TWI388524B - Heat-resistant (or-proof) material for glass melting, glass article production device and production method of glass articles - Google Patents

Description

Heat-resistant material for melting glass, glass article manufacturing device, and method for manufacturing glass article

The present invention relates to an apparatus for manufacturing a glass article, a heat resistant material constituting the same, and a method of manufacturing a glass article using the same.

The manufacturing techniques of various glass articles have been developed by breaking through many difficult issues. For example, various glass article manufacturing techniques represented by thin-tube glass used as a thin plate glass and a liquid crystal backlight used in an image display surface, which is one of the main components of various information devices such as a flat panel display, have been developed. The technology has been further improved by the company's commitment to achieving high dimensional accuracy and high homogeneity.

Reasons for impeding the homogeneity of glass articles are: unmelted or crystallized precipitates in molten glass, streaks (threads, strings, streaks, cords), scratches, knots, cords, scratches. (striae), cat scratches (catscratch), reeds, etc., but bubbles (seed, buble, blister) in molten glass are also one of the commonly known defects. The increase in the number of bubble defects in the molten glass not only degrades the quality of the glass article, but also does not improve the manufacturing efficiency of the glass article.

From the above point of view, in order to reduce the number of bubbles in the molten glass, a number of inventions have been developed so far. In particular, a problem that has been attracting attention in recent years is that there are oxygen bubbles having a fine size which are defects in glass articles in molten glass. This is a problem in which oxygen bubbles are generated at the interface between the platinum-containing glass manufacturing apparatus and the molten glass, and as a countermeasure, Patent Document 1 It is assumed that the generation of oxygen-containing bubbles in the molten glass is caused by the fact that hydrogen generated by the decomposition of water present in the molten glass is lost to the outside of the system through a platinum constituting the glass melting device, thereby causing residue to be melted. Oxygen in the glass forms bubbles, and the solution is to reduce β-OH in the glass. Further, in the invention developed in Patent Document 2, generation of bubbles can be suppressed by forming a coating film which does not transmit hydrogen or oxygen on the surface of platinum. Further, the invention disclosed in Patent Document 3 controls the partial pressure of hydrogen outside the melting vessel. The invention developed in Patent Document 4 is that the generation of bubbles in the inner container can be minimized by making the molten container into a double configuration.

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2001-500098

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2004-523449

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2001-503008

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2003-95663

However, in order to reduce the fine oxygen bubbles generated in the molten glass, only the previously developed invention is not sufficient. For example, in the case where the glass composition contains chlorine as a method for reducing β-OH in the glass in Patent Document 1, chlorine may be easily generated in the reheating treatment of the glass article, and a technique such as glass flip chip bonding may be used. In the case of a glass substrate of a precision wiring structure of chip-on-glass, there is a problem that it is difficult to achieve high performance due to chlorine generated. Further, when a coating film is formed on the surface of platinum as in Patent Document 2, the coating film is easily broken due to thermal shock or mechanical shock generated by the glass manufacturing conditions, and even if a little damaged portion is formed on the coating film, There is a risk of fatal defects in the molten glass. Further, as disclosed in Patent Document 3, in order to control the hydrogen partial pressure, the partial pressure of water vapor is adjusted, sometimes due to the accompanying steps. The temperature difference is subjected to the partial pressure control in a high-temperature environment, so that it becomes difficult to continuously obtain the balance between the steps and stabilize the same at the same time, and it is difficult to maintain stable production for a long period of time. Further, as in the configuration of the double structure in Patent Document 4, even if it can be realized in a limited portion of the melting device, the same configuration is employed in all the portions where bubbles may occur, and there are cases where structural limitations are imposed and the phase cannot be realized. Corresponding objects.

In view of the above, the present inventors have found that the object of the present invention is to provide a heat-resistant material for molten glass which can suppress the oxygen-containing bubbles which hinder the homogeneity of the molten glass and which can improve the durability of the melting equipment, and the use of the heat-resistant material. The glass article manufacturing apparatus further provides a glass article manufacturing method that can be realized by the glass article manufacturing apparatus.

In other words, the heat-resistant material for molten glass of the present invention is a heat-resistant material for molten glass which is composed of a platinum-containing material used in a heating apparatus for producing a multi-component series oxide glass, and is characterized in that it has contact with molten glass. The thickness of the platinum-containing material is in the range of 1.1 mm to 50 mm.

Here, in the heat resistant material for molten glass which consists of a platinum-containing material used for the heating apparatus of the multi-component series oxide glass, the thickness of the platinum-containing material which has the surface contact with molten glass is 1.1 mm. The meaning expressed in the range of 50 mm is that the platinum-containing material used in the heating production apparatus for converting the glass composition containing a plurality of oxide components into a molten glass state is directly in contact with the molten glass. The thickness in the direction perpendicular to the plane of the platinum-containing material constituting the plane forming the interface is 1.1 mm or more and 50 mm or less.

Here, the platinum-containing material means a material containing platinum (Pt) as a component thereof, that is, a metal material such as a platinum alloy or platinum, and further means a ceramic material in which platinum is dispersed, but the content of platinum is not limited. However, a material containing platinum as an impurity in the order of ppm is not suitable for use in the present invention.

The reason why the thickness of the platinum-containing material having the surface in contact with the molten glass is in the range of 1.1 mm to 50 mm is that if the thickness of the platinum-containing material having the surface in contact with the molten glass is less than 1.1 mm, oxygen bubbles are sometimes formed. So not good. Moreover, if the thickness of the platinum-containing material is less than 1.1 mm, the structural strength is also affected, which is not preferable. From this point of view, the thickness of the platinum-containing material on the face in contact with the molten glass is preferably thick, preferably 1.2 mm or more, more preferably 1.3 mm or more, more preferably 1.4 mm or more. Preferably, it is 1.5 mm or more, more preferably 1.6 mm or more, and most preferably 2.2 mm or more. On the other hand, the thicker the platinum-containing material having the surface in contact with the molten glass, the higher the cost required to construct the manufacturing equipment. From this point of view, the thickness of the platinum-containing material having the face in contact with the molten glass is preferably as thin as possible, preferably 40 mm or less, more preferably 30 mm or less, and even more preferably 20 mm or less. More preferably, it is less than or equal to 10 mm.

The surface in contact with the molten glass means a portion which is wetted by the molten glass in a liquid phase, that is, a portion which is in direct contact, and a portion indirectly contacted by the molten glass infiltrating into some member or the like does not conform to the so-called contact portion in the present invention. Further, since the surface of the platinum-containing material is wetted by evaporation or volatilization of constituent components in the molten glass, it does not conform to the so-called contact portion in the present invention. That is, the surface in contact with the molten glass in the present invention means immersed in molten metal. The liquid phase of the glass is in contact with it and forms a liquid-solid interface with the molten glass.

Next, a more specific example of the use site of the platinum-containing material that is in direct contact with the molten glass is a container made of a heat-resistant material that contains molten glass, such as an inner wall surface or a bottom surface portion of a crucible, or a tank (tank). ), melting tank (chamber), clarification tank (chamber), agitation tank (chamber), working tank (chamber), crucible, pot, throat, riser, feed Feeder, forehearth, fore bay, drain, dog house, etc. or specific parts of these containers, ie, hearth (or bottom), furnace a refractory material such as a wall (or side wall), a dam (or damwall), a sill, a pipe, and a gutter; or a glass melting furnace constituting a glass article manufacturing apparatus made of a heat resistant metal material a primary platinum-containing material; or a stirrer, a tweel, a needle, a gate, a damper, a blender, or the like for homogenizing molten glass, Rotor, tube, paddler, etc. are made of a heat resistant metal material and re-impregnated in the molten glass. Empty structure of platinum-containing material; and roll, slot, rip tile, skimmer, wet back tile, draw bar, flow A spout, a cup, an orifice, a fusion pipe, a bushing, and a nozzle, a spinning hole, etc., constitute a fire resistant part of a molded part that is indispensable for precision molding of molten glass. Materials or heat resistant materials; platinum-containing materials in direct contact with molten glass.

According to the study by the inventors of the present invention, questions about oxygen bubbles in molten glass The problem is due to the thinning of the platinum plate. In other words, when platinum or a platinum alloy is used in the glass manufacturing apparatus, the equipment cost is increased, and a large amount of platinum is required to manufacture the flat glass for a substrate mounted on the liquid crystal display device. The thickness of the platinum device is made thin. When such measures for reducing the cost of equipment were implemented, it was found that the bubble defects of the glass articles were greatly increased. Next, after the glass manufacturing apparatus was stopped, the platinum apparatus was inspected, and as a result, it was found that many oxygen bubbles were present at or near the contact interface between the platinum apparatus and the molten glass. The inventors of the present invention conducted repeated studies in this respect until the completion of the present invention. Therefore, in each of the platinum-containing materials that form an interface with the molten glass, it is particularly preferable to apply the present invention to a platinum-containing material used in a manufacturing apparatus for manufacturing a flat glass for a substrate mounted on a liquid crystal display device. material.

In the heating manufacturing apparatus of the present invention, the glass frit may be heated by any one of the heat sources. For example, a gaseous fuel such as LPG or oxygen, a solid fossil raw material may be used as a fine powder, and a liquefied fuel may be used. Further, electric heating may be performed using an electrode or the like, or these various methods may be used in combination as needed.

Further, the heat-resistant material for molten glass according to the present invention is characterized in that, in addition to the above, the thickness L of the platinum-containing material having a surface in contact with the molten glass is obtained by the formula 1 when the temperature T of the molten glass is less than 1458.5 °C. Further, when the temperature T of the molten glass is 1458.5 ° C or more, it is obtained by the equation 2, and in any case, L is obtained by any of the following mathematical expressions.

[Number 1] L≧1.1 (T<1458.5°C)

[Number 2] L≧0.012T-16.4 (T≧1458.5°C)

The inventors of the present invention conducted a detailed study on the oxygen bubble characteristics which are defects in the molten glass from the viewpoint different from the conventional invention for preventing oxygen bubbles, and found that the thickness L of the platinum-containing material can be realized. By defining the molten glass temperature T, it is possible to effectively suppress foaming at the interface between the platinum-containing material and the molten glass at a predetermined temperature T, which is to melt the glass by melting the foreign matter contained in the molten glass. The temperature required for sex. Further, it has been confirmed that the desired effect can be achieved by the following design and configuration: for the thickness of the heat-resistant material for molten glass used in the specific portion of the glass article manufacturing apparatus in which the specific molten glass temperature T must be realized, When the temperature T of the molten glass is less than 1458.5 ° C, the predetermined thickness L is represented by the number 1. When the temperature T of the molten glass is 1458.5 ° C or more, the predetermined thickness L indicated by the number 2 is used.

When the temperature T of the molten glass and the thickness L of the platinum-containing material represented by the number 1 or the number 2 are specifically exemplified, the following configuration is preferable: if the temperature T of the molten glass is 1300 ° C, the thickness L of the constituent member is 1.1. Mm, 1.6 mm, 2.2 mm, if the molten glass temperature is 1400 ° C, the thickness L of the platinum-containing material is 1.6 mm, 2.2 mm, and if the molten glass temperature T is 1500 ° C, the thickness L of the platinum-containing material is 1.6 mm, 2.2 mm. 2.8 mm, if the molten glass temperature T is 1600 ° C, the thickness L of the platinum-containing material is 2.8 mm, 4.0 mm.

The number 1 or 2 is based on 100% by weight of the platinum plate. According to the evaluation, when the platinum content of the platinum-containing material is reduced, for example, if it is a material alloyed with platinum, the material other than platinum must have a lower foaming property than the platinum at the contact interface with the molten glass. material. Further, it is necessary to sufficiently examine the properties such as reactivity with molten glass and corrosion resistance.

In addition to the above, when the platinum content of the platinum-containing material is at least 10% by mass, the heat-resistant material for molten glass of the present invention has good corrosion resistance to molten glass even at a high temperature.

Here, the platinum content of the platinum-containing material is at least 10% by mass. It is expressed as a platinum-containing material constituting a heating device having sufficient heat resistance, and the platinum content in the platinum-containing material is greater than or equal to the mass percentage. 10%.

Regarding the platinum-containing material, any platinum content may be 10% or more, depending on the required strength or heat resistance, but in terms of the use site, the required cost and durability, and the reactivity with the glass. It is better to set it as high as possible. From this point of view, the platinum content of the platinum-containing material is preferably 40% or more, more preferably 50% or more, more preferably 60% or more, more preferably 70% or more, most Good is 80% or more.

In the platinum-containing material, the element other than platinum is not particularly limited as long as it can realize long-term heat resistance. Among them, it is preferred that the result of dissolution or the like from the surface of the platinum-containing material does not cause unnecessary coloring of the glass article, for example, Ir (铱), Os (锇), Rh (铑), Zr (zirconium) can be used. ), Ru (钌), Pd (palladium), Si (矽), Y (钇), Ce (铈), La (镧), Gd (釓), Ta (钽), Ti (titanium), Hf (铪), Al (aluminum), Sc (钪), Ca (calcium), Mg (magnesium) or Ba (钡).

Further, in addition to the above, the platinum-containing material is a heat-resistant material for molten glass of the present invention, and in the case of a heating apparatus suitable for continuously melting molten glass, it is possible to mass-produce a glass article which is stable in quality for a long period of time.

Here, the "heating manufacturing apparatus in which the platinum-containing material is applied to the continuous melting of the molten glass" means that the glass melting equipment such as a tank furnace is used instead of the batch heating which can only be intermittently produced. A user who manufactures a device to continuously manufacture a glass article, which is used in a heating apparatus for a glass melting apparatus.

In the case of a glass melting apparatus, if it has a heating device which can be heated to 700 ° C or higher in any configuration, and it is possible to continuously form a homogeneous molten glass, it can be used. Further, the speed at which the molten glass is continuously formed is not particularly limited.

Further, in addition to the above, the platinum-containing material is a heat-resistant material for molten glass of the present invention, and is suitable for a heat-generating device having a molten glass flow portion of 1 liter or more, and impinges on the collision and texture of the homogenization other than the bubble. When the junction or the like is also heated and melted, the platinum-containing material has a sufficient volume of the molten glass to be accommodated, and the molten glass can be made into a more homogeneous state, which is preferable.

Here, the term "a platinum-containing material is suitable for a heating device having a molten glass retention portion of 1 liter or more" means that a heating manufacturing apparatus using the platinum-containing material of the present invention and having a suitable heat source has a function of allowing molten glass to flow. The function is a substantially container-like structure in which the internal volume of the structural portion through which the molten glass flows is 1 × 10 ³ cm ^{3 or more} .

When the volume of the molten glass flow portion exceeds 1 liter, there is a risk that a portion of the molten glass flow portion is formed such that the time until the fine-sized bubbles are formed in the molten glass is sufficient. There is a portion where the flow rate of the molten glass is relatively low, so that the molten glass remains in the same apparatus. This case means that bubbles are more likely to form as the ratio of the rate of formation of bubbles in the molten glass to the relative speed of the flow rate of the molten glass changes. In other words, when the molten glass flow portion is larger than 1 liter, the foreign matter, the knot, and the like in the molten glass can be sufficiently melted in the molten glass, but on the other hand, it is disadvantageous for the purpose of effectively suppressing generation of bubbles in the molten glass. The situation exists. Therefore, in the heating production apparatus having the structure suitable for the above conditions, it is preferable to apply the present invention to suppress generation of bubbles and to form a homogeneous quality.

Further, in addition to the above, at least a part of the surface of the inner surface side of the surface in which the platinum-containing material is in contact with the molten glass is selected from the group consisting of glass, ceramic, crystallized glass, concrete, and mortar. And supported by one or more materials of the group consisting of heat resistant metals, the platinum-containing material can be made long by protecting the platinum-containing material for various physical and chemical loads applied from the outside of the platinum-containing material. It is preferable to continuously support the molten glass at a high temperature.

Here, at least a part of the surface of the inner surface side of the surface of the platinum-containing material in contact with the molten glass is selected from the group consisting of glass, ceramic, crystallized glass, concrete, mortar, and heat resistant metal. Supported by more than one material, meaning relative to and at high temperatures In the surface in which the molten glass is in direct contact, a part of the entire area of the inner surface of the platinum-containing material on the opposite side is in a state of being abutted by other members, and the other components mean glass, ceramic, crystallized glass, At least one of concrete, mortar, and heat resistant metal.

The components that abut the support do not have to be solid, but must have the effect of suppressing the temporal deformation of the platinum-containing material in a high temperature state. Further, the abutting support members need not be one, and a plurality of members may be combined. Further, a material which is less likely to react with a platinum-containing material at a high temperature is preferred.

Further, in the case where the heat-resistant material for molten glass of the present invention contains a clarifying agent such as arsenic (As) which absorbs oxygen by a redox reaction in the molten glass, the effect of suppressing the formation of the corresponding oxygen-containing gas bubbles is also obtained. Particularly excellent effects can be obtained when the present invention is applied in a state where the clarifying agent is not added or the amount of the clarifying agent added is significantly small.

The glass article manufacturing apparatus of the present invention is characterized in that the heat-resistant material for molten glass is provided in a group selected from the group consisting of a hearth surface of a heating manufacturing apparatus, a side wall surface, and an inner surface of a structure for connecting between grooves. Or more than one face.

Here, the heat-resistant material for molten glass is provided in one or more types selected from the group consisting of a hearth surface of a heating manufacturing apparatus, a side wall surface, and an inner surface of a structure for connecting between grooves, and A configuration is adopted in which a heat-resistant material for melting glass having a thickness of a platinum-containing material having a surface in contact with molten glass and containing platinum in a range of 1.1 mm to 50 mm is disposed in a heating device having a molten glass flow, specifically That is, the bottom surface portion of the groove, or the side portion, and between the plurality of grooves and grooves The tube or the groove or the like moves the molten glass from the groove to the groove, that is, at least one of the inner surface portions of the connection structure portion for allowing the molten glass to flow.

In the glass article manufacturing apparatus of the present invention, a single heat-resistant material for melting glass may be applied, or a plurality of heat-resistant materials for melting glass may be used in combination to enhance the effect. Further, the strength of the heat-resistant material for molten glass can be increased by using it in combination with other members.

Further, in the glass article manufacturing apparatus of the present invention, in addition to the above, if the temperature of the molten glass in the apparatus is 700 ° C to 2200 ° C, the following appropriate viscosity range can be formed correspondingly, that is, by making the viscosity of the molten glass a sufficiently low viscosity state, and a defect such as a foreign matter, a knot or a texture other than air bubbles can be made into a homogenous viscosity, and the molten glass can be precisely formed into a specific shape to form an appropriate viscosity range when the glass article is formed; Within this viscosity range, generation and formation of fine bubbles in the molten glass can be surely suppressed.

The temperature of the molten glass in the apparatus is 700 ° C to 2,200 ° C, which is defined by measuring the temperature of the molten glass by a thermocouple or an optical method. When the temperature of the molten glass is more than 2,200 ° C, the viscosity of the molten glass can be effectively lowered, but the disadvantage of shortening the durability of the attached equipment such as the apparatus for heating the molten glass is likely to occur, which is not preferable. In addition, when the temperature of the molten glass is set to a low temperature of less than 700 ° C, there is a problem in that it is difficult to form an appropriate shape or the like to form a glass article during molding of the molten glass, which is not preferable.

Further, in addition to the above, the glass article manufacturing apparatus of the present invention is provided with a heat-resistant material for melting glass and is provided with a physical stirring operation. In the step of the equipment device from the tank to the forming device, that is, in the step of the so-called Downstream process, no fine oxygen-containing bubbles are formed on the wall of the device, so that the possibility of mixing fine bubbles in the shaped glass article is reduced. Small, so better.

Further, the above-mentioned fine oxygen-containing gas bubbles are specifically exemplified, and the floating speed in the molten glass at 1500 ° C is also less than 2.5 cm / hour.

Further, in addition to the above, the glass article manufacturing apparatus of the present invention is preferably an apparatus for producing flat glass, which can further improve the quality of high-quality flat glass which can be used for various purposes.

Here, the apparatus for manufacturing flat glass means that the molten glass is heated and formed in a molten glass heating apparatus, and the flat glass having various sizes is molded by driving various molding apparatuses in a homogenized state. As the forming apparatus, for example, a floating forming apparatus, an overflow down draw forming apparatus, a slot down draw forming apparatus, a roll-out forming apparatus, and a reed low forming apparatus can be used. Various forming devices.

Further, in addition to the above, the glass article manufacturing apparatus of the present invention is preferably a flat glass which can produce a flat panel display having high image quality.

Here, in the case of a flat panel display, no matter what display method is used. That is, for example, a liquid crystal display (LCD), a plasma display panel (PDP), an inorganic or organic EL display, and a field emission display (FED: Field emission) Display: also known as field emission emission flat panel display) or SED (Surface Conduction Emitter Display), vacuum fluorescent display (VFD: Vacuum Fluoresscent Display), electroluminescent display (ELD: Elctro Luminescent Display), illumination LED display (Light Emitting Diode Display), electrochromic display (ECD: Elctro Cromic Display), electrophoretic display (EPD: Electrophoretic Display), and the like.

In addition, in addition to the above, the glass article manufacturing apparatus of the present invention can manufacture liquid crystal displays of various sizes mounted on a small display device to a large-scale display device beyond the sixth generation, in addition to the device for manufacturing flat glass for liquid crystal display device mounting. It is better to use flat glass with high homogeneity quality on the device.

In the case of a liquid crystal display device, the present invention can be applied regardless of the difference in liquid crystal elements and the manner in which the image is displayed. For example, in the case of a liquid crystal, the present invention can be utilized in any category such as a nematic liquid crystal, a smectic liquid crystal, or a cholesteric liquid crystal, and the image display method is also It can be used regardless of various methods such as STN or TFT.

The flat glass mounted on the liquid crystal display device preferably has an alkali-free glass or a glass composition having a low alkali content. For example, if the composition of the glass composition is expressed by mass percentage in terms of oxide, it is 40 to 85% of SiO ₂ , 1 to 28% of Al ₂ O ₃ , and 2 to 45% of RO (RO = MgO + CaO + ZnO + A glass composition such as SrO+BaO) is preferred.

Moreover, the glass material for manufacturing the flat glass for liquid crystal display device mounting In the product manufacturing apparatus, it is important to note that in addition to the bubbles, the formation of platinum particles in the molten glass is suppressed. That is, it is important to minimize the number of platinum particles in the molten glass caused by peeling, recrystallization, and the like of the platinum particles from the platinum-containing material, and it is more preferable to adopt such a device configuration. For example, it is preferable to apply a protective material such as a ceramic having a platinum-coated function to a portion where the platinum particles are easily formed in the glass article manufacturing apparatus.

Further, in addition to the above, the glass article manufacturing apparatus of the present invention is a device for manufacturing a flat glass for a solid-state image sensor, and has a charge coupled device (CCD) and a complementary metal oxide semiconductor (CMOS). It is preferable to use various solid-state imaging elements of various functions such as Complementary Metal Oxide Semiconductor.

In order to manufacture a flat glass for a solid-state imaging device, the glass article manufacturing apparatus of the present invention is further difficult to dissolve even when a trace amount of radioactive elements such as uranium, thorium or radium which can generate α rays reaches ppb (parts per billion). The composition is better.

The glass article manufacturing apparatus of the present invention can be applied to various glass article manufacturing apparatuses which are indispensable for the installation of a structural material to be heated at a high temperature, in addition to the above-mentioned flat glass. For example, it can be used as a high-precision cylindrical glass tube for a light source such as a melting furnace for producing glass fibers, a liquid crystal backlight or a xenon flash lamp, or a lens for an optical component, and can also be used as a refractive index or dispersion and transmission. Various types of optical glass, which are used for the management of glass articles, such as crystallized glass materials for various purposes such as building materials and home appliances, can be used.

The method for producing a glass article of the present invention is characterized in that a glass article is produced using the above-described glass article manufacturing apparatus.

Here, the production of a glass article using the above-described glass article manufacturing apparatus means that the heat-resistant material for melting glass is provided on the hearth surface, the side wall surface, and the groove between the tanks selected from the heating device that flows through the molten glass. A glass article is produced by one or more of the glass article manufacturing apparatuses of the group consisting of the inner surface of the structure, wherein the heat-resistant material for the molten glass is mounted on the heating of the multi-component series oxide glass as described above. The thickness of the platinum-containing material on the surface of the platinum-containing material on the device and in contact with the molten glass is in the range of 1.1 mm to 50 mm.

The glass article manufacturing apparatus of the present invention can be used in combination with other members for homogenizing molten glass and different methods or devices. Significantly, a better effect can be achieved by appropriately combining the present invention with other methods. For example, it can also be used in combination with various mixing apparatuses of molten glass, a decompression apparatus of molten glass, a foaming apparatus of molten glass, and the like.

(1) As described above, the heat-resistant material for molten glass of the present invention is a heat-resistant material for molten glass composed of a platinum-containing material used for a heating apparatus for a multi-component series oxide glass, and has a surface in contact with the molten glass. The thickness of the platinum-containing material is in the range of 1.1 mm to 50 mm, so that the generation of bubbles having a high oxygen content in the glass can be suppressed.

(2) In addition, in the case of the heat resistant material for molten glass of the present invention, when the temperature T of the molten glass is less than 1458.5 ° C, the lower limit value of the thickness of the platinum-containing material is set to 1.1 mm, and the temperature T of the molten glass is greater than or equal to In the case of 1458.5 ° C, the thickness lower limit of the platinum-containing material is set to (0.012 T - 16.4) mm, and therefore the thickness of the platinum-containing material becomes an appropriate size in relation to the temperature of the molten glass.

(3) Further, the heat-resistant material for molten glass of the present invention, even if the platinum content of the platinum-containing material is at least 10% by mass, suppresses the generation of bubbles having a high oxygen content at the interface while achieving a high temperature Durability helps to maintain long-term stable production.

(4) Further, the heat-resistant material for molten glass of the present invention can be excluded even if it is a device for continuously heating a large amount of molten glass if it is characterized in that the platinum-containing material is suitable for use in a heating manufacturing apparatus for continuously melting molten glass. Since the generation of bubbles having a high oxygen content with a fine size is produced, it is preferable to realize stable production at the time of producing a glass article at a high production speed by using the apparatus.

(5) Further, in the heat-resistant material for molten glass of the present invention, at least a part of the surface of the platinum-containing material on the inner surface side opposite to the surface contacting the molten glass is selected from the group consisting of glass, ceramic, crystallized glass, concrete, mortar, and When the material in the group consisting of the heat resistant metal is supported, it can be a material which is supported by the most suitable material according to the temperature or the ambient gas when the platinum-containing material is used, so that high durability can be achieved.

(6) The glass article manufacturing apparatus of the present invention, wherein the heat-resistant material for melting glass is provided in a group of the inner surface of the structure for connecting the hearth surface, the side wall surface, and the groove between the grooves in which the molten glass is retained. In any of the places where the platinum-containing material having a fine oxygen-containing gas bubble is easily formed in the molten glass, the formation of bubbles can be effectively prevented.

(7) Further, in the glass article manufacturing apparatus of the present invention, if the temperature of the molten glass in the apparatus is in the range of 700 ° C to 2,200 ° C, the apparatus can be applied in a temperature range in which bubbles are easily formed, and the oxygen content is lowered. The proportion of the bubbles is formed, so that it is easy to form a molten glass in a homogeneous state.

(8) Further, in the glass article manufacturing apparatus of the present invention, in the case of manufacturing a flat glass, it is easy to manufacture a flat glass for various uses in an environment where bubbles having a high oxygen content are difficult to be mixed. .

(9) In addition, the glass article manufacturing apparatus of the present invention is a device for manufacturing flat glass for flat panel displays, and can be stably produced in large quantities regardless of the size of the flat glass even if it is used for a flat glass having various sizes. Flat glass with high homogeneity.

(10) In addition, the apparatus for producing a glass article of the present invention can continuously form a large-area thin plate glass in which fine bubbles having a high oxygen content are not formed, as long as it is a device for producing a flat glass for mounting a liquid crystal display device. In the state of homogeneity of customer satisfaction, a flat glass having a large-area size required for mounting on a large-screen display is manufactured.

(11) Further, if the glass article manufacturing apparatus of the present invention is a device for manufacturing flat glass for a solid-state image sensor, it is possible to manufacture a flat glass having high homogeneity which is indispensable in a high pixel image sensor. .

(12) The method for producing a glass article of the present invention is a method for producing a glass article by using the above-described glass article manufacturing apparatus, so that the number of bubbles having a high oxygen content rate generated in the melting step can be minimized.

Hereinafter, according to the embodiment, the heat-resistant material for molten glass of the present invention and the glass article manufacturing apparatus using the heat-resistant material, and the method of manufacturing the glass article using the glass article manufacturing apparatus will be specifically described.

[Example 1]

First, the evaluation contents of the test stage level performed by the inventors at the time of developing the present invention will be described below.

An alkali-free glass having a β-OH amount of 518 ppm in the glass by pre-melting (the glass composition expressed by mass percentage in terms of oxide is SiO ₂ 59 wt%, Al ₂ O ₃ 17 wt%, B ₂ O ₃ 10 wt%, MO (M = Ca, Mg, Ba, Sr, Zn) 14 wt%) were homogenized, and a thickness of 0.7 mm was equivalent to a thin plate glass shape in which both sides of the light-transmitting surface were mirror-finished. In order to be mounted on a liquid crystal display device, the glass is made into a thin plate glass, but the glass must still be cut into a rectangular sheet of 50×50×0.7 mm, and then washed with pure water in an indirect drying furnace at 150 ° C for 10 hours. Prepare to dry under the conditions. Next, 22 sheets of the flat glass sample were laminated on the upper edge of a platinum crucible (bottom diameter 40 mm, upper end diameter 55 mm, height 20 mm) having a specific thickness and having a composition of 100 wt% of platinum. In this state, it is placed in a box-type heating resistor furnace. Using the heating procedure of the heating resistor furnace, the temperature was raised to 1200 ° C at 10 ° C / min, and then placed in another box-shaped test furnace at a specific test temperature for 30 minutes, after which the platinum crucible was taken out from the test furnace and cooled to the chamber. The temperature is used as an observation sample. The observation was carried out in a state where the molten glass which did not flow was kept for a certain period of time to perform evaluation under severe conditions. Next, in the sample for observation, the presence or absence of an oxygen-containing bubble generated at the interface between the glass and platinum at the bottom of the crucible was observed and investigated. The investigation was performed using a naked eye and a 20x solid microscope. Further, since the flat glass is easily removed during softening deformation, and air bubbles or the like are mixed, and bubbles having a clear size, shape, and generation portion which are generated irrespective of the present invention are excluded from the investigation object, A reproducible evaluation can be performed.

The results of investigation of the thickness and heating and holding temperature of various platinum crucibles in the above order are summarized in Table 1. In Table 1, it is indicated by ○ that no foaming was observed at the interface between the glass and the platinum, and that the foam was observed at the interface portion by ×. Among them, regarding the nature of the test, the mixed bubbles generated between the laminated glass sheets have been excluded from the observation. For the mixed bubbles, since the bubble size is different from the size of the bubbles generated in the platinum interface, it can be accurately excluded by observing the appearance of the bubbles.

As shown in Table 1, when the temperature was maintained at 1300 ° C or 1400 ° C, if the thickness of platinum was 0.4 mm or more, that is, 1.1 mm, 1.6 mm, and 2.2 mm, no foaming of oxygen-containing bubbles was observed. On the other hand, in the interface portion which was investigated when the thickness was 0.4 mm at 1600 ° C, for example, it was confirmed that many oxygen-containing bubbles were generated. However, if it is thick at 1500 ° C When the degree is greater than or equal to 1.6 mm, ie 1.6 mm, 2.2 mm, no foaming occurs. Further, since platinum having a thickness of 0.4 mm used at 1300 ° C and 1400 ° C is weak as a structural material, it is expected that the strength is weak and difficult to use in actual use.

According to the above-mentioned series of investigations, the inventors of the present invention have confirmed the relationship between the platinum-containing material and the molten glass temperature as indicated by the numbers 1 and 2, and found that the structural material has a predetermined thickness according to the relationship. The glass article manufacturing apparatus is required to have a predetermined temperature, and a glass article in which oxygen bubbles are not mixed is obtained.

[Embodiment 2]

Next, an example of a platinum-containing material which is a heat-resistant material for molten glass of the present invention, which is applied to a glass article manufacturing apparatus, is as follows.

Fig. 1 is an explanatory view of a glass article manufacturing apparatus to which the present invention is applied. Fig. 1(A) is a cross-sectional view along the longitudinal direction, and Fig. 1(B) is a cross-sectional view taken along the line X-X of Fig. 1(A). This large-sized glass melting apparatus is configured to be further connected to the forming portion and to form the molten glass in the forming portion, but only the main portions for explaining the present invention are partially exemplified herein.

The glass article manufacturing apparatus 10 is a structure in which the glass melting tank 20 and the glass clarification tank 30 are connected by the throat 50. Moreover, the glass clarification tank 30 is configured to be connected to the feeder 40. This feeder 40 is configured such that the surface of the platinum-containing heat resistant alloy material F is in direct contact with the molten glass G, and the platinum-containing heat resistant alloy material F has a composition of platinum of 90% to 10% when expressed by mass percentage. The thickness of this platinum-containing material F, side The wall thickness is 1.1 mm and the hearth surface thickness is 1.3 mm (see Figure 1(B)). Moreover, in order to achieve thermal insulation function and sufficient structural strength, a platinum block material F made of a platinum-containing heat-resistant alloy is provided with a ceramic barrier material R, and the pillar material of the ceramic barrier material R supports the platinum-containing material. F.

Next, the glass article manufacturing apparatus 10 described above is used to produce SiO ₂ 59 wt%, Al ₂ O ₃ 16 wt%, B ₂ O ₃ 9 wt%, MO (M=Ca, Mg) in terms of oxide-based weight percentage. A procedure for using an alkali-free glass article of 16 wt% (Ba, Sr, Zn) (used as a flat glass for an image display unit mounted on a liquid crystal display device or a cover glass for a solid-state imaging device).

A plurality of glass raw materials are pre-weighed, and then only 10 wt% of cullet is added and mixed, and then fed by a raw material feeder (screw feeder) 22 from a blower 21 provided on the glass melting tank 20. The adjusted glass raw material M is continuously introduced into the glass melting tank 20. The glass raw material M to be charged is heated in the glass melting tank 20 by using the burner 23 and the electrode 24 as a heat source to generate a high-temperature chemical reaction, and on the other hand, various gases such as carbon dioxide gas, oxygen gas, and water vapor are generated, and on the other hand, it is melted. In the state, the reaction is further carried out to be converted into a molten glass state. The molten glass G thus produced is subjected to a homogenization operation by the bubbling action B, and then flows into the glass clarification tank 30 through the throat 50. After the molten glass G is clarified to form a homogeneous state in the glass clarification tank 30 having an internal volume of about 30 liters, the homogenized molten glass G is used as the heat-resistant material for molten glass of the present invention, and flows into the side wall and the hearth. Platinum-containing material F in the feeder 40. In the case where the heat-resistant material for molten glass of the present invention is not provided in the feeder 40 in which the temperature of the molten glass G is 1300 ° C to 1400 ° C, the fine content contained in the interface between the molten glass G and the platinum-containing material F is contained. Oxygen bubbles flow into a molding portion (not shown) located on the front end side of the feeder 40 to cause blistering failure, but by applying the present invention, it is possible to suppress the formation of the interface between the molten glass G and the platinum-containing material F. The production of fine oxygenated bubbles.

In addition, since the temperature T of the molten glass is less than 1458.5 ° C as described above, and the thickness of the platinum-containing material F is 1.1 mm or more with 1.1 mm as the lower limit value, the effect of suppressing the generation of the above-mentioned bubbles can be obtained. Further, unlike the above case, when the platinum-containing material F is used in a portion where the molten glass temperature T is 1458.5 ° C or more (for example, the side wall surface of the clarification tank 30), the thickness of the platinum-containing material F can be set to It is greater than or equal to (0.012 T-16.4) mm, and the effect of suppressing the generation of the above-mentioned bubbles is confirmed.

As described above, a glass article manufacturing apparatus suitable for the heat-resistant material for molten glass of the present invention can be used to obtain a homogeneous glass article without mixing fine oxygen-containing bubbles which are a problem in the glass article.

10‧‧‧Glass manufacturing equipment

20‧‧‧Glass melting tank

21‧‧‧Blowing machine

22‧‧‧Material feeder

23‧‧‧ Burner

24‧‧‧ electrodes

30‧‧‧Glass clarification tank

40‧‧‧ feeder

50‧‧‧ throat

B‧‧‧bubble

M‧‧‧ glass raw materials

G‧‧‧ molten glass

R‧‧ refractory

F‧‧‧ platinum-containing materials

Fig. 1 is a partial cross-sectional view showing a glass article manufacturing apparatus of the present invention, wherein Fig. 1(A) is a longitudinal cross-sectional view, and Fig. 1(B) is a cross-sectional view showing a main portion of the X-X cross section of Fig. 1(A).

10‧‧‧Glass manufacturing equipment

20‧‧‧Glass melting tank

21‧‧‧Blowing machine

22‧‧‧Material feeder

23‧‧‧ Burner

24‧‧‧ electrodes

30‧‧‧Glass clarification tank

40‧‧‧ feeder

50‧‧‧ throat

B‧‧‧bubble

F‧‧‧ platinum-containing material

G‧‧‧ molten glass

M‧‧‧ glass raw materials

R‧‧ refractory

Claims (11)

A heat-resistant material for melting glass, which is composed of a platinum-containing material used in a heating manufacturing apparatus of a multi-component series oxide glass, characterized in that a platinum-containing material having a surface in contact with the molten glass has a thickness of 1.1 mm. In the range of ~50 mm, at least a part of the surface of the inner surface side of the surface of the platinum-containing material in contact with the molten glass is one selected from the group consisting of glass, ceramic, crystallized glass, concrete, mortar, and heat resistant metal or Supported and constructed by more than one material. The heat-resistant material for molten glass according to claim 1, wherein when the temperature T of the molten glass is less than 1458.5 ° C, the lower limit of the thickness of the platinum-containing material is set to 1.1 mm, and the temperature of the molten glass is When T is greater than or equal to 1458.5 ° C, the lower limit of the thickness of the platinum-containing material is set to (0.012 T - 16.4) mm. The heat-resistant material for molten glass according to the first or second aspect of the invention, wherein the platinum-containing material has a platinum content of at least 10% by mass. The heat-resistant material for molten glass according to the second aspect of the invention, wherein the platinum-containing material is applied to a heating manufacturing apparatus for continuously melting molten glass. A glass article manufacturing apparatus characterized in that the heat resistant material for molten glass according to any one of claims 1 to 4 is provided in a furnace bed surface, a side wall surface, and a groove selected from the group consisting of a heating manufacturing apparatus One or more of the groups of the inner surface of the structure for connection. The glass article manufacturing device according to claim 5, The temperature of the molten glass in the apparatus is 700 ° C to 2200 ° C. A glass article manufacturing apparatus according to claim 5 or 6, which is for manufacturing flat glass. A glass article manufacturing apparatus according to claim 5 or 6, which is a device for manufacturing flat glass for a flat panel display. The glass article manufacturing apparatus according to claim 5, which is for manufacturing a flat glass for mounting a liquid crystal display device. A glass article manufacturing apparatus according to claim 5, which is a device for producing flat glass for a solid-state image sensor. A method for producing a glass article, which is a method for producing a glass article using the glass article manufacturing apparatus according to any one of claims 5 to 10.