JP6562240B2 - Manufacturing method of silicate glass and silica raw material for silicate glass - Google Patents

Description

  The present invention relates to a method for producing a silicate glass, a silicate glass, and a silica raw material for a silicate glass. For example, a method for producing a silicate glass suitable for a substrate such as a liquid crystal display and an organic EL display, the silicate glass and the silicate The present invention relates to a silica raw material for glass.

Silicate glass is produced by preparing various glass raw materials to obtain a glass batch, and then melting and molding the glass batch. As is well known, silicate glass is glass mainly composed of SiO ₂ . For this reason, the ratio of the silica raw material which occupies in a glass batch increases compared with another glass raw material.

  In the case of display applications, the silica raw material has been required to have high purity in order to improve the quality of silicate glass. That is, hitherto, silica raw materials with few impurities have been used.

  Moreover, as a silicate glass used for a liquid crystal display or the like, non-alkali glass (silicate glass having an alkali metal oxide content of less than 0.5% by mass in the glass composition) is used. Since alkali-free glass is hardly soluble, it has a feature that it is difficult to melt compared to alkali-containing glass. Under such circumstances, it has been studied to adjust the particle size of the silica raw material within a predetermined range to enhance the solubility of the glass batch.

For example, Patent Document 1 discloses reducing chromite foreign matter in a silicate glass by using a silica raw material having a low content of Cr ₂ O ₃ that is a hardly soluble impurity. Patent Document 2 discloses that the homogeneity of silicate glass is improved by using a silica raw material having an average particle diameter D _{50 of} 30 to 60 μm. Patent Document 3 discloses that the foam quality of silicate glass is enhanced by using a silica raw material having an average particle diameter D _{50 of} 70 to 200 μm.

JP 2012-201524 A JP 2004-0667408 A JP2013-107801A

By the way, in order to improve the foam quality of the silicate glass, a refining agent that generates a refining gas at the time of melting is used. In a hardly soluble silicate glass such as an alkali-free glass, for example, a vitrification reaction occurs at a temperature of 1200 to 1300 ° C., and defoaming and homogenization are performed at a high temperature of 1400 ° C. or higher. For this reason, As ₂ O ₃ that generates a clarified gas in the vicinity of 1200 to 1600 ° C. is used as a clarifier of the hardly soluble silicate glass, and Sb ₂ O ₃ that generates a clarified gas in the vicinity of 1200 to 1300 ° C. Was used. However, As ₂ O ₃ and Sb ₂ O ₃ are environmentally hazardous substances, and their use is being restricted.

SnO ₂ is promising as an alternative fining agent for As ₂ O ₃ and Sb ₂ O ₃ . SnO ₂ has a property of releasing a clarified gas when it is divalent at a temperature of 1400 ° C. or higher.

On the other hand, SnO ₂ has a property that does not release a clarified gas so much at an initial melting temperature (for example, 1000 to 1400 ° C.). For this reason, SnO ₂ is difficult to reduce the amount of dissolved gas in the glass, and tends to induce reboil later. In particular, when As ₂ O ₃ and Sb ₂ O ₃ are reduced as a fining agent, the tendency becomes remarkable.

  As a method of supplementing the fining power at the initial melting temperature, it is assumed that the particle size of the glass raw material is adjusted. However, although the silica raw materials described in Patent Documents 1 to 3 have the effect of increasing the solubility of the glass batch, they are poor in the effect of supplementing the fining power and hardly contribute to the improvement of the reboiling property.

The present invention has been made in view of the above circumstances, and the technical problem thereof is a silica raw material that can supplement the fining power at the initial melting temperature even when As ₂ O ₃ and Sb ₂ O ₃ are reduced as a fining agent. Is to improve the foam quality of hardly soluble silicate glass, especially alkali-free glass.

As a result of intensive studies, the present inventors have introduced a silica raw material containing a small amount of an alkaline earth metal component into a glass batch, and CO ₂ gas (carbon dioxide gas) is generated at the initial melting temperature. This CO ₂ gas is clarified. It has been found that it can contribute to the improvement of reboilability by increasing the properties and reducing the dissolved gas, and is proposed as the present invention. That is, the method for producing a silicate glass of the present invention is a method for producing a silicate glass in which a glass batch is melted and molded to obtain a silicate glass. In the glass batch, an alkaline earth metal component is converted into an oxide. A silica raw material containing 0.01 to 2% by mass is introduced. Here, the “silica raw material” refers to a raw material having a SiO ₂ content of 95% by mass or more. The CO ₂ gas also has an effect of increasing the homogeneity of the silicate glass by stirring the molten glass at a temperature at the initial stage of melting.

As is well known, the carbonate raw material does not generate CO ₂ gas at the initial melting temperature because decomposition is completed at a low temperature. Surprisingly, the inventors' investigation has revealed that CO ₂ gas is generated even at a temperature of 1200 ° C. or higher when a silica raw material containing a small amount of an alkaline earth metal component is used.

  2ndly, it is preferable that the manufacturing method of the silicate glass of this invention introduce | transduces the silica raw material which contains 0.01-0.3 mass% of Mg components in conversion of MgO in a glass batch. If it does in this way, it will become possible to generate gas exactly at the temperature of the initial stage of melting.

  Thirdly, it is preferable that the manufacturing method of the silicate glass of this invention introduce | transduces the silica raw material which contains 0.01-0.5 mass% of Ca components in conversion of CaO in a glass batch. If it does in this way, it will become possible to generate gas exactly at the temperature of the initial stage of melting.

Fourth, the manufacturing method of the silicate glass of the present invention, in the glass batch, it is preferable to introduce a silica raw material including 0.001 to 0.008 wt% of Fe component in terms _{of Fe} 2 _{O 3.} If it does in this way, coloring of silicate glass can be controlled, suppressing the cost of a silica raw material.

Fifth, in the method for producing a silicate glass of the present invention, it is preferable to introduce a silica raw material that generates CO ₂ gas in a temperature range of 1000 to 1400 ° C. into a glass batch. In this way, the refining power can be compensated accurately at the temperature at the beginning of melting.

Sixth, the method for producing a silicate glass of the present invention preferably introduces a silica raw material that generates CO ₂ gas and H ₂ O gas (water vapor) in a temperature range of 1000 to 1400 ° C. in a glass batch. .

As is well known, since a hydroxide raw material is decomposed at a low temperature, H ₂ O gas is not generated at an initial melting temperature. Surprisingly, the inventors' investigation has revealed that when a silica raw material containing a small amount of an alkaline earth metal component is used, a large amount of H ₂ O gas is generated even at a temperature of 1200 ° C. or higher. The H ₂ O gas generated in the high temperature range can improve the refinability by reducing the dissolved gas while improving the clarity. Further, the H ₂ O gas has an effect of increasing the homogeneity of the silicate glass by stirring the molten glass at a temperature at the initial stage of melting.

Seventh, the method for producing a silicate glass of the present invention produces a silicate glass so that the content of the S component in the glass composition of the silicate glass is less than 0.01% by mass in terms of SO _3. It is preferable. In this way, reboilability can be improved.

Eighth, in the method for producing a silicate glass of the present invention, the content of As ₂ O ₃ in the glass composition of the silicate glass is less than 0.05 mass%, and the content of Sb ₂ O ₃ is 0.05 mass. It is preferable to prepare the glass batch so that the SnO ₂ content is 0.01 to 1% by mass. If it does in this way, it will become easy to raise the bubble quality of silicate glass, meeting the recent environmental demand.

  Ninthly, in the method for producing a silicate glass of the present invention, it is preferable to prepare a glass batch so that the content of alkali metal oxide in the glass composition of the silicate glass is less than 0.5% by mass. . If it does in this way, silicate glass can be applied to substrates, such as a liquid crystal display and an organic EL display.

Tenth, in the method for producing a silicate glass of the present invention, the glass composition of the silicate glass is by mass%, SiO ₂ 50-80%, Al ₂ O ₃ 5-25%, B ₂ O ₃ 0-20. %, MgO 0-15%, CaO 1-15%, SrO 0-15%, BaO 0-15% are preferably prepared. If it does in this way, it will become easy to satisfy required characteristics, such as devitrification resistance, a high strain point, low density, and acid resistance.

  11thly, it is preferable to shape | mold the manufacturing method of the silicate glass of this invention in a flat plate shape by the overflow downdraw method or the float glass method. If it does in this way, it will become easy to aim at enlargement and thickness reduction of silicate glass.

  12thly, the silicate glass of this invention was produced by said manufacturing method of silicate glass.

  13thly, it is preferable that the silica raw material for silicate glass of this invention contains 0.01 mass% or more of alkaline-earth metal components in conversion of an oxide.

  14thly, it is preferable that the silica raw material for silicate glass of this invention contains 0.01-0.3 mass% of Mg components in conversion of MgO.

  15thly, it is preferable that the silica raw material for silicate glass of this invention contains 0.01-0.5 mass% of Ca components in conversion of CaO.

Sixteenth, silicate glass silica material of the present invention preferably contains 0.001 to 0.008 wt% of Fe component in terms _{of Fe} 2 _{O 3.}

Seventeenth, the silica raw material for silicate glass of the present invention is characterized by generating CO ₂ gas in a temperature range of 1000 to 1400 ° C.

Eighteenth, the silica raw material for silicate glass of the present invention is characterized by generating CO ₂ gas and H ₂ O gas in a temperature range of 1000 to 1400 ° C.

  Nineteenth, the silica raw material for silicate glass of the present invention is preferably natural silica sand.

In sample No. 1 according to [Example 1]. For 1,2, the measurement data indicating the release of CO ₂ gas when the temperature range is heated at a heating rate of 8 ° C. / minute from 200 ° C. to 1300 ° C.. In sample No. 1 according to [Example 1]. For 1,2, the measurement data indicating the release of the H _{2 O} gas when the temperature range is heated at a heating rate of 8 ° C. / minute from 200 ° C. to 1300 ° C..

  Hereinafter, the manufacturing method of the silicate glass of this invention is explained in full detail.

  First, the glass raw material used as the introduction source of each component is prepared and mixed so that it may become a desired glass composition, and a glass batch batch is produced. If necessary, glass cullet may be used as a glass raw material. Glass cullet is glass waste discharged in a glass manufacturing process or the like.

  Next, the obtained glass batch is put into a glass melting kiln and melted and vitrified. The glass batch is normally charged continuously into the glass melting furnace, but may be intermittent. Moreover, the melting temperature of the glass batch in a glass melting furnace is about 1500-1650 degreeC in the case of an alkali free glass. In this way, the glass raw material is melted to obtain molten glass.

  Subsequently, after clarifying and stirring the molten glass, the molten glass is supplied to a molding apparatus, and the molten glass is formed into a flat plate shape so as to have a predetermined thickness and surface quality. As a molding method, an overflow downdraw method, a float method, or the like can be employed.

  The flat plate-like silicate glass thus produced is used as a substrate for a liquid crystal display, for example.

  Next, the silica raw material according to the present invention will be described.

  The silica raw material according to the present invention preferably contains the following trace components. Content of an alkaline-earth metal component is 0.01-2 mass% in conversion of an oxide, Preferably it is 0.03-1 mass%, More preferably, it is 0.05-0.5 mass%. When there is too little content of an alkaline-earth metal component, it will become difficult to discharge | release gas at the temperature of the fusion | melting initial stage. On the other hand, when the content of the alkaline earth metal component is too large, the glass batch is unreasonably blown up at the initial stage of melting, and the durable life of the glass melting furnace tends to be reduced. The alkaline earth metal component is preferably contained in the form of carbonate.

  The content of the Mg component is preferably 0.01 to 0.3% by mass, 0.01 to 0.2% by mass, 0.02 to 0.1% by mass, particularly 0.02 to 0.05% in terms of MgO. % By mass. When there is too little content of Mg component, it will become difficult to discharge | release gas at the temperature of the fusion | melting initial stage. On the other hand, if the content of the Mg component is too large, the glass batch is unreasonably blown up at the initial stage of melting, and the durable life of the glass melting furnace tends to be reduced.

  The content of the Ca component is preferably 0.01 to 0.5% by mass, 0.01 to 0.3% by mass, 0.01 to 0.2% by mass, and 0.02 to 0.1% in terms of CaO. %, In particular 0.02 to 0.05% by weight. When there is too little content of Ca component, it will become difficult to discharge | release gas at the temperature of the fusion | melting initial stage. On the other hand, if the content of the Ca component is too large, the glass batch is unreasonably blown up at the initial stage of melting, and the durable life of the glass melting furnace tends to be reduced.

The content of the Fe component is preferably 0.001 to 0.008% by mass, particularly 0.002 to 0.004% by mass in terms of Fe ₂ O ₃ . When there is too little content of Fe component, the raw material cost of a silica raw material will rise easily. On the other hand, when there is too much content of Fe component, it will become easy to color silicate glass.

The content of Ti component, 0.0005 to 0.008 wt% in terms of TiO _2, in particular 0.001 to 0.004 weight% is preferred. When there is too little content of Ti component, the raw material cost of a silica raw material will rise easily. On the other hand, when there is too much content of Ti component, it will become easy to color silicate glass.

The method of manufacturing a silicate glass of the present invention, in the glass batch, it is preferred to introduce the silica raw material for generating CO ₂ gas in a temperature range of 1000 to 1400 ° C., the CO ₂ gas in a temperature range of 1200 to 1400 ° C. It is preferable to introduce a silica raw material that generates water. In this way, the refining power can be compensated accurately at the temperature at the beginning of melting.

The method of manufacturing a silicate glass of the present invention, in the glass batch, it is preferred to introduce the silica raw material for generating CO ₂ gas and the _{H 2} O gas in a temperature range of 1000 to 1400 ° C., a temperature of 1200 to 1400 ° C. It is more preferable to introduce a silica raw material that generates CO ₂ gas and H ₂ O gas in the region. In this way, the refining power can be compensated accurately at the temperature at the beginning of melting.

  As a method for introducing a small amount of the alkaline earth metal component into the silica raw material, a chemical synthesis method may be adopted, but from the viewpoint of raw material cost, it is preferable to use a natural raw material containing a small amount of the alkaline earth metal component. For example, it is preferable to collect a high-purity silica sand layer formed by the erosion action of the dolomite deposit and use it as a silica raw material.

The method of manufacturing a silicate glass of the present invention, is less than 0.05 wt% the content of _As 2 _{O 3} in the glass composition of the silicate glass, the content of _Sb 2 _{O 3} is less than 0.05 wt%, SnO It is preferable to prepare the glass batch so that the content of ₂ is 0.01 to 1% by mass. If it does in this way, it will become easy to raise the bubble quality of silicate glass, meeting the recent environmental demand.

SnO ₂ is a component that has a good clarification action in a high temperature range, a component that increases the strain point, and a component that decreases high temperature viscosity. The content of SnO ₂ is preferably 0.01 to 1% by mass, 0.05 to 0.5% by mass, particularly 0.1 to 0.3% by mass. When the content of SnO ₂ is too large, the devitrified crystal of SnO ₂ is likely to precipitate, and the precipitation of the devitrified crystal of ZrO ₂ is easily promoted. Incidentally, when the content of SnO ₂ is less than 0.01 wt%, it becomes difficult to enjoy the above-mentioned effects.

As ₂ O ₃ and Sb ₂ O ₃ are also effective as fining agents. However, the silicate glass according to the present invention does not completely exclude the inclusion of these components, but it is preferable not to use these components from an environmental viewpoint. Furthermore, when As ₂ O ₃ is contained in a large amount, the resistance to solarization tends to decrease. The content of As ₂ O ₃ is preferably less than 0.05% by mass, and the content of Sb ₂ O ₃ is also preferably less than 0.05% by mass.

In the method for producing a silicate glass of the present invention, the content of the S component in the glass composition of the silicate glass is less than 0.01% by mass (desirably less than 0.005% by mass) in terms of SO ₃ , It is preferable to produce a silicate glass, and the glass so that the content of the S component in the glass composition of the silicate glass is less than 0.01% by mass (desirably less than 0.005% by mass) in terms of SO _3. It is preferred to prepare the batch. SO ₃ acts as a fining agent, but if its content is too high, SO ₂ reboil tends to be generated.

Incidentally, as another refining agent, F, halides such as Cl, may be introduced CeO _2. When a halide such as F or Cl is introduced as a fining agent, H ₂ O generated from the silica raw material is released as HF gas or HCl gas.

In the manufacturing method of the silicate glass of this invention, it is preferable to prepare a glass batch so that content of the alkali metal oxide in the glass composition of silicate glass may be less than 0.5 mass%. In this way, it becomes easy to prevent the situation where alkali ions diffuse in the semiconductor material in the manufacturing process of the display. Specifically, the content of the alkali metal oxide is preferably less than 0.5% by mass, less than 0.3% by mass, particularly 0.01 to 0.2% by mass. The content of Li ₂ O and Na ₂ O is preferably less than 0.3% by mass and particularly less than 0.2% by mass for each component. The content of K ₂ O is preferably less than 0.5% by mass, less than 0.3% by mass, particularly 0.01 to 0.2% by mass.

In the method for producing silicate glasses of the present invention, the glass composition of the silicate glass, in _{mass%, SiO 2 50~80%, Al} 2 O 3 5~25%, B 2 O 3 0~20%, MgO 0 It is preferable to prepare the glass batch so as to contain -15%, CaO 1-15%, SrO 0-15%, BaO 0-15%. The reason for limiting the glass composition of the silicate glass as described above is shown below. In addition, in description of the containing range of each component,% display points out the mass%.

SiO ₂ is a component that forms a glass skeleton. The content of SiO ₂ is preferably 50 to 80%, 54 to 70%, 56 to 66%, particularly 58 to 64%. When the content of SiO ₂ is too small, the density becomes too high, the acid resistance is likely to decrease. On the other hand, if the content of SiO ₂ is too large, the high-temperature viscosity becomes high and the meltability tends to decrease, and devitrification crystals such as cristobalite are likely to precipitate, and the liquidus temperature is likely to rise. Become.

Al ₂ O ₃ is a component that forms a glass skeleton, a component that increases the strain point and Young's modulus, and a component that further suppresses phase separation. The content of Al ₂ O ₃ is preferably 5 to 25%, 12 to 24%, 15 to 22%, particularly 16 to 21%. When the content of Al ₂ O ₃ is too small, the strain point, the Young's modulus tends to decrease, also tends glass phase separation. On the other hand, when the content of Al ₂ O ₃ is too large, devitrification crystals such as mullite and anorthite are likely to precipitate, and the liquidus temperature is likely to rise.

B ₂ O ₃ is a component that enhances meltability and increases devitrification resistance. The content of B ₂ O ₃ is preferably 0 to 20%, 0 to 12%, 0 to 10%, 0.5 to 8%, particularly 1 to 7%. When B ₂ content of O ₃ is too small, it tends to decrease. Meltability and devitrification resistance, also resistance tends to decrease with respect to hydrofluoric acid chemical. On the other hand, when the content of B ₂ O ₃ is too large, the Young's modulus and the strain point tends to decrease.

  MgO is a component that lowers the viscosity at high temperature and increases the meltability, and among alkaline earth metal oxides, it is a component that significantly increases the Young's modulus. The content of MgO is preferably 0 to 15%, 0 to 8%, 0 to 7%, 0 to 6%, 0 to 3%, particularly 0 to 2%. When there is too little content of MgO, a meltability and a Young's modulus will fall easily. On the other hand, when there is too much content of MgO, devitrification resistance will fall easily and a strain point will fall easily.

  CaO is a component that lowers the high-temperature viscosity without significantly reducing the strain point and significantly increases the meltability. Further, among the alkaline earth metal oxides, since the introduced raw material is relatively inexpensive, it is a component that lowers the raw material cost. The content of CaO is preferably 1 to 15%, 3 to 11%, 4 to 10%, particularly 5 to 9%. When there is too little content of CaO, it will become difficult to receive the said effect. On the other hand, when there is too much content of CaO, while glass will become easy to devitrify, a thermal expansion coefficient will become high easily.

  SrO is a component that suppresses phase separation and increases devitrification resistance. Furthermore, it is a component that lowers the high-temperature viscosity without increasing the strain point and increases the meltability, and also suppresses the rise in the liquidus temperature. The content of SrO is preferably 0 to 15%, 0.1 to 9%, particularly 0.5 to 6%. When there is too little content of SrO, it will become difficult to receive the said effect. On the other hand, when the content of SrO is too large, strontium silicate devitrification crystals are likely to precipitate, and devitrification resistance is likely to be lowered.

  BaO is a component that significantly increases devitrification resistance. The content of BaO is preferably 0 to 15%, 0 to 12%, 0.1 to 9%, particularly 1 to 7%. When there is too little content of BaO, it will become difficult to receive the said effect. On the other hand, when there is too much content of BaO, while a density will become high too much, a meltability will fall easily. Further, devitrified crystals containing BaO are likely to precipitate, and the liquidus temperature is likely to rise.

ZrO ₂ functions to increase the strain point and Young's modulus. However, when the content of ZrO ₂ is too large, the devitrification resistance is significantly decreased. In particular, when SnO ₂ is contained, it is preferable to strictly regulate the content of ZrO ₂ . The content of ZrO ₂ is preferably 0.4% or less, 0.3% or less, and particularly preferably 0.01 to 0.2%.

  In addition to the above components, for example, the following components may be added. In addition, the content of other components other than the above components is preferably 10% or less, and particularly preferably 5% or less in total, from the viewpoint of accurately enjoying the effects of the present invention.

In the method for producing silicate glass of the present invention, the glass batch is used so that the temperature of silicate glass at 10 ^2.5 dPa · s is preferably 1500 ° C. or higher, 1530 ° C. or higher, 1540 ° C. or higher, 1550 ° C. or higher. Is preferably prepared. The temperature at 10 ^2.5 dPa · s corresponds to the melting temperature, and the higher this temperature, the less soluble it becomes. As described above, the less soluble the silicate glass, the higher the necessity of supplementing the clarification power at the initial melting temperature, and the effect of the present invention is relatively increased.

  The silicate glass of the present invention is produced by the above-described method for producing a silicate glass. The technical characteristics of the silicate glass of the present invention are already described in the explanation column of the method for producing the silicate glass of the present invention. Therefore, detailed description of the silicate glass of the present invention is omitted.

The silica raw material for silicate glass of the present invention is characterized by containing 0.01 to 2% by mass of an alkaline earth metal component in terms of oxide. Further, the silica feedstock silicate glass of the present invention is characterized in that to generate CO ₂ gas at a temperature range of 1000 to 1400 ° C.. Furthermore, it is preferable that the silica raw material for silicate glass of the present invention generates CO ₂ gas and H ₂ O gas in a temperature range of 1000 to 1400 ° C. The technical characteristics of the silica raw material for silicate glass of the present invention are already described in the explanation column of the method for producing the silicate glass of the present invention. Therefore, detailed description is abbreviate | omitted about the silica raw material for silicate glass of this invention.

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

  Sample No. 1 is an example of the present invention, which is a silica raw material (silica sand) collected from a high-purity silica sand layer formed by the erosion action of a dolomite deposit. Sample No. 2 is a comparative example of the present invention, which is a conventional silica raw material (silica sand) that is generally used.

  Sample No. Table 1 shows the contents of trace components of 1 and 2.

Next, sample No. Regarding 1 and 2, the amount of CO ₂ released when a temperature range from 200 ° C. to 1300 ° C. was heated at a rate of temperature increase of 8 ° C./min was measured by a quadrupole mass spectrometer. The result is shown in FIG. Furthermore, sample no. 1 and 2, the amount of H ₂ O released when the temperature range from 200 ° C. to 1300 ° C. was heated at a rate of temperature increase of 8 ° C./min was measured by a quadrupole mass spectrometer. The result is shown in FIG. In the figure, (1) indicates the sample No. 1 (2) indicates the sample No. 2 points to data.

As can be seen from FIGS. 1, CO ₂ gas and H ₂ O gas are generated in a wide temperature range from 600 ° C. to 1200 ° C. On the other hand, sample No. In No. ₂ , CO ₂ gas was hardly generated during high-temperature heating, and the amount of H ₂ O gas generated was small.

General carbonate decomposition occurs at temperatures around 800 ° C. 1, the generation of CO ₂ gas was observed at a temperature around 800 ° C. Furthermore, sample no. In No. 1, the generation of CO ₂ gas was observed even in the temperature range where the decomposition of the carbonate was completed, that is, at a high temperature of 1000 ° C. or higher. This phenomenon takes time until the alkaline earth carbonate present in the silica particles is released as CO ₂ gas from the surface of the silica particles. As a result, the CO ₂ gas is heated at a high temperature of 1000 ° C. or more. It is thought that it was released. For the same reason, sample no. In No. 1, it is considered that the generation of H ₂ O gas was observed even in the temperature range where the decomposition of the hydroxide salt was completed, that is, at a high temperature of 1000 ° C. or higher.

As a silica supply source, Sample No. After preparing a glass batch using the silica raw material which concerns on 1 and 2, the alkali free glass was produced in accordance with the conventional method. Specifically, the silicate glass has a glass composition of SiO ₂ 60%, Al ₂ O ₃ 19%, B ₂ O ₃ 6.5%, MgO 2.3%, CaO 6%, SrO 0 by mass%. Various glass raw materials were prepared so as to contain 0.5%, BaO 5.5%, and SnO ₂ 0.2% to prepare glass batches. Next, the obtained glass batch is put into a continuous melting furnace and melted at 1500 to 1600 ° C., then the molten glass is clarified and stirred, and then supplied to a molding apparatus, and 0.7 mm thick by an overflow downdraw method. It shape | molded in flat plate shape, and also cut | disconnected to 1800 mm x 1500 mm size, and obtained the glass plate. Finally, the amount of SO ₃ remaining in the obtained glass plate was measured. Sample No. No. 1 and No. 1 glass plate sample. The glass plate according to No. 2 has the same manufacturing conditions as the silica raw material.

As a result, sample no. The glass plate according to Sample No. 2 Compared with the glass plate according to No. 1, the amount of SO ₃ remaining was 1.3 times. Sample No. The glass plate according to Sample No. 2 Compared to the glass plate according to 1, the number of bubbles was 10 times. This is the sample No. When the silica raw material according to 1 is used, CO ₂ gas is generated at a temperature around 1200 ° C. at the time of melting, and the amount of H ₂ O gas generated is large. This is considered to be due to a decrease in the amount of dissolved gas in the molten glass.

  The phenomenon obtained in the above experiment is considered to occur similarly in the materials (sample Nos. A to I) shown in Table 2.

Claims (16)

In the manufacturing method of the silicate glass which melts and shape | molds a glass batch and obtains silicate glass,
In the glass batch comprises an alkali earth metal carbonate, an alkaline earth metal component 0.01 to 2 wt% seen containing an oxide basis, to generate CO ₂ gas and 1000 to 1400 in a temperature range of ℃ A method for producing a silicate glass, wherein a silica raw material is introduced.   The method for producing a silicate glass according to claim 1, wherein a silica raw material containing 0.01 to 0.3 mass% of Mg component in terms of MgO is introduced into the glass batch.   The method for producing a silicate glass according to claim 1 or 2, wherein a silica raw material containing 0.01 to 0.5 mass% of the Ca component in terms of CaO is introduced into the glass batch. In the glass batch, silicate glass according to any one of claims 1 to 3, characterized in that introducing the silica raw material including 0.001 to 0.008 wt% of Fe component in terms _{of Fe} 2 _{O 3} Manufacturing method. The silicate glass according to any one of claims 1 to 4 , wherein a silica raw material that generates CO ₂ gas and H ₂ O gas in a temperature range of 1000 to 1400 ° C is introduced into the glass batch. Manufacturing method. As the content of the S component in the glass composition of the silicate glass is less than 0.01 mass% converted to SO _3, any one of claim 1 to 5, characterized in that to produce a silicate glass The manufacturing method of the silicate glass as described in 2. The content of As ₂ O ₃ in the glass composition of the silicate glass is less than 0.05% by mass, the content of Sb ₂ O ₃ is less than 0.05% by mass, and the content of SnO ₂ is 0.01 to 1% by mass. A glass batch is prepared so that it may become%, The manufacturing method of the silicate glass as described in any one of Claims 1-6 characterized by the above-mentioned. The glass batch is prepared so that the content of the alkali metal oxide in the glass composition of the silicate glass is less than 0.5% by mass, according to any one of claims 1 to 7 , Manufacturing method of silicate glass. Glass composition of silicate glass, in _{mass%, SiO 2 50~80%, Al} 2 O 3 5~25%, B 2 O 3 0~20%, 0~15% MgO, CaO 1~15%, SrO The method for producing a silicate glass according to any one of claims 1 to 8 , wherein a glass batch is prepared so as to contain 0 to 15% and BaO 0 to 15%. The method for producing a silicate glass according to any one of claims 1 to 9 , wherein the silicate glass is formed into a flat plate shape by an overflow downdraw method or a float method. It comprises an alkali earth metal carbonate, 0.01 to 2 wt% observed containing the oxide equivalent alkaline earth metal component, and is characterized in that to generate CO ₂ gas at a temperature range of 1000 to 1400 ° C. Silica raw material for silicate glass. The silica raw material for silicate glass according to claim 11 , wherein the Mg component is contained in an amount of 0.01 to 0.3% by mass in terms of MgO. The silica raw material for silicate glass according to claim 11 or 12 , comprising a Ca component in an amount of 0.01 to 0.5 mass% in terms of CaO. The Fe component _Fe 2 _{O 3,} characterized in that it comprises 0.001 to 0.008 wt% in terms of claims 11 to 13, any silicate glass silica material according to one of. The silica raw material for silicate glass according to any one of claims 11 to 14 , wherein CO ₂ gas and H ₂ O gas are generated in a temperature range of 1000 to 1400 ° C. The silica raw material for silicate glass according to any one of claims 11 to 15 , wherein the silica raw material is natural silica sand.