GLASS PLATE AND METHOD FOR MANUFACTURING GLASS PLATE

Abstract

A glass sheet of the present invention releases CO.sub.2 gas in an amount of 5.0 μL/g or less when the glass sheet is subjected to heat treatment under the conditions of 1,500° C. and 4 hours after having been subjected to preheating under the conditions of 900° C. and 1 hour.

Claims

1. A glass sheet, which releases CO.sub.2 gas in an amount of 5.0 μL/g or less when the glass sheet is subjected to heat treatment under the conditions of 1,500° C. and 4 hours after having been subjected to preheating under the conditions of 900° C. and 1 hour.

2. The glass sheet according to claim 1, wherein the glass sheet comprises as a glass composition, in terms of the following oxides in mass %, 50% to 70% of SiO.sub.2, 15% to 22% of Al.sub.2O.sub.3, 0.1% to 15% of B203, 0% to 8% of MgO, 3% to 10% of CaO, 0% to 8% of SrO, and 0% to 15% of BaO, and is substantially free of an alkali metal oxide.

3. The glass sheet according to claim 1, wherein the glass sheet has a temperature at 10.sup.2.5 dPa.Math.s of from 1,530° C. to 1,680° C.

4. The glass sheet according to claim 1, wherein the glass sheet is used as a substrate of a liquid crystal display or an OLED display.

5. A method of manufacturing a glass sheet, comprising: a blending step of blending and mixing glass raw materials so that a glass having a temperature at 10.sup.2.5 dPa.Math.s of from 1,530° C. to 1,680° C. is obtained, to thereby produce a glass batch; a melting step of loading the glass batch into a melting furnace to obtain molten glass; a stirring step of stirring the molten glass at a temperature of 1,550° C. or less; and a forming step of, after supplying the molten glass after the stirring into a forming apparatus, forming the molten glass into a sheet shape to obtain a glass sheet.

6. The method of manufacturing a glass sheet according to claim 5, wherein the forming step comprises forming the molten glass into a sheet shape to obtain a glass sheet which releases CO.sub.2 gas in an amount of 8.0 μL/g or less when the glass sheet is subjected to heat treatment at 1,500° C. for 4 hours after having been subjected to preheating at 900° C. for 1 hour.

7. The glass sheet according to claim 2, wherein the glass sheet has a temperature at 10.sup.2.5 dPa.Math.s of from 1,530° C. to 1,680° C.

8. The glass sheet according to claim 2, wherein the glass sheet is used as a substrate of a liquid crystal display or an OLED display.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0022] FIG. 1 is a graph showing CO.sub.2 gas release rates of a glass A and a glass B in the section of Examples when the glasses are each subjected to heat treatment at 1,500° C. for 4 hours.

DESCRIPTION OF EMBODIMENTS

[0023] In a glass sheet of the present invention, the amount of CO.sub.2 gas released when the glass sheet is subjected to heat treatment under the conditions of 1,500° C. and 4 hours after having been subjected to preheating under the conditions of 900° C. and 1 hour is 5.0 μL/g or less, preferably 3.0 μL/g or less, more preferably 2.0 μL/g or less. When the amount of CO.sub.2 gas released when the glass sheet is subjected to the heat treatment is too large, the number of bubbles in glass caused by stirring reboil becomes excessively large.

[0024] As methods of reducing the amount of CO.sub.2 gas released when the glass sheet is subjected to the heat treatment (the amount of CO.sub.2 gas dissolved in the glass), there are given the following methods (1) to (4): (1) using an oxide raw material instead of using a carbonate raw material as a glass raw material; (2) subjecting glass raw materials to preheating to remove impurities each containing carbon; (3) reducing a CO.sub.2 concentration in a melting atmosphere; and (4) subjecting molten glass to decompression treatment.

[0025] It is preferred that the glass sheet of the present invention comprise as a glass composition, in terms of the following oxides in mass %, 50% to 70% of SiO.sub.2, 15% to 22% of Al.sub.2O.sub.3, 0.1% to 15% of B.sub.2O.sub.3, 0% to 8% of MgO, 3% to 10% of CaO, 0% to 8% of SrO, and 0% to 15% of BaO, and be substantially free of an alkali metal oxide. The reason why the glass composition of the glass sheet is limited as described above is shown below. In the description of the content range of each component, the expression “%” represents “mass %”.

[0026] SiO.sub.2 is a component that forms the skeleton of the glass. The content of SiO.sub.2 is preferably from 50% to 70%, from 54% to 68%, or from 56% to 66%, particularly preferably from 58% to 64%. When the content of SiO.sub.2 is too low, a density becomes too high, and acid resistance is liable to be reduced. Meanwhile, when the content of SiO.sub.2 is too high, a viscosity at high temperature is liable to be increased to reduce meltability. Besides, a devitrified crystal such as cristobalite is liable to precipitate, and a liquidus temperature is liable to be increased.

[0027] Al.sub.2O.sub.3 is a component that forms the skeleton of the glass, and is also a component that enhances a strain point and a Young's modulus. Further, Al.sub.2O.sub.3 is a component that suppresses phase separation. The content of Al.sub.2O.sub.3 is preferably from 15% to 22%, particularly preferably from 16% to 21%. When the content of Al.sub.2O.sub.3 is too low, the strain point and the Young's modulus are liable to be reduced, and besides, the glass is liable to undergo phase separation. Meanwhile, when the content of Al.sub.2O.sub.3 is too high, a devitrified crystal, such as mullite or anorthite, is liable to precipitate, and the liquidus temperature is liable to be increased.

[0028] B.sub.2O.sub.3 is a component that enhances the meltability, and also enhances devitrification resistance. The content of B.sub.2O.sub.3 is preferably from 0.1% to 15%, from 0.3% to 10%, or from 0.5% to 8%, particularly preferably from 1% to 7%. When the content of B.sub.2O.sub.3 is too low, the meltability and the devitrification resistance are liable to be reduced, and besides, resistance to a hydrofluoric acid-based chemical liquid is liable to be reduced. Meanwhile, when the content of B.sub.2O.sub.3 is too high, the Young's modulus and the strain point are liable to be reduced.

[0029] MgO is a component that reduces the viscosity at high temperature to enhance the meltability, and is a component that remarkably enhances the Young's modulus among alkaline earth metal oxides. The content of MgO is preferably from 0% to 8%, from 0% to 7%, from 0% to 6%, or from 0% to 3%, particularly preferably from 0% to 2%. When the content of MgO is too low, the meltability and the Young's modulus are liable to be reduced. Meanwhile, when the content of MgO is too high, the devitrification resistance is liable to be reduced, and besides, the strain point is liable to be reduced.

[0030] CaO is a component that reduces the viscosity at high temperature to remarkably enhance the meltability without reducing the strain point. In addition, a raw material for introducing CaO is relatively inexpensive among those for alkaline earth metal oxides, and hence CaO is a component that achieves a reduction in raw material cost. The content of CaO is preferably from 3% to 10% or from 4% to 10%, particularly preferably from 5% to 9%. When the content of CaO is too low, it becomes difficult to exhibit the above-mentioned effects. Meanwhile, when the content of CaO is too high, the glass is liable to devitrify, and besides, a thermal expansion coefficient is liable to be increased.

[0031] SrO is a component that suppresses the phase separation, and enhances the devitrification resistance. Further, SrO is a component that reduces the viscosity at high temperature to enhance the meltability without reducing the strain point, and is also a component that suppresses an increase in liquidus temperature. The content of SrO is preferably from 0% to 8% or from 0.1% to 7%, particularly preferably from 0.5% to 6%. When the content of SrO is too low, it becomes difficult to exhibit the above-mentioned effects. Meanwhile, when the content of SrO is too high, a strontium silicate-based devitrified crystal is liable to precipitate, and the devitrification resistance is liable to be reduced.

[0032] BaO is a component that remarkably enhances the devitrification resistance. The content of BaO is preferably from 0% to 15%, from 0% to 12%, or from 0.1% to 9%, particularly preferably from 1% to 7%. When the content of BaO is too low, it becomes difficult to exhibit the above-mentioned effects. Meanwhile, when the content of BaO is too high, the density becomes too high, and the meltability is liable to be reduced. In addition, a devitrified crystal containing BaO is liable to precipitate, and the liquidus temperature is liable to be increased.

[0033] SnO.sub.2 is a component that acts as a fining agent. The content of SnO.sub.2 is preferably from 0% to 1% or from 0.1% to 0.5%, particularly preferably from 0.2% to 0.4%. When the content of SnO.sub.2 is too high, a devitrified crystal is liable to precipitate, and the liquidus temperature is liable to be increased.

[0034] It is preferred that the glass sheet be substantially free (that is, 0.1% or less) of alkali metal oxides (Li.sub.2O, Na.sub.2O, and K.sub.2O).

[0035] In addition to the above-mentioned components, any other components, for example, a component, such as ZrO.sub.2, ZnO, P.sub.2O.sub.5, or Mo, may be added. The content of the other component than the above-mentioned components is preferably 10% or less, particularly preferably 5% or less in terms of total content, from the viewpoint of appropriately exhibiting the effects of the present invention.

[0036] In the glass sheet of the present invention, the strain point is preferably 680° C. or more or 690° C. or more, particularly preferably 700° C. or more. When the strain point is too low, the glass sheet is liable to be thermally shrunk in heat treatment in a manufacturing process for a display. Meanwhile, when the strain point is too high, the manufacturing cost of the glass sheet is liable to rise.

[0037] In the glass sheet of the present invention, the temperature at 10.sup.2.5 dPa.Math.s is preferably from 1,530° C. to 1,680° C., more preferably from 1,550° C. to 1,650° C., particularly preferably from 1,580° C. to 1,630° C. When the temperature at 10.sup.2.5 dPa.Math.s is too low, the glass sheet is liable to be thermally shrunk in heat treatment in a manufacturing process for a display. Meanwhile, when the temperature at 10.sup.2.5 dPa.Math.s is too high, the meltability is reduced, and hence the manufacturing cost of the glass sheet is liable to rise. As the temperature at 10.sup.2.5 dPa.Math.s becomes higher, bubbles caused by the stirring reboil are liable to remain. Accordingly, as the temperature at 10.sup.2.5 dPa.Math.s becomes higher, the effects of the present invention relatively increase.

[0038] A method of manufacturing a glass sheet of the present invention is characterized by comprising: a blending step of blending and mixing glass raw materials so that a glass having a temperature at 10.sup.2.5 dPa.Math.s of from 1,530° C. to 1,680° C. is obtained, to thereby produce a glass batch; a melting step of loading the glass batch into a melting furnace to obtain molten glass; a fining step of fining the molten glass; a stirring step of stirring the molten glass after the fining step at a temperature of 1,550° C. or less; and a forming step of, after supplying the molten glass after the stirring into a forming apparatus, forming the molten glass into a sheet shape to obtain a glass sheet. Now, the method of manufacturing a glass sheet of the present invention is described in detail.

[0039] First, the glass raw materials serving as introduction sources for the respective components are blended and mixed so that a glass having a temperature at 10.sup.2.5 dPa.Math.s of from 1,530° C. to 1,680° C. is obtained, to thereby produce a glass batch. A glass cullet may be used as the glass raw material as required. The glass cullet is a glass waste discharged in, for example, a glass manufacturing process. The method of mixing the glass raw materials is not particularly limited, and may be appropriately selected in accordance with the masses of the glass raw materials to be mixed at one time or the kinds of the glass raw materials. An example thereof is a mixing method with a pan-type mixer or a rotary mixer.

[0040] From the viewpoint of reducing the amount of CO.sub.2 gas released from the glass sheet in the heat treatment, it is preferred that an oxide raw material be used as the glass raw material, instead of a carbonate raw material, and it is also preferred that the glass raw materials be subjected to preheating to remove impurities each containing carbon.

[0041] Next, the obtained glass batch is loaded into a melting furnace. The loading of the glass batch into the melting furnace is typically continuously performed by a raw material feeder such as a screw charger, but may also be intermittently performed.

[0042] The glass batch loaded into the melting furnace is heated by, for example, a combustion atmosphere provided by a burner or the like, or an electrode arranged inside of the melting furnace to become molten glass. The melting temperature of the glass batch is from about 1,530° C. to about 1,680° C. From the viewpoint of reducing the amount of CO.sub.2 gas released from the glass sheet in the heat treatment, it is preferred that the CO.sub.2 concentration in a melting atmosphere be reduced, and it is also preferred that the molten glass be subjected to decompression treatment.

[0043] Subsequently, the obtained molten glass is subjected to the fining step, the stirring step, and a supplying step, and is then gradually cooled in order to be loaded into the forming apparatus.

[0044] A process temperature in the stirring step is 1,550° C. or less, preferably 1,500° C. or less, more preferably 1,450° C. or less. When the process temperature in the stirring step is too high, the stirring reboil is hardly suppressed.

[0045] In the method of manufacturing a glass sheet of the present invention, when the process temperature in the stirring step is regulated to 1,550° C. or less, the amount of CO.sub.2 gas released from the glass sheet to be obtained when the glass sheet is subjected to heat treatment under the conditions of 1,500° C. and 4 hours after having been subjected to preheating under the conditions of 900° C. and 1 hour is 8.0 μL/g or less, preferably 5.0 μL/g or less, more preferably 3.0 μL/g or less, particularly preferably 2.0 μL/g or less. When the amount of CO.sub.2 gas released from the glass sheet when the glass sheet is subjected to the heat treatment is too large, the number of bubbles in the glass caused by the stirring reboil becomes excessively large.

[0046] After that, the molten glass is supplied into the forming apparatus and formed into a flat sheet shape having a predetermined thickness and surface quality, and then cut into a predetermined size to become a glass product (glass sheet). As a forming method, for example, an overflow down-draw method or a float method may be adopted. In particular, an overflow down-draw method is preferred because a glass sheet having a smooth surface without polishing can be produced.

[0047] The glass sheet produced as described above is used as a substrate of, for example, a liquid crystal display or an OLED display.

EXAMPLES

[0048] <Production of Base Glass>

[0049] A glass batch was obtained by blending and mixing glass raw materials so that a glass comprising as a glass composition, in terms of the following oxides in mass %, 58.8% of SiO.sub.2, 19% of Al.sub.2O.sub.3, 6.5% of B.sub.2O.sub.3, 2.5% of MgO, 6.5% of CaO, 0.5% of SrO, 6% of BaO, and 0.2% of SnO.sub.2 was obtained. A base glass was obtained by melting and forming the glass batch. The base glass had a strain point of 690° C. and a temperature at 10.sup.2.5 dPa.Math.s of 1,540° C.

[0050] <Production of Glass A>

[0051] 100 g in total of a base glass having a particle diameter of 5.6 mm or less was weighed, and then was loaded into a platinum crucible to be melted under the conditions of 1,500° C. and 1 hour, and then the temperature was increased to 1,650° C. After completion of the temperature increase, the resultant was decompressed to 10 kPa and was kept for 2 hours. After that, the molten glass in the platinum crucible was cooled, and removed from the platinum crucible to produce a bulk-form glass A.

[0052] <Production of Glass B>

[0053] 100 g in total of the bulk-form base glass was weighed, and then was loaded into a platinum crucible to be melted under the conditions of 1,500° C. and 1 hour. After that, the molten glass in the platinum crucible was cooled without decompression treatment, and removed from the platinum crucible to produce a bulk-form glass B.

[0054] <Measurement of Dissolved Amount of CO.sub.2 Gas>

[0055] The glass A and the glass B were partially pulverized to have a particle diameter of from 2.0 mm to 5.6 mm, classified, washed, and then dried. 1.0 g in total of the glasses after the classification were weighed, and then the glasses were subjected to preheating under the conditions of 900° C. and 1 hour to remove CO.sub.2 gas adsorbed on glass surfaces, and were then subjected to heat treatment under the conditions of 1,500° C. and 4 hours. The total amounts of CO.sub.2 gas released during this period of time were each measured with a mass spectrometer.

[0056] <Production of Foreign Glass 1>

[0057] A glass batch was obtained by blending and mixing glass raw materials so that a glass comprising as a glass composition, in terms of the following oxides in mass %, 64.8% of SiO.sub.2, 16.5% of Al.sub.2O.sub.3, 5.5% of B.sub.2O.sub.3, 2% of MgO, 5.5% of CaO, 0.5% of SrO, 5% of BaO, and 0.2% of SnO.sub.2 was obtained. 100 g of the glass batch was loaded into a platinum crucible to be melted under the conditions of 1,500° C. and 2 hours, and then the temperature was increased to 1,650° C. After completion of the temperature increase, the resultant was kept for 1 hour. After that, the obtained glass was subjected to water granulation, was dried, and was then pulverized to have a particle diameter of 5.6 mm or less. The resultant was melted again under the conditions of 1,500° C. and 2 hours. The melting operation was repeated twice. The obtained glass was further subjected to water granulation, was dried, and was then pulverized to have a particle diameter of 5.6 mm or less. The resultant was loaded into a platinum crucible and was melted under the conditions of 1,600° C. and 1 hour. The resultant was decompressed to 10 kPa, and was then kept for 1 hour after the temperature was increased to 1,650° C. After that, the molten glass in the platinum crucible was cooled, and was removed from the platinum crucible to produce a foreign glass 1 which was in a bulk form, homogeneous, and free of bubbles.

[0058] <Stirring Test: Sample No. 1>

[0059] 50 g of the glass A and 50 g of the foreign glass 1 were loaded into a platinum crucible while being superimposed on each other, and the resultant was subjected to preheating under the conditions of 900° C. and 2 hours to remove CO.sub.2 gas adsorbed on the surface, and was then heated to melt under the conditions of 1,450° C. and 10 minutes.

[0060] After the melting, a stirrer made of platinum (paddle type: 20 mm×10 mm×2 mm, shaft diameter: 6 mm) was slowly inserted from above to a position at about 10 mm from a bottom surface of the platinum crucible, and the resultant was kept for 1 hour to remove air bubbles included at the time of the insertion. Next, stirring was performed with a stirrer at 10 rpm for 5 minutes, and after the stirring, the stirrer was slowly taken out. After that, the molten glass in the platinum crucible was cooled and removed from the platinum crucible to produce a bulk-form glass (Sample No. 1).

[0061] In the obtained bulk-form glass, the number of bubbles included in a region (φ20 mm×10 mm) stirred with the stirrer was counted, and the number density of bubbles was calculated. After that, a gas component of the bubbles was analyzed with a mass spectrometer.

[0062] <Stirring Test: Sample No. 2>50 g of the glass B and 50 g of the foreign glass 1 were loaded in a platinum crucible while being superimposed on each other, and the resultant was subjected to preheating under the conditions of 900° C. and 2 hours to remove CO.sub.2 gas adsorbed on the surface, and was then heated to melt under the conditions of 1,450° C. and 10 minutes.

[0063] After the melting, a stirrer made of platinum (paddle type: 20 mm×10 mm×2 mm, shaft diameter: 6 mm) was slowly inserted from above to a position at about 10 mm from a bottom surface of the platinum crucible, and the resultant was kept for 1 hour to remove air bubbles included at the time of the insertion. Next, stirring was performed with a stirrer at 10 rpm for 5 minutes, and after the stirring, the stirrer was slowly taken out. After that, the molten glass in the platinum crucible was cooled and removed from the platinum crucible to produce a bulk-form glass (Sample No. 2).

[0064] In the obtained bulk-form glass, the number of bubbles included in a region (φ20 mm×10 mm) stirred with the stirrer was counted, and the number density of bubbles was calculated. After that, a gas component of the bubbles was analyzed with a mass spectrometer.

[0065] <Test Results>

[0066] Example (Sample No. 1) and Comparative Example (Sample No. 2) of the present invention are shown in Table 1.

TABLE-US-00001 TABLE 1 Sample No. 1 Sample No. 2 Glass used Glass A 1.6 Glass B 5.8 Dissolved amount of CO.sub.2 gas (μL/g) Number density of 1,000 6,100 bubbles (bubbles/kg) Main component of N.sub.2 CO.sub.2 bubbles

[0067] Further, CO.sub.2 gas release rates of the glass A and the glass B when the glasses were each subjected to heat treatment under the conditions of 1,500° C. and 4 hours were measured. The results are shown in FIG. 1.

[0068] As apparent from Table 1 and FIG. 1, the glass A had a smaller dissolved amount of CO.sub.2 gas than the glass B. As a result, the number density of bubbles of Sample No. 1 was smaller than that of Sample No. 2. In addition, while the bubbles of Sample No. 1 contained, as a main component, N.sub.2 derived from air occurring at the time of the insertion of the stirrer and at the time of stirring, the bubbles of Sample No. 2 contained, as a main component, CO.sub.2 derived from stirring reboil. From the results of the foregoing, it is found that when the dissolved amount of CO.sub.2 gas in the glass is reduced, the stirring reboil can be suppressed.

[0069] <Production of Foreign Glass 2>

[0070] A glass batch was obtained by blending and mixing glass raw materials so that a glass comprising as a glass composition, in terms of the following oxides in mass %, 67.8% of SiO.sub.2, 15% of Al.sub.2O.sub.3, 5% of B.sub.2O.sub.3, 2% of MgO, 5% of CaO, 0.5% of SrO, 4.5% of BaO, and 0.2% of SnO.sub.2 was obtained. After that, a foreign glass 2 which was in a bulk form, homogeneous, and free of bubbles was produced by the same method as in the case of the foreign glass 1.

[0071] <Stirring Test: Sample No. 3>

[0072] The same stirring test as described above was performed using a combination of 50 g of the glass B and 50 g of the foreign glass 2 to provide Sample No. 3.

[0073] <Stirring Test: Samples No. 4 and No. 5>

[0074] Each of a combination of 50 g of the glass B and 50 g of the foreign glass 1 and a combination of 50 g of the glass B and 50 g of the foreign glass 2 was subjected to preheating under the conditions of 900° C. and 2 hours to remove CO.sub.2 gas adsorbed on the surface, and was then heated to melt under the conditions of 1,600° C. and 10 minutes. The stirring test was hereinafter performed under the same conditions as described above to provide Samples No. 4 and No. 5.

[0075] <Test Results>

[0076] Example (Sample No. 3) and Comparative Examples (Samples No. 4 and No. 5) of the present invention are shown in Table 2.

TABLE-US-00002 TABLE 2 Sample No. 3 Sample No. 4 Sample No. 5 Glass Glass B Glass B Glass B composition Foreign Foreign Foreign glass 2 glass 1 glass 2 Stirring 1,450 1,600 1,600 temperature (° C.) Number Density of 2,800 190,000 280,000 bubbles (bubbles/kg)

[0077] As apparent from Table 2, Sample No. 3 had a stirring temperature of 1,450° C., and hence had a smaller number density of bubbles than each of Samples No. 4 and No. 5. Accordingly, it is found that, when the molten glass is stirred at low temperature, the stirring reboil can be suppressed.