sample surface was observed with a field emission scanning electron microscope (S-4300SE, manufactured by Hitachi High-Technologies Corporation). The results are shown in FIGS. 8 to 11 show sample Nos. Images of the sample surfaces 5 and 7 to 9 observed with a field emission scanning electron microscope are shown. As can be seen from FIGS. 5, 7 to 9 had a phase separation structure.

[Sample No. About 7-9]
Sample No. after the above slow cooling treatment (not heat-treated). 7 to 9 were processed to a thickness of 0.7 mm, and both surfaces were mirror-polished, and then the thickness was measured with a spectrophotometer (Spectrophotometer UV-2500PC manufactured by Shimadzu Corporation) for wavelengths of 300 to 800 nm. The total light transmittance and diffuse transmittance in the direction were measured. The results are shown in FIGS. As can be seen from FIGS. Nos. 7 to 9 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. About 9]
Sample No. after the above slow cooling treatment (not heat-treated). The glass plate (plate thickness 0.7mm) which concerns on 9 was produced, and ITO (thickness 100nm) was vapor-deposited as a transparent electrode layer on the surface of this glass plate using the mask. Subsequently, 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 are doped by 6% by mass on a glass plate. After forming CBP (thickness 30 nm), hole blocking layer BAlq (thickness 10 nm), electron transport 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. For the obtained organic EL device, a luminance meter (BM-9 manufactured by Topcon Corporation) 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. 9 a glass plate that does not undergo phase separation have comparable refractive index n _d for the case of manufacturing the organic EL device incorporates (thickness 0.7 mm) is also measured front luminance in the same manner, the current efficiency evaluated. As a result, sample no. When the glass plate according to 9 was incorporated, the current efficiency at 20 mA / cm ² was improved by 22% 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 37.6%, Al}}} 2 O 3 1.5%, CaO 5.9%, SrO 4.9%, BaO 25.2 %, ZrO ₂ 3.2%, TiO ₂ 6.7%, P ₂ O ₅ 1.8%, La ₂ O ₃ 3.8%, Nb ₂ O ₅ 9.4%, refractive index n _d is 1.70.

[Sample No. About 7]
Sample No. after the above slow cooling treatment (not heat-treated). 7 (plate thickness 0.7 mm) was prepared, and ITO (thickness 100 nm) was deposited on the glass plate surface as a transparent electrode layer using a mask. Subsequently, 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 are doped by 6% by mass on a glass plate. After forming CBP (thickness 30 nm), hole blocking layer BAlq (thickness 10 nm), electron transport 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. For the obtained organic EL device, a luminance meter (BM-9 manufactured by Topcon Corporation) 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 used in [Example 8], the front luminance was measured in the same manner to evaluate the current efficiency. did. As a result, sample no. When the glass plate according to 7 was incorporated, the current efficiency at 20 mA / cm ² was improved by 11% as compared with the case where the glass plate according to the comparative example was incorporated.

Claims

After the refractive index n d was molded 1.65 or more phase separation glass by heat-treating phase separation glass obtained, and characterized by obtaining a phase-separated glass containing at least a first phase and a second phase A method for producing phase-separated glass.
The method for producing phase-separated glass according to claim 1, wherein the content of SiO 2 in the first phase is larger than the content of SiO 2 in the second phase.
The phase-separated glass contains, as a glass composition, 30% to 75% SiO 2 , 0 to 35% Al 2 O 3 , and 10 to 50% BaO by mass%. A method for producing phase-separated glass.
The method for producing a phase separation glass according to any one of claims 1 to 3, wherein the phase separation glass is formed into a flat plate shape.
The method for producing a phase separation glass according to any one of claims 1 to 4, wherein the phase separation glass is used for organic EL illumination.
A phase-separated glass produced by the method for producing a phase-separated glass according to any one of claims 1 to 5.
The phase-separated glass according to claim 6, wherein the glass has a wavelength of haze value of 5% or more at a wavelength of 400 to 700 nm.
Refractive index n d is not less than 1.65, and when subjected to heat treatment for 24 hours at 900 ° C., from the state where no phase separation, to have the property of phase separation into at least a first phase and a second phase A phase separation glass characterized by
Refractive index n d is not less than 1.65, a phase separation structure comprising at least a first phase and a second phase, the difference between the maximum value and the minimum value of total light transmittance at a wavelength 400 ~ 700 nm A phase separation glass characterized by being 40% or less.
The phase-separated glass according to claim 9, wherein the particle size of the phase-separated particles is 100 nm or more.
The phase separation glass according to claim 9 or 10, wherein the diffuse transmittance at a wavelength of 400 to 700 nm is 10% or more.
The phase-separated glass contains, by mass%, SiO2 30 to 75%, Al 2 O 3 0 to 35%, BaO 10 to 50% as a glass composition. The phase separation glass described.
The phase-separated glass according to any one of claims 9 to 12, wherein the thickness is 5 to 500 µm.
The phase-separated glass according to any one of claims 9 to 13, which is used for organic EL lighting.
A composite substrate obtained by bonding a phase separation glass plate and a substrate, wherein the phase separation glass plate comprises the phase separation glass according to any one of claims 9 to 14.
The composite substrate according to claim 15, wherein the substrate is a glass substrate.
Composite substrate according to claim 15 or 16 refractive index n d of the substrate is characterized by a 1.50 greater.
The composite substrate according to any one of claims 15 to 17, wherein the phase-separated glass plate and the substrate are joined by optical contact.
19. The composite substrate according to claim 15, which is used for organic EL lighting.
Refractive index n d is not less than 1.65, at least a first phase and which has a phase separation structure comprising a second phase, the content of SiO 2 in the first phase, in the second phase A phase-separated glass characterized by being larger than the content of SiO 2 .
21. The phase separation glass according to claim 20, wherein the glass composition contains, by mass%, SiO 2 30 to 75%, Al 2 O 3 0 to 35%, BaO 10 to 50%.
The phase-separated glass according to claim 20 or 21, wherein the content of Al 2 O 3 in the glass composition is less than 7% by mass.
The phase-separated glass according to any one of claims 20 to 22, wherein the content of B 2 O 3 in the glass composition is 20% by mass or less.
The phase-separated glass according to any one of claims 20 to 23, wherein the content of P 2 O 5 in the glass composition is 0.001 to 10 mass%.
The phase-separated glass according to any one of claims 20 to 24, wherein the content of La 2 O 3 in the glass composition is 0.001 to 15 mass%.
The phase-separated glass according to any one of claims 20 to 25, wherein the content of Nb 2 O 5 in the glass composition is 0.001 to 20 mass%.
The phase-separated glass according to any one of claims 20 to 26, which has a haze value of 5% or more at a wavelength of 400 to 700 nm.
The phase separation glass according to any one of claims 20 to 27, wherein the total light transmittance at a wavelength of 400 to 700 nm is 10% or more.
The phase-separated glass according to any one of claims 20 to 28, which has a flat plate shape.
The phase-separated glass according to any one of claims 20 to 29, which is not subjected to a separate heat treatment step.
31. The current efficiency of the organic EL element is higher when incorporated into an organic EL element than when a non-phase-separated glass having the same refractive index nd is incorporated. The phase-separated glass according to crab.
The phase separation glass according to any one of claims 20 to 31, which is used for organic EL lighting.
An organic EL device comprising the phase separation glass according to any one of claims 1 to 32.