WO2013046683A1 - ガラス板の製造方法及びガラス板製造装置 - Google Patents

ガラス板の製造方法及びガラス板製造装置 Download PDF

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Publication number
WO2013046683A1
WO2013046683A1 PCT/JP2012/006175 JP2012006175W WO2013046683A1 WO 2013046683 A1 WO2013046683 A1 WO 2013046683A1 JP 2012006175 W JP2012006175 W JP 2012006175W WO 2013046683 A1 WO2013046683 A1 WO 2013046683A1
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WIPO (PCT)
Prior art keywords
glass
glass ribbon
space
furnace
cutting
Prior art date
Application number
PCT/JP2012/006175
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
浩幸 苅谷
公彦 中嶋
Original Assignee
ＡｖａｎＳｔｒａｔｅ株式会社
アヴァンストレート コリア インコーポレイテッド
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
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Application filed by ＡｖａｎＳｔｒａｔｅ株式会社, アヴァンストレート コリア インコーポレイテッド filed Critical ＡｖａｎＳｔｒａｔｅ株式会社
Priority to CN201280003073.5A priority Critical patent/CN103124701B/zh
Priority to JP2012557742A priority patent/JP5288388B1/ja
Priority to KR1020127029109A priority patent/KR101346939B1/ko
Publication of WO2013046683A1 publication Critical patent/WO2013046683A1/ja

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B33/00—Severing cooled glass
    • C03B33/02—Cutting or splitting sheet glass or ribbons; Apparatus or machines therefor
    • C03B33/0215—Cutting or splitting sheet glass or ribbons; Apparatus or machines therefor the ribbon being in a substantially vertical plane
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B17/00—Forming molten glass by flowing-out, pushing-out, extruding or drawing downwardly or laterally from forming slits or by overflowing over lips
    • C03B17/06—Forming glass sheets
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B17/00—Forming molten glass by flowing-out, pushing-out, extruding or drawing downwardly or laterally from forming slits or by overflowing over lips
    • C03B17/06—Forming glass sheets
    • C03B17/067—Forming glass sheets combined with thermal conditioning of the sheets
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B18/00—Shaping glass in contact with the surface of a liquid
    • C03B18/02—Forming sheets
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B18/00—Shaping glass in contact with the surface of a liquid
    • C03B18/02—Forming sheets
    • C03B18/20—Composition of the atmosphere above the float bath; Treating or purifying the atmosphere above the float bath
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/133302—Rigid substrates, e.g. inorganic substrates

Definitions

  • the present invention relates to a glass plate manufacturing method and a glass plate manufacturing apparatus by a downdraw method.
  • a down draw method is used as a method for forming a glass substrate used in a flat panel display such as a liquid crystal display.
  • a flat panel display such as a liquid crystal display.
  • Patent Document 2 in the method for producing a glass sheet by the downdraw method, the atmospheric pressure of the furnace outside atmosphere (furnace outside space) of the forming furnace and / or the slow cooling furnace is applied in order to reduce the plane distortion of the glass sheet.
  • produces along a glass ribbon in a slow cooling furnace is disclosed.
  • the glass plate manufactured is requested
  • the glass ribbon after the slow cooling is generally cut into a desired size in a glass ribbon cutting chamber disposed below the slow cooling furnace to form a glass plate.
  • edge part which has thickness larger than the center part of the width direction of a glass plate is formed in the both ends of the width direction of a glass plate.
  • the ear portion is cut in the ear cutting chamber after the glass plate is conveyed to the ear cutting chamber adjacent to the glass ribbon cutting chamber so as to allow ventilation.
  • Patent Document 2 when an air flow rising from the cutting chamber into the slow cooling furnace is generated, glass particles flowing into the glass ribbon cutting chamber from the ear cutting chamber are generated in the air flow. Since it is contained, the glass particles may flow into the slow cooling furnace and adhere to the glass ribbon flowing in the slow cooling furnace.
  • glass ribbon is slowly cooled with glass particles adhering to the surface of the glass ribbon, bubbles and microprotrusions are formed on the surface of the glass ribbon by the glass particles. The surface quality of the glass plate may deteriorate.
  • an object of the present invention is to provide a method for producing a glass plate that suppresses deterioration of the surface quality of the glass plate when the glass plate is produced by the downdraw method.
  • a first aspect of the present invention is a method for producing a glass plate by a downdraw method, A melting process for melting glass raw material to obtain molten glass; Forming the glass ribbon by supplying the molten glass to a molded body provided in a molding furnace; and A slow cooling step of cooling the glass ribbon in the slow cooling furnace by pulling with a roller provided in the slow cooling furnace; A glass ribbon cutting step of cutting the cooled glass ribbon in a glass ribbon cutting space; And an ear cutting step of cutting the ear formed at both ends in the width direction of the cut glass ribbon in the ear cutting space.
  • the air pressure in the glass ribbon cutting space In order for the air pressure in the glass ribbon cutting space to be higher than the air pressure in the ear cutting space, The air pressure of at least one of the glass ribbon cutting space and the ear cutting space is adjusted.
  • the pressure of at least one of the glass ribbon cutting space and the ear cutting space is such that the difference between the pressure of the glass ribbon cutting space and the pressure of the ear cutting space is 40 Pa or less. It has been adjusted to be.
  • the pressure in the glass ribbon cutting space is adjusted so as to be lower than the pressure in the furnace internal space.
  • the slow cooling step At the center in the width direction of the glass ribbon, so that tension acts in the flow direction of the glass ribbon, At least in the temperature region where the temperature of the central portion in the width direction of the glass ribbon is a temperature obtained by adding 150 ° C. to the annealing point temperature of the glass and subtracting 200 ° C. from the strain point temperature of the glass, The temperature is controlled so that the cooling rate at the center in the width direction of the glass ribbon is faster than the cooling rate at both ends in the width direction.
  • the temperature in the center portion of the glass ribbon in the width direction is equal to or higher than the softening point temperature of the glass
  • the temperature in the center portion where both ends in the width direction of the glass ribbon are sandwiched between the both ends.
  • Lower and control the temperature of the glass ribbon so that the temperature of the central portion is uniform
  • In the central portion of the glass ribbon in the width direction in the region where the temperature of the central portion of the glass ribbon is less than the softening point temperature of the glass and the strain point temperature of the glass or higher so that the tension in the flow direction of the glass ribbon works.
  • the temperature of the glass ribbon is controlled so that the temperature of the temperature distribution in the width direction of the glass ribbon decreases from the central part toward the both end parts,
  • the temperature of the glass ribbon is controlled so that there is no temperature gradient between the both end portions in the width direction of the glass ribbon and the central portion in the temperature region where the temperature of the central portion of the glass ribbon is the strain point temperature of the glass. .
  • each of the first to fifth preferred forms is applied, and a composite form combining at least two of the first to fifth preferred forms is also available. Can be applied.
  • a second aspect of the present invention is an apparatus for producing a glass plate by a downdraw method, A melting tank for melting glass raw material to obtain molten glass; A molding furnace for forming the glass ribbon by supplying the molten glass to a molded body provided in the molding furnace, A slow cooling furnace that pulls the glass ribbon with a roller provided in the slow cooling furnace and cools the glass ribbon in the slow cooling furnace; A glass ribbon cutting device for cutting the cooled glass ribbon in a glass ribbon cutting space; An ear cutting device for cutting ears formed at both ends in the width direction of the cut glass ribbon in an ear cutting space; Adjusting means for adjusting the air pressure of at least one of the glass ribbon cutting space and the ear cutting space so that the air pressure of the glass ribbon cutting space is higher than the air pressure of the ear cutting space.
  • the adjusting means includes In the glass ribbon cutting space and the ear cutting space, a pressure sensor for measuring the pressure of the atmospheric pressure, a blower for sending air from the atmosphere into the glass ribbon cutting space and the ear cutting space, and the gas ribbon cutting space, At least one device of a dust collector that sucks and collects air in the ear cutting space, and a control device that adjusts the device according to the measurement result of the pressure sensor.
  • the blower provided in the glass ribbon cutting space when the inner space of the molding furnace provided with the molded body and the inner space of the slow cooling furnace provided with the rollers are used as the furnace inner space.
  • at least one of the dust collectors adjusts the intake of air from the atmosphere and the air suction of the cutting space so that the pressure in the glass ribbon cutting space becomes lower than the pressure in the furnace internal space. And adjusting the pressure of the glass ribbon cutting space.
  • a cooling unit is provided in the internal space of the molding furnace, and a temperature adjustment unit is provided in the internal space of the slow cooling furnace, At least one of the cooling unit and the temperature adjustment unit is In a region where the temperature of the center portion in the width direction of the glass ribbon is equal to or higher than the softening point temperature of the glass, both ends in the width direction of the glass ribbon are lower than the temperature of the center portion sandwiched between the both ends, and the center Control the temperature of the glass ribbon so that the temperature of the part is uniform, In the central portion of the glass ribbon in the width direction, in the region where the temperature of the central portion of the glass ribbon is less than the softening point temperature of the glass and the strain point temperature of the glass or higher so that the tension in the flow direction of the glass ribbon works.
  • the temperature of the glass ribbon is controlled so that there is no temperature gradient between the both end portions in the width direction of the glass ribbon and the central portion in the temperature region where the temperature of the central portion of the glass ribbon is the strain point temperature of the glass. .
  • a temperature adjustment unit is provided in the internal space of the annealing furnace, The temperature adjustment unit is The temperature of the temperature distribution of the glass ribbon in the region where the temperature of the central portion of the glass ribbon is lower than the strain point temperature of the glass so that the tension in the flow direction of the glass ribbon works at the central portion in the width direction of the glass ribbon.
  • the temperature of the glass ribbon is controlled so as to become lower from the both end portions toward the central portion.
  • the glass plate manufacturing method and glass plate manufacturing apparatus of the above aspect it is possible to suppress deterioration of the surface quality of the glass plate.
  • FIG. 1 is a diagram showing a flow of a glass plate manufacturing method according to the present embodiment.
  • the center part of sheet glass means the center of the width direction of sheet glass among the width
  • the edge part of sheet glass means the range within 100 mm from the edge of the width direction of sheet glass.
  • the strain point temperature refers to the temperature of a glass plate having a log ⁇ of 14.5 when the glass viscosity is ⁇ .
  • the annealing point temperature refers to the temperature of glass having a log ⁇ of 13.
  • the softening point temperature refers to the temperature of glass having a log ⁇ of 7.6.
  • the glass transition temperature refers to the temperature of the glass when the supercooled liquid changes to the glass state.
  • the glass plate manufacturing method includes a melting step (ST1), a refining step (ST2), a homogenizing step (ST3), a supplying step (ST4), a forming step (ST5), and a slow cooling step (ST6).
  • the glass ribbon cutting step (ST7) and the ear portion cutting step (ST8) are mainly included.
  • a plurality of glass plates that have a grinding process, a polishing process, a cleaning process, an inspection process, a packing process, and the like and are stacked in the packing process are conveyed to a supplier.
  • FIG. 2 is a diagram schematically showing an apparatus for performing the melting step (ST1) to the ear cutting step (ST8).
  • the apparatus mainly includes a melting device 200, a forming device 300, a glass ribbon cutting device 400, and an ear cutting device 500.
  • the melting apparatus 200 includes a melting tank 201, a clarification tank 202, a stirring tank 203, a first pipe 204, and a second pipe 205.
  • the molding apparatus 300 will be described later.
  • molten glass is obtained by heating and melting the glass raw material supplied into the melting tank 201.
  • the clarification step (ST2) is mainly performed in the clarification tank 202 to reduce bubbles contained in the molten glass.
  • the homogenization step (ST3) the molten glass in the stirring tank 203 supplied through the first pipe 204 is stirred using a stirrer to homogenize the glass components.
  • the supplying step (ST4) the molten glass is supplied to the molding apparatus 300 through the second pipe 205.
  • a molding process (ST5) and a slow cooling process (ST6) are performed.
  • the forming step (ST5) the molten glass is formed into a glass ribbon G (see FIG. 3), and a flow of the glass ribbon G is created.
  • an overflow down draw method using a molded body 310 described later is used.
  • the slow cooling step (ST6) cooling is performed so as not to cause plane distortion and to further increase the thermal shrinkage rate.
  • the glass ribbon cutting step (ST7) the glass ribbon cutting device 400 cuts the glass ribbon G supplied from the forming device 300 into a predetermined length, thereby obtaining a plate-like glass plate G1 (see FIG. 3). .
  • the ear cutting device 500 cuts the ear G2 (see FIG. 3) formed at both ends in the width direction of the glass plate G1.
  • the ear portion G2 is formed at both end portions in the width direction of the glass ribbon G in the forming step (ST5) and the slow cooling step (ST6), and is in contact with a later-described cooling roller 330 and conveying rollers 350a to 350h.
  • edge part G2 is larger than the thickness of the center part of the width direction of the glass ribbon G.
  • the glass plate G1 of a target size is produced by cutting the glass plate G1 after the ear cutting step into a predetermined size.
  • FIG. 3 and 4 are diagrams mainly showing a configuration of the glass sheet forming apparatus 300
  • FIG. 3 mainly shows a schematic side view of the forming apparatus 300
  • FIG. 4 is a schematic front view of the forming apparatus 300.
  • the glass plate molded by the molding apparatus 300 is preferably used for, for example, a glass substrate for liquid crystal display, a glass substrate for organic EL display, and a cover glass.
  • the glass plate formed by the forming apparatus 300 can also be used as a display for a portable terminal device, a cover glass for a casing, a touch panel plate, a glass substrate of a solar cell, or a cover glass.
  • LTPS Low Temperature Poly Silicon
  • the forming furnace 40 for performing the forming step (ST5) and the slow cooling furnace 50 for performing the slow cooling step (ST6) are surrounded by a furnace wall composed of a refractory material such as a refractory brick, a refractory heat insulating brick, or a fiber-based heat insulating material.
  • the molding furnace 40 is provided vertically above the slow cooling furnace 50.
  • the forming furnace 40 and the slow cooling furnace 50 are collectively referred to as a furnace 30.
  • the molded body 310 forms molten glass (indicated by reference numeral MG in FIGS. 3 and 4) flowing from the melting device 200 through the second pipe 205 into a glass ribbon G.
  • the molded body 310 is a long and narrow structure formed of refractory bricks or the like, and has a wedge-shaped cross section as shown in FIG.
  • a groove 312 serving as a flow path for guiding the molten glass is provided on the top of the molded body 310.
  • the molten glass overflowing from the groove 312 travels down the side walls on both sides of the molded body 310 and flows down vertically.
  • the molten glass that has flowed through the side walls merges at the lower end 313 of the molded body 310 shown in FIG. 3, and one glass ribbon G is formed. As a result, the glass ribbon G flows down toward the slow cooling furnace 50.
  • an atmosphere partition member 320 is provided.
  • the atmosphere partition member 320 is a pair of plate-like heat insulating members and is configured to sandwich the glass ribbon G from both sides in the thickness direction. That is, a gap is formed in the atmosphere partition member 320 so as not to contact the glass ribbon G.
  • the atmosphere partition member 320 blocks the movement of heat between the furnace internal space above the atmosphere partition member 320 and the furnace internal space below by partitioning the molding furnace internal space.
  • a cooling roller 330 is provided below the atmosphere partition member 320.
  • the cooling roller 330 is in contact with the glass ribbon G surface in the vicinity of both ends in the width direction of the glass ribbon G and pulls the glass ribbon G downward to form a glass ribbon G having a desired thickness. Cool the vicinity of both ends of G.
  • a cooling unit 340 is provided below the cooling roller 330.
  • the cooling unit 340 cools the glass ribbon G that has passed through the cooling roller 330.
  • the cooling unit 340 includes, for example, an air amount adjustment unit, and an air amount for air-cooling both ends of the glass ribbon can be adjusted by a control device 600 described later.
  • the driving of the cooling roller 330 can be adjusted via a motor (not shown).
  • conveying rollers 350a to 350h are provided at predetermined intervals, and pull the glass ribbon G downward.
  • the space below the cooling unit 340 is a furnace internal space of the slow cooling furnace 50.
  • the conveyance rollers 350a to 350h can be driven by a motor (not shown).
  • a pressure sensor 355 that measures the atmospheric pressure in the furnace internal space is provided in the furnace internal space of the molding furnace 40.
  • the pressure sensor 355 is provided at the same position as the molded body 310 in the height direction (vertically upward direction).
  • the height direction is the left direction in FIG. 3 and the upward direction in FIG. Since the glass ribbon G flows vertically downward from the molded body 310, the flow direction of the glass ribbon G is opposite to the height direction.
  • Pressure sensors 360 a to 360 c are provided in the furnace internal space of the slow cooling furnace 50.
  • temperature adjusting units 370 a to 370 c in which a plurality of heating sources are arranged along the width direction of the glass ribbon G are provided along the glass ribbon G in the furnace internal space of the forming furnace 40. The heating temperature of each heating source of the temperature adjustment units 370a to 370c can be adjusted.
  • furnace exterior spaces S1, S2, S3a to S3c are provided outside the furnace wall of the forming furnace 40.
  • Each of these spaces is partitioned by floor surfaces 411, 412, 413a to 413c in the height direction. That is, the molding apparatus 300 is provided in a building B having a plurality of floors, and furnace external spaces (partial spaces) S1, S2, S3a to S3c divided into a plurality by the floor surface are provided on each floor.
  • a space S4 (glass ribbon cutting space) partitioned by walls on the floor 414 is provided below the furnace external space S3c.
  • a space S5 (ear cutting space) partitioned by walls on the floor 414 is provided adjacent to the space S4.
  • a furnace wall is not provided in the spaces S4 and S5.
  • the air pressure in these spaces is adjusted by blowers 421, 422, 423a, 423b, 423c, 424, and 425, which will be described later.
  • the furnace outside space S1 is a space vertically above the position in the height direction of the molded body 310, and a pressure sensor 415 for measuring the pressure in the furnace outside space is provided in the furnace outside space S1.
  • the furnace exterior space S2 is a space provided on the floor surface 412, and the molded body 310 is disposed in the furnace interior space corresponding to this space.
  • a pressure sensor 416 for measuring the atmospheric pressure in the furnace external space S2 is provided in the furnace external space S2.
  • a pressure sensor 355 for measuring the pressure in the furnace inner space is provided at the same position in the height direction of the pressure sensor 416.
  • the furnace outside spaces S3a to S3c are spaces provided below the furnace outside space S2 in the order of the furnace outside spaces S3a to 3c from the highest in the height direction.
  • the furnace outer spaces S3a to 3c are provided on the floor surfaces 413a to 413c.
  • pressure sensors 417a to 417c for measuring the atmospheric pressure in the furnace external spaces 3a to 3c are provided in the furnace external spaces S3a to S3c, respectively.
  • pressure sensors 360a to 360c for measuring the pressure in the furnace inner space are provided at the same position in the height direction of the pressure sensors 417a to 417c.
  • the pressure sensors 355, 360a to 360c are provided at each position in the furnace internal space, but the pressure sensor may be inserted into each position in the furnace internal space to measure the pressure. .
  • voltage between a furnace exterior space and a furnace interior space is not specifically limited, As an example of the measuring method of a differential pressure, it can measure using a differential pressure gauge. Further, the differential pressure between each of the furnace external spaces S2, S3a to S3c, S4, and S5 can be measured using a differential pressure gauge.
  • pressure sensors 418 and 419 for measuring the atmospheric pressure in the spaces S4 and S5 are provided in the spaces S4 and S5, respectively.
  • a communication hole (not shown) that communicates the spaces S4 and S5 is formed in the wall 420 that divides the spaces S4 and S5 in order to convey the glass plate G1 in the space S4 to the space S5. That is, the spaces S4 and S5 can be ventilated through the communication holes.
  • the size of this communication hole is as small as possible in order to reduce the inflow amount of glass particles (such as chips and dust) generated when cutting the ear portion G2 into the space S4 in the space S5.
  • the glass plate G1 It is preferable that the main surface is formed in a size that allows the glass plate G1 to be transported to the space S5 in a state along the transport direction from the space S4 to the space S5.
  • a transport device not shown
  • portions of the glass plate G1 that are not included in the product for example, an upper end portion and a lower end of the glass plate G1.
  • the glass plate G1 may be transported by holding both sides in the thickness direction of the glass plate G1 at a portion or at the four sides of the main surface.
  • the transfer device when a portion of the glass plate G1 included in the product, for example, a central portion of the main surface of the glass plate G1, or the like is not held by the transfer device, the amount of air flowing from the space S5 to the space S4 is large. When the glass plate G1 is conveyed, the portion may be bent by the air flowing from the space S5 into the space S4. On the other hand, in this embodiment, since the atmospheric pressure in the space S4 and the space S5 is adjusted as described later, it is possible to prevent the air in the space S5 from flowing into the air in the space S4.
  • a blower is provided for each of the furnace outside spaces S1, S2, S3a to S3c, the space S4 and the space S5. 421, 422, 423a, 423b, 423c, 424, 425 are provided.
  • the air sent from the atmospheric pressure by each blower is supplied to each of the furnace external spaces S1, S2, S3a to S3c, the space S4 and the space S5 through the pipes.
  • the amount of air sent by each blower is determined by a drive signal from a drive unit 510 described later.
  • FIG. 5 is a schematic diagram of a control system that controls the amount of air that the blowers 421, 422, 423a, 423b, 423c, 424, and 425 send.
  • the control system includes pressure sensors 355, 360a to 360c provided in the furnace internal space, pressure sensors 415, 416, 417a to 417c, 418, 419 provided in the external space of the furnace, a control device 600, and a drive. It has a unit 610 and blowers 421, 422, 423a, 423b, 423c, 424, 425.
  • the control device 600 includes a pressure measurement result in the furnace internal space sent from each pressure sensor provided in the furnace internal space, and a pressure measurement result in the furnace external space sent from each pressure sensor provided in the furnace external space.
  • the generated control signal is sent to the drive unit 610.
  • the amount of air sent by each blower is set, for example, in advance so that the reference value range of the atmospheric pressure is set in advance for each furnace external space, and the atmospheric pressure in each furnace external space is included in the reference value range. It may be adjusted.
  • the drive unit 610 generates a drive signal for individually adjusting the amount of air sent by the blower based on the control signal.
  • the drive unit 610 sends a drive signal for each blower.
  • control device 600 is electrically connected to the cooling unit 340, the temperature adjustment units 370a to 370c, the cooling roller 330, and the transport rollers 350a to 350h via the drive unit 610.
  • the control device 600 controls the heating temperature of the cooling unit 340 via the drive unit 610, adjusts the heating temperature of the heating source of the temperature adjustment units 370a to 370c, adjusts the driving and temperature of the cooling roller 330, and The driving of the transport rollers 350a to 350h can be adjusted.
  • the control device 600 and the drive unit 610 automatically control the air feed amount, but the operator may manually adjust the air feed amount.
  • the atmospheric pressure control is performed using the blower as an example of the atmospheric pressure control method
  • the atmospheric pressure control method is not limited to the method.
  • the atmospheric pressure control may be performed by using a dust collector (not shown) that collects dust by sucking glass particles generated when the glass is cut.
  • the dust collectors are provided in the vicinity of the glass ribbon cutting device 400 in the space S4 and the ear cutting device 500 in the space S5, and the air is sucked into the space S4 and the space S5 to suck the air. It is configured to be able to collect the particles of glass contained therein.
  • the air pressure in the space S4 and the space S5 can be controlled by controlling the amount of air sucked by the dust collector in each of the space S4 and the space S5. Moreover, you may perform the atmospheric
  • the glass particle (glass chips, dust, etc.) adhering to a glass plate in the manufacturing process of a glass plate is mentioned.
  • the glass ribbon after the slow cooling step is cut into a desired size in a glass ribbon cutting chamber disposed below the slow cooling furnace, thereby forming a glass plate.
  • edge part which has thickness larger than the center part of the width direction of a glass plate is formed in the both ends of the width direction of a glass plate.
  • the ear portion is cut in the ear cutting chamber after the glass plate is conveyed to the ear cutting chamber adjacent to the glass ribbon cutting chamber so as to allow ventilation.
  • glass particles generated when the ear is cut are scattered in the ear cutting chamber, and the glass particles flow into the glass ribbon cutting chamber adjacent to the ear cutting chamber. There is a case.
  • the amount of air sent from the blowers 424 and 425 is adjusted in each space such that the air pressure in the space S4 is higher than the air pressure in the space S5.
  • air pressure in the space S4 becomes lower than the air pressure in the space S5
  • air particles flowing into the space S4 contain glass particles scattered in the space S5
  • Glass particles may adhere to the glass ribbon G.
  • the difference in atmospheric pressure between the space S4 and the space S5 is more than 0 to 40 Pa, preferably 1 to 35 Pa, more preferably 2 to 30 Pa, still more preferably 3 to 25 Pa, More preferably, it is 4 to 15 Pa. If the difference in the atmospheric pressure exceeds the above range, a large amount of air may flow out of the communication hole from the space S4 toward the space S5. In this case, the glass plate G1 conveyed from the space S4 to the space S5 may be damaged during the conveyance due to vibration or deflection caused by the air.
  • the amount of air sent into each blower is such that the air pressure in the furnace external space S2, S3a to S3c is lower than the air pressure in the furnace internal space at the same position in the height direction. Adjusted.
  • the difference in atmospheric pressure between the furnace inner space and the furnace outer space S2 of the molding furnace 40 is more than 0 to 40 Pa, preferably 4 to 35 Pa, more preferably 8 to 30 Pa, and more preferably 10 to 27 Pa. It is more preferable that the pressure is 10 to 25 Pa.
  • the pressure difference is less than the above range, air may flow from the gap between the furnace walls from the furnace outer space S2 toward the furnace inner space, which may cause temperature fluctuations in the furnace inner space.
  • the difference in atmospheric pressure it is possible to prevent low temperature air from flowing into the furnace internal space of the molding furnace 40 from the furnace external space S2. For this reason, the temperature fluctuation of the furnace internal space can be suppressed. That is, it is possible to prevent only a portion of the molten glass or glass ribbon G that is in contact with the air flowing into the forming furnace 40 from being rapidly cooled.
  • the viscosity of the quenched portion is increased, and when the glass ribbon G is stretched by a roller on the downstream side of the conveyance path, Since the portion where the viscosity is high cannot be sufficiently stretched, there arises a problem that the deviation of the thickness of the glass plate is caused.
  • the atmospheric pressure range to the above range, it is possible to suppress the variation in the cooling rate, and hence the variation in the thickness of the glass ribbon G.
  • the difference in atmospheric pressure between the inner space of the slow cooling furnace 50 and the outer space S3a to S3c is more than 0 to 40 Pa, preferably 2 to 35 Pa, more preferably 2 to 25 Pa, The pressure is more preferably 3 to 23 Pa, and further preferably 5 to 20 Pa.
  • the difference in the atmospheric pressure exceeds the above range, a large amount of air may flow out of the gap between the furnace walls from the furnace inner space toward the furnace outer space S3a to S3c, increasing the rise of air in the furnace inner space. .
  • the difference in the atmospheric pressure is less than the above range, air may flow from the furnace outer space S3a to S3c through the gap between the furnace walls toward the furnace inner space, and the temperature distribution in the furnace inner space varies.
  • the difference in the atmospheric pressure it is possible to prevent low temperature air from flowing into the furnace internal space of the slow cooling furnace 50 from the furnace external spaces S3a to S3c, so that the temperature variation in the furnace internal space can be suppressed.
  • variation in heat shrink can be suppressed.
  • the problem caused by the temperature variation in the furnace internal space will be described in detail.
  • the temperature profile in the width direction of the glass ribbon G is controlled in order to suppress warping of the glass ribbon G and the like. Specifically, in the transport region of the glass ribbon G, in the transport region where the temperature of the central portion in the width direction of the glass ribbon G is equal to or higher than the annealing temperature + 5 ° C., both end portions in the width direction of the glass ribbon G The temperature of the glass ribbon G is controlled so that the temperature increases toward the center in the width direction.
  • the width direction of the glass ribbon G is controlled so that the temperature difference between the center portion and both end portions in the width direction becomes small.
  • the glass ribbon G in the transport region of the glass ribbon G, in the transport region where the temperature in the center in the width direction of the glass ribbon G is equal to or higher than the annealing temperature + 5 ° C., the glass ribbon G is locally localized due to, for example, inflow of low-temperature air. If the temperature is rapidly cooled, the temperature profile cannot be realized, and the glass ribbon G warps. Further, in the conveyance region where the temperature of the glass ribbon G is (annealing point temperature + 5 ° C.) to (strain point temperature ⁇ 50 ° C.) in the conveyance region of the glass ribbon G, both end portions in the width direction of the glass ribbon G The temperature of the glass ribbon G is controlled so that the temperature is substantially uniform with the central portion in the width direction.
  • the residual stress of the glass ribbon G can be reduced, and the plane distortion of the glass plate can be reduced. Further, the longer the temperature of the glass ribbon G is within the range of (annealing point temperature + 5 ° C.) to (strain point temperature ⁇ 50 ° C.), the more heat shrinkage of the glass plate can be reduced. it can.
  • the glass ribbon G is locally rapidly cooled by, for example, inflow of low-temperature air in the conveyance region where the temperature of the glass ribbon G is (slow cooling point temperature + 5 ° C.) to (strain point temperature ⁇ 50 ° C.) Since the plane strain is generated in the rapidly cooled portion or the thermal shrinkage rate of the portion is increased, there arises a problem that the plane strain is increased and the thermal shrinkage is uneven.
  • the problem described above is that the difference in pressure in the furnace internal space is prevented by adjusting the pressure difference to the above range to prevent low temperature air from flowing into the furnace internal space of the slow cooling furnace 50 from the furnace external spaces S3a to S3c. It can be reduced by suppressing.
  • the pressure in the furnace outer space is adjusted so that the pressure in all the furnace outer spaces is lower than the pressure in the furnace inner space at the same position in the height direction.
  • the pressure in the outer space of the furnace may be adjusted so that the pressure in at least a part of the furnace becomes lower than the pressure in the furnace inner space at the same position in the height direction.
  • the atmospheric pressure in the outside space of the furnace is high. It is preferable to adjust so that it may become low with respect to the atmospheric
  • the position corresponding to the annealing point temperature is, for example, a position in the height direction of the furnace outside space S3a
  • the position corresponding to the strain point temperature is, for example, a position in the height direction of the furnace outside space S3b.
  • the glass ribbon G is solidified and most affects the plane distortion and thermal shrinkage of the glass. Therefore, the air pressure is efficiently adjusted in the above region to suppress the inflow of air from the outside space of the furnace. By doing so, it is preferable to suppress variations in temperature in the furnace internal space.
  • the glass ribbon G is one continuous plate until it is cut from the molding furnace 40.
  • the warp shape of the glass ribbon G changes in the region where the temperature of the glass ribbon G is less than (strain point temperature ⁇ 50 ° C.)
  • the glass ribbon in the region where the temperature becomes (strain point temperature ⁇ 50 ° C.) or more is also affected.
  • heat shrinkage variation occurs. As described above, that is, by suppressing the variation in temperature in the region where the temperature of the glass ribbon G is less than (strain point temperature ⁇ 50 ° C.), it is possible to suppress the variation in warpage, plane strain, and thermal shrinkage. .
  • the pressure sensor 415 at a position in the height direction where there is no furnace internal space is used to adjust the furnace external space S1 by the blower 421 so that air does not flow from the furnace external space S1 into the furnace internal space. Measure the atmospheric pressure.
  • the pressure sensor 418 is used for adjusting the atmospheric pressure in the space S4 by the blower 424 and measuring the atmospheric pressure in the space S4. For example, it is preferable that the air pressure in the space S4 is adjusted so that the space S4 is further lower than the lowest air pressure in the furnace internal space. By adjusting the atmospheric pressure in the space S4 as described above, the air flowing from the space S4 to the furnace internal space can be reduced.
  • the air blowers 421, 422, 423a, 423b, 423c, 424, and 425 send air to the furnace external spaces S1, S2, S3a to S3c, the space S4, and the space S5, so that the air pressure in any space is relative to the atmospheric pressure.
  • the reason why the atmospheric pressure in these spaces is made higher than the atmospheric pressure is that a large amount of air and the air are contained in the furnace outside spaces S1, S2, S3a to S3c, the space S4 and the space S5. This is to prevent particles from flowing in from the outside of the building B, and to efficiently adjust the atmospheric pressure in the furnace outer space S1, S2, S3a to S3c, the space S4, and the space S5.
  • the atmospheric pressure in the furnace internal space is controlled such that the higher the position in the height direction, the higher the atmospheric pressure.
  • the atmospheric pressure in the external space of the furnace is adjusted according to the atmospheric pressure distribution. This is to prevent air from flowing into the furnace internal space due to the difference between the pressure in the furnace outer space and the pressure in the furnace inner space, or to prevent air convection from leaking into the furnace outer space.
  • a pressure sensor is provided in the furnace inner space at the same position in the height direction as the pressure sensor provided in each of the furnace outer space.
  • the difference between the atmospheric pressure in the furnace external space and the atmospheric pressure in the furnace internal space at the same position in the height direction of the furnace external space is calculated as the position in the height direction. It is preferable to adjust so that it may change with. For example, when a comparison is made between the uppermost furnace outer space S2 and the lowermost furnace outer space S3c among the furnace outer spaces S2, S3a to S3c in which the furnace inner space exists at the same position in the height direction, It is preferable that the difference in atmospheric pressure is adjusted so as to be larger than the difference in atmospheric pressure at the bottom. For example, the difference in the atmospheric pressure may be set so as to increase as the position in the height direction increases.
  • air pressure of a furnace exterior space becomes so high that the position of a height direction is high.
  • the air pressure in the space S4 is adjusted to be lower than the air pressure in the furnace internal space. Therefore, it is possible to prevent the air in the space S ⁇ b> 4 including the glass particles generated when the glass ribbon G is cut from moving upward due to the rising airflow. That is, even if air flows into the space S4 from the space S5, it is possible to prevent the glass particles contained in the air that has flown from moving into the furnace internal space due to the rising airflow. For this reason, since it can prevent that the glass particle adheres to the glass ribbon G, it can suppress that the surface quality of the glass plate G1 shape
  • the cooling of the glass ribbon G can be controlled for each form described below in the forming space S6 and the slow cooling space S7 shown in FIG.
  • the temperature of the cooling unit 340, the temperature adjustment units 370a to 370c, and the cooling roller 330 can be controlled in accordance with instructions from the control device 600 to cool the glass ribbon G as described below.
  • the glass ribbon G is caused to flow downstream in the slow cooling space S7 by using the cooling roller 330 or the transport rollers 350a to 350h
  • the glass ribbon G is caused by effectively exerting tension in the flow direction of the glass ribbon G. Can be suppressed.
  • the temperature of the central portion in the width direction of the glass ribbon S is equal to or higher than the softening point temperature of the glass.
  • the temperature of the glass ribbon G is controlled so that both end portions (ear portions) in the width direction of the glass ribbon G are lower than the temperature of the central portion and the temperature of the central portion is uniform. Further, in a region where the temperature in the central portion of the glass ribbon G in the width direction is lower than the softening point temperature and higher than the strain point temperature so that a tensile stress in the transport direction acts on the central portion in the width direction of the glass ribbon G.
  • the temperature of the glass ribbon G is controlled so that the temperature of the temperature distribution (temperature profile) in the width direction decreases from the center toward both ends. Further, in the temperature region in which the temperature in the center of the glass ribbon G in the width direction becomes the strain point temperature of the glass, the glass ribbon G has a glass gradient G so that there is no temperature gradient between both ends (ears) and the center in the width direction.
  • the temperature of the ribbon G is controlled. As a result, a tensile stress in the conveying direction is applied to the central portion in the width direction of the glass ribbon G, and the corrugation of the glass ribbon G or the adjacent region adjacent to the flowing portion sandwiched by the rollers of the lath ribbon G Can be prevented from occurring.
  • the temperature in the central portion in the width direction of the glass ribbon G is lower than the strain point temperature of the glass so that the tension in the transport direction acts on the central portion in the width direction of the glass ribbon G. It is also possible to control the temperature of the glass ribbon G so that the temperature of the temperature distribution (temperature profile) of the ribbon G decreases from both ends (ear portions) in the width direction toward the center in the width direction of the glass ribbon G. Thereby, in the region below the vicinity of the strain point temperature in the central portion of the glass ribbon G in the width direction, tensile stress can always be applied in the transport direction at the central portion in the width direction of the glass ribbon G, and the warp of the glass ribbon G Can be suppressed.
  • the cooling rate of the formed glass ribbon G by adjusting the cooling rate of the formed glass ribbon G, it is possible to suppress the deformation of the glass plate, suppress the warpage, and further reduce the absolute value of the heat shrinkage rate.
  • the glass ribbon G is heated from the temperature obtained by adding 150 ° C. to the slow cooling point temperature of the glass ribbon G. A temperature region from the strain point temperature of the ribbon G to a temperature subtracted by 200 ° C. is determined.
  • the cooling rate at the center in the width direction of the glass ribbon G is faster than the cooling rate at both ends of the glass ribbon G, and the temperature at the center in the width direction of the glass ribbon G is It is preferable to change the glass ribbon G from a state higher than the both end portions to a state where the temperature of the central portion is lower than both end portions. Thereby, it is possible to cause a tensile stress to act in the flow direction of the glass ribbon G at the center in the width direction of the glass ribbon G. Since tensile stress acts in the flow direction of the glass ribbon G, the warp of the glass ribbon G and eventually the glass plate can be further suppressed.
  • Examples of the glass composition of the glass plate used in the present embodiment include the following.
  • the content rate display of the composition shown below is mass%.
  • SiO 2 50 to 70%
  • B 2 O 3 5 to 18%
  • Al 2 O 3 0 to 25%
  • RO 5 to 20% (where R is at least one selected from Mg, Ca, Sr and Ba, and the glass plate contains)
  • R is at least one selected from Mg, Ca, Sr and Ba, and the glass plate contains
  • the glass plate may contain a trace amount of alkali metals.
  • the alkali metal is contained, the total of R ′ 2 O exceeds 0.20% and is 2.0% or less (provided that R ′ is at least one selected from Li, Na, and K, and is contained in the glass plate). It is preferable to contain.
  • the content of iron oxide in the glass is more preferably 0.01 to 0.2% from the viewpoint of reducing the specific resistance.
  • Li 2 O, Na 2 O, and K 2 O are components that may be eluted from the glass and deteriorate the characteristics of the TFT. Therefore, they are applied as glass substrates for liquid crystal displays and glass substrates for organic EL displays. When it does, it is preferable not to contain substantially. However, by deliberately containing a specific amount of the above components in the glass, the basicity of the glass is increased while the deterioration of TFT characteristics is suppressed, and the oxidation of metals with variable valences is facilitated to demonstrate clarity. It is possible to make it. Therefore, the total amount of Li 2 O, Na 2 O and K 2 O is 0 to 2.0%, more preferably 0.1 to 1.0%, and still more preferably 0.2 to 0.5%.
  • Li 2 O, Na 2 O is without substantially containing, in the component, most glass eluted from be contained hardly K 2 O which deteriorates the characteristics of the TFT are preferred.
  • the content of K 2 O is 0 to 2.0%, more preferably 0.1 to 1.0%, and further preferably 0.2 to 0.5%.
  • This embodiment is suitable for manufacturing a glass plate having a thickness of 0.05 mm to 1.5 mm.
  • the thinner the glass plate the easier it is to bend due to the air flow caused by the pressure difference, making it difficult to convey stably. Therefore, a glass plate having a thickness of 0.05 to 0.5 mm is broken during transportation by applying the method of the present embodiment in which the pressure difference is set within a predetermined range between the space S4 and the space S5. The effect of reducing the number of glass plates is great.
  • the length in the width direction of the glass plate of this embodiment is, for example, 500 mm to 3500 mm, and the length in the vertical direction of the glass plate is also, for example, 500 mm to 3500 mm.
  • the method of the present embodiment in which the atmospheric pressure difference between the space S4 and the space S5 is set within a predetermined range, the effect of reducing the number of glass plates that are broken during conveyance is great.
  • the effect of this embodiment becomes remarkable, so that the length of the glass plate in the width direction becomes 2000 mm or more.
  • this embodiment is suitable for manufacturing a glass plate having a length in the width direction of 2000 mm to 3500 mm and a length in the length direction of 2000 mm to 3500 mm.
  • the glass plate manufacturing method was variously changed to manufacture a glass plate, and further, the deterioration evaluation of the surface quality of the glass plate and the damage evaluation during the conveyance of the glass plate were performed.
  • the evaluation of the deterioration of the surface quality of the glass plate was obtained by calculating the ratio of the glass plate in which scratches including bubbles and microprojections occurred on the surface of the glass plate formed in the glass ribbon cutting space, and calculating the value of the comparative example as ⁇ It is a numerical value obtained as a ratio to the comparative example when “1.0”.
  • the number of samples of the evaluated glass plate is 1000 sheets each.
  • Example 1 After melting, clarifying, and stirring the glass raw material, a glass ribbon was formed using the overflow down draw method, and then gradually cooled. And after the glass ribbon was cut
  • the manufactured glass plate is a glass substrate for a liquid crystal display, and has a size of 2200 mm ⁇ 2500 mm and a thickness of 0.7 mm.
  • the glass composition of the glass plate was as follows. The content rate is expressed by mass%. SiO 2 60% Al 2 O 3 19.5% B 2 O 3 10% CaO 5.3% SrO 5% SnO 2 0.2%
  • Example 2 A glass substrate for a liquid crystal display was produced in the same manner as in Example 1 except that the pressure in the glass ribbon cutting space was higher than the pressure in the ear cutting space and the pressure difference was 25 Pa.
  • Example 3 A glass substrate for a liquid crystal display was produced in the same manner as in Example 1 except that the pressure in the glass ribbon cutting space was higher than the pressure in the ear cutting space and the pressure difference was 35 Pa.
  • Example 4 A glass substrate for a liquid crystal display was produced in the same manner as in Example 1 except that the pressure in the glass ribbon cutting space was higher than the pressure in the ear cutting space and the pressure difference was 40 Pa.
  • Example 5 A glass substrate for a liquid crystal display was produced in the same manner as in Example 1 except that the pressure in the glass ribbon cutting space was higher than the pressure in the ear cutting space and the pressure difference was 45 Pa.
  • Comparative Example The same method as in Example 1 except that the pressure difference between the glass ribbon cutting space and the ear cutting space is -5 Pa (that is, the pressure in the glass ribbon cutting space is lower than the pressure in the ear cutting space).
  • the glass substrate for liquid crystal display was manufactured.
  • Table 1 below shows the evaluation results when the deterioration evaluation of the surface quality of the glass plate was obtained for Examples 1 to 5 and Comparative Example.
  • the air pressure between the glass ribbon cutting space and the furnace internal space is prevented in order to prevent an upward air flow from the glass ribbon cutting space toward the furnace internal space along the glass ribbon. Control was performed so that the difference was constant.
  • Table 2 below shows the results of breakage evaluation during transportation of the glass plates in Examples 1 to 5.
  • cooling roller 340 Cooling units 350a to 350h Conveying rollers 355, 360a, 360b, 360c, 415, 416, 417a, 417b, 417 c, 418, 419 Pressure sensor 400 Cutting device 411, 412, 413a, 413b, 413c, 414 Floor surface 421, 422, 423a, 423b, 423c, 424, 425 Blower 500 Ear cutting device 600 Control device 610 Drive unit

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PCT/JP2012/006175 2011-09-29 2012-09-27 ガラス板の製造方法及びガラス板製造装置 WO2013046683A1 (ja)

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US8707737B2 (en) 2009-11-30 2014-04-29 Corning Incorporated Method and apparatus for pressure control of glass-making thickness-control zone
WO2014168149A1 (ja) * 2013-04-10 2014-10-16 日本電気硝子株式会社 保持部付ガラス基板、ガラス基板の熱処理方法、及びガラス基板支持ユニット
JP2019510724A (ja) * 2016-04-06 2019-04-18 コーニング インコーポレイテッド ガラスリボンの生産方法
WO2021070588A1 (ja) * 2019-10-09 2021-04-15 日本電気硝子株式会社 ガラス板の製造方法及びその製造装置
CN114364608A (zh) * 2019-12-10 2022-04-15 日本电气硝子株式会社 玻璃板的制造方法

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WO2016100417A1 (en) * 2014-12-19 2016-06-23 Corning Incorporated Apparatus for manufacturing a glass ribbon
JP6708968B2 (ja) * 2016-11-11 2020-06-10 日本電気硝子株式会社 板ガラス製造装置及び板ガラス製造方法
TW201904892A (zh) * 2017-06-14 2019-02-01 美商康寧公司 具有可動式端塊組件之玻璃成形設備
JPWO2021124801A1 (ko) * 2019-12-18 2021-06-24
WO2024049694A1 (en) * 2022-08-31 2024-03-07 Corning Incorporated Methods and apparatus for manufacturing a glass ribbon

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Cited By (9)

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Publication number Priority date Publication date Assignee Title
US8707737B2 (en) 2009-11-30 2014-04-29 Corning Incorporated Method and apparatus for pressure control of glass-making thickness-control zone
US9296635B2 (en) 2009-11-30 2016-03-29 Corning Incorporated Method and apparatus for pressure control of glass-making thickness-control zone
WO2014168149A1 (ja) * 2013-04-10 2014-10-16 日本電気硝子株式会社 保持部付ガラス基板、ガラス基板の熱処理方法、及びガラス基板支持ユニット
JP2014205579A (ja) * 2013-04-10 2014-10-30 日本電気硝子株式会社 保持部付ガラス基板、ガラス基板の熱処理方法、及びガラス基板支持ユニット
JP2019510724A (ja) * 2016-04-06 2019-04-18 コーニング インコーポレイテッド ガラスリボンの生産方法
WO2021070588A1 (ja) * 2019-10-09 2021-04-15 日本電気硝子株式会社 ガラス板の製造方法及びその製造装置
JP2021059478A (ja) * 2019-10-09 2021-04-15 日本電気硝子株式会社 ガラス板の製造方法及びその製造装置
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CN114364608A (zh) * 2019-12-10 2022-04-15 日本电气硝子株式会社 玻璃板的制造方法

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