WO2013001834A1 - ガラス板の製造方法及びガラス板の製造装置 - Google Patents

ガラス板の製造方法及びガラス板の製造装置 Download PDF

Info

Publication number
WO2013001834A1
WO2013001834A1 PCT/JP2012/004231 JP2012004231W WO2013001834A1 WO 2013001834 A1 WO2013001834 A1 WO 2013001834A1 JP 2012004231 W JP2012004231 W JP 2012004231W WO 2013001834 A1 WO2013001834 A1 WO 2013001834A1
Authority
WO
WIPO (PCT)
Prior art keywords
furnace
space
glass
atmospheric pressure
glass ribbon
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2012/004231
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
浩幸 苅谷
公彦 中嶋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Avanstrate Inc
Avanstrate Korea Inc
Avanstrate Asia Pte Ltd
Original Assignee
Avanstrate Inc
Avanstrate Korea Inc
Avanstrate Asia Pte Ltd
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
Publication date
Application filed by Avanstrate Inc, Avanstrate Korea Inc, Avanstrate Asia Pte Ltd filed Critical Avanstrate Inc
Priority to KR1020127034182A priority Critical patent/KR101442384B1/ko
Priority to JP2012530008A priority patent/JP5235249B1/ja
Priority to CN201280002970.4A priority patent/CN103108840B/zh
Priority to KR1020127020852A priority patent/KR101300934B1/ko
Publication of WO2013001834A1 publication Critical patent/WO2013001834A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • C03B18/04—Changing or regulating the dimensions of the molten glass ribbon
    • C03B18/06—Changing or regulating the dimensions of the molten glass ribbon using mechanical means, e.g. restrictor bars, edge rollers
    • 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
    • C03B18/18—Controlling or regulating the temperature of the float bath; Composition or purification of the float bath

Definitions

  • the present invention relates to a glass plate manufacturing method and a glass plate manufacturing apparatus by a downdraw method.
  • the overflow downdraw method includes a step of forming a glass ribbon below the formed body by allowing molten glass to overflow from the top of the formed body in a forming furnace, and a step of gradually cooling the glass ribbon in a slow cooling furnace. Including.
  • the slow cooling furnace draws the glass ribbon between the pair of rollers and stretches the glass ribbon to a desired thickness, and then slowly cools the glass ribbon so as to reduce distortion and thermal shrinkage inside the glass ribbon. Thereafter, the glass ribbon is cut into a predetermined size to form a glass plate, which is laminated on a bundle of glass plates, or conveyed to the next step.
  • the downdraw method it describes in the following patent document 1, for example.
  • a TFT Thin Film Transistor
  • the glass plate is heat-treated at a temperature of 400 ° C. to 600 ° C. in the display manufacturing process. There is a case. This minute change in dimensions may cause a displacement of the TFT formation position formed on the glass plate with respect to the target position (pixel position), and as a result, display defects of the liquid crystal display may occur.
  • a glass plate on which a TFT is formed and a glass plate on which a color filter is formed for each pixel are opposed to each other, and a liquid crystal is provided between the glass plates.
  • the glass plate on which the TFT is formed undergoes a minute dimensional change due to heat shrinkage, accurate alignment may not be possible in pixel units with the glass plate on which the color filter is formed. For this reason, in order to reduce the change of the dimension of a glass plate, it is calculated
  • Patent Document 2 in order to reduce the plane distortion of the glass plate, the pressure outside the furnace (space outside the furnace) of the forming furnace and / or the slow cooling furnace is pressurized and generated along the glass ribbon in the slow cooling furnace.
  • the technique which suppresses the temperature fluctuation in a slow cooling furnace by reducing the upward airflow to perform is disclosed.
  • the air in the furnace outer space may flow into the inner space of the forming furnace or the slow cooling furnace.
  • the temperature in the outer space of the furnace is about 200 to 1200 ° C. lower than the temperature in the furnace atmosphere (space inside the furnace) of the forming furnace or the slow cooling furnace.
  • an air flow that rises from a cooling chamber, a cutting chamber, or the like into the slow cooling furnace may occur, but even if an air flow occurs, the air flow remains in the slow cooling furnace. As the temperature rises, the effect on temperature fluctuations in the furnace interior space is small.
  • the temperature in the slow cooling furnace cannot be maintained at the set temperature, and the variation in thermal shrinkage of the glass plate may increase.
  • the glass plate is required to have a small variation in thermal shrinkage, for example, a glass plate for flat panel display (in particular, a glass substrate for liquid crystal display, a glass substrate for organic EL display, or an oxide semiconductor thin film transistor).
  • a glass plate for flat panel display in particular, a glass substrate for liquid crystal display, a glass substrate for organic EL display, or an oxide semiconductor thin film transistor.
  • an object of the present invention is to provide a method for producing a glass plate that efficiently reduces variation in thermal shrinkage when producing a glass plate by a downdraw method.
  • One aspect of the present invention is a method for producing a glass plate by a downdraw method, A melting step of 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 forming a flow of the glass ribbon; 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 cutting step of cutting the cooled glass ribbon in a cutting space.
  • the furnace The external space is a space partitioned by a partition with respect to the atmospheric pressure atmosphere, and the atmospheric pressure of at least a part of the furnace external space is relative to the atmospheric pressure of the furnace internal space at the same position in the flow direction of the glass ribbon.
  • the atmospheric pressure is adjusted to be low.
  • the atmospheric pressure in the outer space of the furnace is in a region between a position in the slow cooling furnace corresponding to the slow cooling point temperature of the glass ribbon and a position in the slow cooling furnace corresponding to the strain point temperature of the glass ribbon. It is preferable that the atmospheric pressure is adjusted so as to be lower than the atmospheric pressure at the same position in the furnace internal space.
  • the difference between the pressure in the furnace internal space and the pressure in the furnace external space is 40 Pa or less at the same position in the flow direction of the glass ribbon with respect to the pressure of the at least part of the furnace external space.
  • the pressure outside the furnace is adjusted to be higher than the atmospheric pressure.
  • the furnace outer space has an upper space located above the ceiling surface of the inner space of the molding furnace, and the upper space does not allow air to flow from the upper space into the furnace inner space. It is preferable that the air pressure in the upper space is adjusted.
  • the flow direction of the glass ribbon is a vertical direction, and the forming furnace is provided vertically above the slow cooling furnace.
  • the furnace external space is divided into a plurality of partial spaces in the vertical direction, and the difference between the respective atmospheric pressure of the partial space and the atmospheric pressure of the furnace internal space at the same position in the vertical direction of the partial space,
  • the atmospheric pressure is adjusted such that the difference at the uppermost portion is larger than the difference at the lowermost portion. It is preferable.
  • the difference in the atmospheric pressure in the partial space increases as it goes upward.
  • the glass plate is, for example, a glass substrate for liquid crystal display on which a TFT (Thin Film Transistor) is formed.
  • TFT Thin Film Transistor
  • the furnace When the outer space of the furnace includes a first partial space at the same position as the formed body in the flow direction of the glass ribbon, the furnace at the same position in the flow direction of the glass ribbon and the atmospheric pressure of the first partial space
  • the difference in atmospheric pressure in the internal space is preferably greater than 0 and 40 Pa or less.
  • the furnace external space includes a second partial space located at the same position as the slow cooling furnace in the flow direction of the glass ribbon, and the difference between the atmospheric pressure of the furnace internal space of the slow cooling furnace and the atmospheric pressure of the second partial space is 0 It is preferably 40 Pa or less.
  • the furnace external space includes a first partial space located at the same position as the formed body and a second partial space located at the same position as the slow cooling furnace in the flow direction of the glass ribbon, and the first partial space and the first When two partial spaces are separated by a wall and adjacent to each other, the atmospheric pressure in the first partial space of the furnace external space is larger than the atmospheric pressure in the second partial space, and the atmospheric pressure in the first partial space and the second It is preferable that the difference in the atmospheric pressure of the partial space is smaller than 20 Pa.
  • the furnace outer space includes a plurality of second partial spaces at the same position as the slow cooling furnace, and the plurality of second partial spaces have higher atmospheric pressure toward the upstream side in the flow direction of the molten glass. preferable.
  • the slow cooling step includes In the central part of the width direction of the glass ribbon, so that a tensile stress works in the flow direction of the glass ribbon, At least in a temperature range from a temperature obtained by adding 150 ° C. to the annealing point temperature of the glass ribbon to a temperature obtained by subtracting 200 ° C. from the strain point temperature of the glass ribbon,
  • the cooling rate of the central part in the width direction of the glass ribbon is faster than the cooling rate of the both end parts, It is preferable that the glass ribbon is changed from a state where the temperature of the central portion in the width direction of the glass ribbon is higher than the both end portions to a state where the temperature of the central portion is lower than the both end portions.
  • the slow cooling step includes a first cooling step, a second cooling step, and a third cooling step
  • the first cooling step is a step of cooling at the first average cooling rate until the temperature of the central portion in the width direction of the glass ribbon reaches the annealing point temperature
  • the second cooling step is a step of cooling at the second average cooling rate until the temperature of the central portion in the width direction of the glass ribbon reaches the strain point temperature of ⁇ 50 ° C. from the annealing point temperature
  • the third cooling step is a step of cooling at a third average cooling rate until the temperature of the central portion in the width direction of the glass ribbon becomes a strain point temperature of ⁇ 50 ° C. to a strain point temperature of ⁇ 200 ° C.
  • the first average cooling rate is 5.0 ° C./second or more, the first average cooling rate is faster than the third average cooling rate, and the third average cooling rate is the second It is preferable that the cooling rate is higher than the average cooling rate.
  • the average cooling rate of the central portion of the glass ribbon in the first cooling step is preferably 5.5 ° C./second to 50.0 ° C./second.
  • the average cooling rate of the glass ribbon in the second cooling step is preferably 0.5 to less than 5.5 ° C./second.
  • the cooling rate of the central portion of the glass ribbon in the third cooling step is preferably 1.5 ° C./second to 7.0 ° C./second.
  • the strain point temperature of the glass is preferably 675 ° C. or higher, and the strain point temperature is 675 ° C. to 750 ° C. More preferably, it is ° C.
  • Another embodiment of the present invention is a glass plate manufacturing apparatus using a downdraw method.
  • the manufacturing equipment A melting apparatus for melting glass raw material to obtain molten glass;
  • the molten glass is supplied to a molded body provided in a molding furnace to form a glass ribbon, the flow of the glass ribbon is created, and the glass ribbon is pulled by a roller provided in the slow cooling furnace, and the slow cooling furnace A molding device for cooling inside, And a cutting device for cutting the cooled glass ribbon in a cutting space.
  • the furnace When the internal space of the molding furnace provided with the molded body and the internal space of the slow cooling furnace provided with the roller are furnace internal spaces, and the external space of the molding furnace and the slow cooling furnace is a furnace external space, the furnace The external space is a space partitioned by a partition wall with respect to the atmospheric pressure atmosphere.
  • An air pressure control device for adjusting the air pressure is provided in the molding apparatus so that the air pressure in at least a part of the furnace outer space is lower than the air pressure in the furnace inner space at the same position in the flow direction of the glass ribbon. It has been.
  • the air pressure control device is a device that adjusts the inflow of air with the atmosphere in order to control the air pressure in the furnace outer space.
  • FIG. 2 is a diagram schematically showing an apparatus for performing a melting step to a cutting step according to the present embodiment. It is a schematic side view of the glass plate shaping
  • the center part of a glass ribbon means the center of the width direction of a glass ribbon among the widths of the width direction of a glass ribbon.
  • the edge part of a glass ribbon means the range within 100 mm from the edge of the width direction of a glass ribbon.
  • 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 a glass plate having a log ⁇ of 13.
  • FIG. 1 is a diagram showing a flow of a glass plate manufacturing method according to the present embodiment.
  • the glass plate manufacturing method includes a melting step (ST1), a clarification step (ST2), a homogenization step (ST3), a supply step (ST4), a forming step (ST5), and a slow cooling step (ST6). And a cutting step (ST7).
  • 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 a glass plate manufacturing apparatus that performs the melting step (ST1) to the cutting step (ST7).
  • the apparatus mainly includes a melting apparatus 200, a molding apparatus 300, and a cutting apparatus 400.
  • the dissolution apparatus 200 includes a dissolution 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.
  • the glass raw material supplied into the melting tank 201 is heated and melted with a flame and an electric heater (not shown) to obtain molten glass.
  • the clarification step (ST2) is performed in the clarification tank 202, and by heating the molten glass in the clarification tank 202, oxygen and SO 2 bubbles contained in the molten glass grow by the oxidation-reduction reaction of the clarifier. The bubble gas component is released by rising to the liquid surface, or the gas component in the bubble is absorbed into the molten glass and the bubble disappears.
  • 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 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.
  • molten glass is supplied to a formed body provided in a forming furnace to form a glass ribbon G (see FIG. 3).
  • an overflow down draw method using a molded body 310 described later is used.
  • the glass ribbon G that has been molded and flowed has a desired thickness, and is cooled by being pulled by a roller so as not to cause a plane distortion and a thermal contraction rate. .
  • the 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 cut glass plate G1 is further cut into a predetermined size to produce a glass plate G1 having a target size.
  • the glass end face is ground and polished, then cleaned, and further inspected for the presence of abnormal defects such as bubbles and striae, and then the glass plate G1 that has passed the inspection is packed as the final product. Is done.
  • 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 suitably used for a glass substrate for flat panel display or a cover glass, for example.
  • the glass substrate for a flat panel display include a glass substrate for a liquid crystal display, a glass substrate for an organic EL display, and a display glass on which an oxide semiconductor thin film transistor is formed.
  • the glass plate molded by the molding apparatus 300 can also be used as a display for a portable terminal device, a cover glass for a housing, a touch panel plate, a glass substrate of a solar cell, or a cover glass. Particularly, it is suitable for a glass substrate for a liquid crystal display using a polysilicon TFT.
  • 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.
  • a furnace inner space surrounded by the furnace wall of the furnace 30 a molded body 310, an atmosphere partition member 320, a cooling roller 330, a cooling unit 340, conveying rollers 350a to 350h, pressure sensors 355, 360a to 360c ( 4). As shown in FIG.
  • the molded body 310 forms molten glass flowing from the melting device 200 through the second pipe 205 into a glass ribbon G. Thereby, the flow of the glass ribbon G of the vertically lower direction is made in the forming apparatus 300.
  • the molded body 310 is a long and narrow structure made of refractory brick 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 groove 312 is connected to the second pipe 205 at a supply port 311 (see FIG. 4) provided in the molding apparatus 300.
  • the molten glass flowing through the second pipe 205 flows along the groove 312.
  • the depth of the groove 312 is shallower toward the downstream side of the flow of the molten glass, so that the molten glass overflows vertically downward from the groove 312. 3 and 4, the molten glass is represented by the reference symbol MG.
  • 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.
  • the glass ribbon G flows down toward the slow cooling furnace 50.
  • the viscosity of the glass ribbon G at the time of starting to flow down after leaving the molded body 310 is, for example, 10 5.7 to 10 7.5 poise.
  • 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 surface of the glass ribbon G in the vicinity of both ends in the width direction of the glass ribbon G, pulls the glass ribbon G downward, and sets the thickness of the glass ribbon G to a desired thickness in the vicinity of both ends. At the same time, the glass ribbon G is cooled (rapidly cooled). Due to the rapid cooling by the cooling roller 330, the viscosity at both ends of the glass ribbon becomes, for example, 10 9.0 to 10 10.5 poise.
  • the viscosity at both ends of the glass ribbon G is, for example, 10 10.5 to 10 14.5 poise due to cooling with a cooling function lower than the cooling function in the rapid cooling.
  • 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. By the cooling by the cooling unit 340, the warp of the glass ribbon G is suppressed.
  • 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.
  • Each of the transport rollers 350a to 350h has a pair of rollers and is provided at both end portions in the width direction of the glass ribbon G so as to sandwich both sides of the glass ribbon G.
  • a pressure sensor 355 for measuring the pressure inside 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 upward direction of the drawing in FIGS. 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 360a to 360c are provided in the furnace internal space of the slow cooling furnace 50.
  • furnace exterior spaces S1, S2, S3a to S3c are provided outside the furnace wall of the forming furnace 40.
  • the furnace outer space S ⁇ b> 1 is an upper space located further above the ceiling surface of the inner space of the molding furnace 40.
  • Each of these spaces is delimited by floor surfaces (floor walls) 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 (cutting space) partitioned by walls on the floor 414 is provided below the furnace external space S3c.
  • the air pressure in these spaces is adjusted by blowers 421, 422, 423a, 423b, 423c, and 424, 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 internal space is provided at the same position in the height direction of the pressure sensor 416 (see FIG. 4).
  • 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 internal space are provided at the same position in the height direction of the pressure sensors 417a to 417c (see FIG. 4).
  • 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. .
  • the fans 421, 422, 423a, 423b, 423c, and 424 are provided outside the partition walls separating the furnace outside spaces S1, S2, S3a to S3c and the space S4.
  • Air sent from the atmosphere by the blowers 421, 422, 423a, 423b, 423c, and 424 is supplied to each of the furnace external spaces S1, S2, S3a to S3c, and the space S4 through a pipe.
  • the amount of air sent by the blowers 421, 422, 423a, 423b, 423c, 424 is determined by a drive signal from the drive unit 510 described later.
  • the blowers 421, 422, 423a, 423b, 423c, and 424 are pressure control that adjusts the inflow of air to the atmosphere in order to control the respective air pressures in the furnace exterior spaces S1, S2, S3a to S3c, and the space S4 Functions as a device.
  • FIG. 5 is a schematic diagram of a control system that controls the amount of air that the blowers 421, 422, 423a, 423b, 423c, and 424 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 provided in the furnace external space, the control device 500, and the drive unit 510. And blowers 421, 422, 423a, 423b, 423c, and 424.
  • the control device 500 includes a measurement result of the atmospheric pressure in the furnace internal space sent from each of the pressure sensors 355, 360a to 360c, and a measurement result of the atmospheric pressure in the furnace external space sent from the pressure sensors 415, 416, 417a to 417c, 418.
  • the blowers 421, 422, 423a, 423b, 423c, 424 are sent from the atmosphere so that the difference in atmospheric pressure at the same position in the height direction in the furnace inner space and the furnace outer space is adjusted to a set range.
  • a control signal for adjusting the amount of air is generated.
  • the generated control signal is sent to the drive unit 510.
  • the drive unit 510 generates a drive signal for individually adjusting the amount of air sent by the blowers 421, 422, 423a, 423b, 423c, and 424 based on the control signal.
  • the drive unit 510 sends drive signals to the fans 421, 422, 423a, 423b, 423c, and 424, respectively.
  • the control device 500 and the drive unit 510 automatically control the air feed amount, but the operator may adjust the air feed amount manually.
  • the amount of air sent from the fans 421, 422, 423a, 423b, 423c, 424 is such that the pressure in the furnace outer space S2, S3a to S3c is lower than the pressure in the furnace inner space at the same position in the height direction.
  • 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 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 S2, and the air rise in the furnace inner space is increased.
  • the difference between the atmospheric pressures is less than the above range, air may flow in from the gap between the furnace walls from the furnace outer space S2 toward the furnace inner space, and the temperature distribution in the furnace inner space varies.
  • 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. Particularly preferred is 10 to 20 Pa. If 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 air rise in the furnace inner space. .
  • the difference in the atmospheric pressure is less than the above range, air may flow in from the gaps in the furnace wall from the furnace outer space S3a to S3c 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 difference in atmospheric pressure between the furnace outer spaces S3a to S3c and the furnace inner space increases as it goes upward. It is considered that the temperature of the furnace internal space becomes higher as it goes upward, and the influence of the inflow of air at a temperature lower than that of the furnace internal space is increased.
  • the pressure difference between the furnace external space S3c and the space S4 is preferably 0 ⁇ (pressure in the furnace external space S3c ⁇ pressure in the space S4), and 0 ⁇ (pressure in the furnace external space S3c ⁇ pressure in the space S4).
  • Atmospheric pressure) ⁇ 20 Pa is more preferable, and 1 Pa ⁇ (atmospheric pressure in the furnace outer space S3c ⁇ atmospheric pressure in the space S4) ⁇ 15 Pa is further preferable, and 2Pa ⁇ (atmospheric pressure in the outer furnace space S3c ⁇ atmospheric pressure in the space S4). More preferably, it is ⁇ 15 Pa.
  • the pressure difference between the furnace outside lower space S2 and the furnace outside space S3a is preferably 0 ⁇ (the pressure in the furnace outside lower space S2 ⁇ the pressure in the furnace outside space S3a), and 0 ⁇ (the furnace outside space S2 More preferably, the atmospheric pressure—the atmospheric pressure of the furnace outer space S3a) ⁇ 20 Pa, and more preferably 1 Pa ⁇ (the atmospheric pressure of the outer furnace space S2—the atmospheric pressure of the outer furnace space S3a) ⁇ 15 Pa, more preferably 2 Pa ⁇ (the outer furnace space). It is more preferable that the pressure of S2 ⁇ the pressure of the furnace outer space S3a) ⁇ 15 Pa.
  • the pressure difference between the furnace outside space S1 and the furnace outside space S2 is preferably 0 ⁇ (atmosphere pressure in the furnace outside space S1 ⁇ atmospheric pressure in the furnace outside space S2), and 0 ⁇ (atmospheric pressure in the furnace outside space S1 ⁇ It is more preferable that the pressure in the furnace outer space S2) ⁇ 30 Pa, and it is more preferable that 1 Pa ⁇ (the pressure in the furnace outer space S1 ⁇ the pressure in the furnace outer space S2) ⁇ 25 Pa, more preferably 2 Pa ⁇ (in the furnace outer space S1). More preferably, the pressure is equal to the atmospheric pressure of the furnace outer space S2.
  • the furnace outside space S1 If the pressure difference between the furnace outside space S3c and the space S4, the pressure difference between the furnace outside space S2 and the furnace outside space S3a, and the pressure difference between the furnace outside space S1 and the furnace outside space S2 are too large, the furnace outside space S1
  • the absolute values of the atmospheric pressure in the furnace outer space S2 and the furnace outer spaces S3a to S3c become too large, and air flows from the furnace outer space into the furnace inner space. For this reason, there exists a possibility that the problem that the temperature in a furnace interior space may fluctuate arises. Furthermore, there is a possibility that the local airflow concentration in the external space of the furnace or the flow velocity of the airflow is locally increased, and the atmospheric pressure stability of the external space of the furnace may be lowered. There is also a possibility that the problem that the temperature varies will occur.
  • 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 air from the external space of the furnace Inflow can be suppressed, and variations in temperature in this region can be suppressed, and warpage of the glass ribbon G can be prevented by this suppression.
  • the glass ribbon G is one continuous plate until it is cut from the molding furnace 40. Therefore, if the warp shape of the glass ribbon G changes in a region where the temperature of the glass ribbon G is equal to or lower than the strain point temperature, it also affects the glass ribbon in the region where the temperature is higher than the strain point temperature, resulting in variations in plane strain and thermal shrinkage. Will occur. As described above, that is, by suppressing variations in temperature in the region where the temperature of the glass ribbon G is equal to or lower than the strain point temperature, variations in warpage, plane strain, and thermal shrinkage can be suppressed.
  • 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. It is preferable to measure the atmospheric pressure.
  • the space of the forming furnace 40 in the furnace internal space is located at the most upstream position in the furnace internal space, and the atmospheric pressure is high and the temperature in the space is also high. It is not preferable that air flows out from the ceiling surface of the internal space of the forming furnace 40 to the external space S1 because the flow of air in the internal space of the furnace is promoted by the chimney effect. Therefore, in order to prevent the outflow of air to the furnace exterior space S1, the atmospheric pressure in the furnace exterior space S1 is increased. However, if the atmospheric pressure in the furnace external space S1 is excessively increased, air tends to easily flow from the furnace external space S1 into the furnace internal space.
  • the cold air flowing from the furnace outer space S1 is not preferable because it forms the glass ribbon with the molded body 310 in the space of the molding furnace 40 and affects the viscosity of the molten glass being molded. It also affects the cooling of the glass ribbon in the slow cooling step.
  • the pressure sensor 415 measures the atmospheric pressure in the furnace external space S1 in order to adjust the furnace external space S1 by the blower 421 so that air does not flow into the furnace internal space from the furnace external space S1. That is, on the ceiling surface of the molding furnace 40 in which no cooling roller or conveyance roller is provided, the pressure in the molding furnace external space S1 is set so that air does not flow from the gap between the ceiling surfaces into the furnace internal space from the furnace external space S1. It is preferably adjusted by the blower 421.
  • the pressure sensor 418 is used for measuring the atmospheric pressure in the space S4.
  • 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.
  • the pressure in the space S4 is adjusted to be equal to or higher than the atmospheric pressure.
  • the atmospheric pressure in the space S4 is adjusted to be equal to or higher than atmospheric pressure and lower than a predetermined pressure.
  • the pressure in the space S4 is adjusted to be equal to or higher than the atmospheric pressure and equal to or lower than the lowest pressure in the furnace internal space (the lowest pressure in the furnace internal space).
  • the pressure in the space S4 is preferably 0 ⁇ (the pressure in the space S4 ⁇ the atmospheric pressure), more preferably 0 ⁇ (the pressure in the space S4 ⁇ the atmospheric pressure) ⁇ 40 Pa, more preferably 5Pa ⁇ (the space S4 (Atmospheric pressure ⁇ atmospheric pressure) ⁇ 40 Pa is more preferable.
  • the air blowers 421, 422, 423a, 423b, 423c, 424 are adjusted so that the air pressure in any space is higher than the atmospheric pressure by sending air into the furnace outer spaces S1, S2, S3a to S3c and the space S4.
  • increasing the atmospheric pressure of these spaces with respect to the atmospheric pressure prevents a large amount of air from flowing from the outside of the building B into the outside space S1, S2, S3a to S3c and the space S4.
  • This is for efficiently adjusting the atmospheric pressure in the spaces S1, S2, S3a to S3c, S4.
  • the atmospheric pressure in the furnace internal space becomes higher as the position in the height direction is higher. This is due to the fact that the air that has reached a high temperature moves upward in an ascending current.
  • the atmospheric pressure in the external space of the furnace is adjusted according to the atmospheric pressure distribution. This is to suppress the flow of air into the furnace internal space due to the difference between the pressure in the furnace external space and the pressure in the furnace internal space, and to suppress the occurrence of air convection due to air leakage into the furnace external space. It is. For this reason, 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 is so high that the position of the height direction is high, ie, the upstream position of the flow direction of a glass ribbon.
  • produces along a furnace wall can be reduced in a furnace exterior space.
  • the cooling rate at the center in the width direction of the glass ribbon is faster than the cooling rate at both ends of the glass ribbon, and the temperature at the center in the width direction of the glass ribbon is higher than both ends of the glass ribbon. It is preferable to change the glass ribbon from a higher state to a state where the temperature at the center is lower than both ends. Thereby, a tensile stress can work in the flow direction of the glass ribbon at the center in the width direction of the glass ribbon. By applying a tensile stress in the flow direction of the glass ribbon, it is possible to further suppress the warpage of the glass ribbon, and thus the glass plate.
  • the slow cooling step can include a first cooling step, a second cooling step, and a third cooling step.
  • the first cooling step is a step of cooling at the first average cooling rate until the temperature of the central portion in the width direction of the glass ribbon reaches the annealing point temperature.
  • the second cooling step is a step of cooling at the second average cooling rate until the temperature of the central portion in the width direction of the glass ribbon reaches the strain point temperature of ⁇ 50 ° C. from the annealing point temperature.
  • the third cooling step is a step of cooling at the third average cooling rate until the temperature of the central portion in the width direction of the glass ribbon changes from the strain point temperature of ⁇ 50 ° C. to the strain point temperature of ⁇ 200 ° C.
  • the first average cooling rate is 5 ° C./second or more
  • the first average cooling rate is faster than the third average cooling rate
  • the third average cooling rate is the second average cooling rate. It is preferable to make it faster. That is, the average cooling rate is, in descending order, the first average cooling rate, the third average cooling rate, and the second average cooling rate.
  • the average cooling rate of the central portion of the glass ribbon in the first cooling step is preferably 5.5 ° C./second to 50 ° C./second. If the average cooling rate at the central portion of the glass ribbon in the first cooling step is less than 5.5 ° C./second, the productivity is lowered.
  • the average cooling rate at the center of the glass ribbon in the first cooling step is more preferably 8 ° C./second to 16.5 ° C./second.
  • the average cooling rate of the glass ribbon in the second cooling step is preferably 0.5 to 5.5 ° C./second.
  • the average cooling rate at the center of the glass ribbon in the second cooling step is more preferably 0.5 ° C./second to 5.5 ° C./second.
  • the cooling rate of the central portion of the glass ribbon in the third cooling step is not particularly limited, but is preferably 1.5 ° C./second to 7 ° C./second. If the cooling rate of the central part of the glass ribbon in the third cooling step is less than 1.5 ° C./second, the productivity is lowered. On the other hand, at 7 ° C./second or more, the glass ribbon may be cracked due to excessive quenching of the glass ribbon.
  • the cooling rate of the central portion of the glass ribbon in the third cooling step is preferably 1.5 ° C./second to 7 ° C./second, more preferably 2 ° C./second to 5.5 ° C./second. It is.
  • the cooling rate in the flow direction of the glass ribbon affects the heat shrinkage of the glass plate to be manufactured.
  • the slow cooling step by setting the cooling rate, it is possible to obtain a glass plate having a suitable heat shrinkage rate while improving the production amount of the glass plate.
  • Such a cooling rate is performed by controlling the temperature using a heater (not shown) provided in the furnace internal space.
  • a thermal contraction rate can also be made small by providing a thermal contraction reduction process (offline annealing) process separately after a slow cooling process.
  • the slow cooling process preferably includes a heat shrinkage reduction process.
  • the said 2nd cooling process corresponds to a thermal contraction reduction process process among slow cooling processes.
  • Glass plate As the glass used for the glass plate of the present embodiment, for example, borosilicate glass, aluminosilicate glass, aluminoborosilicate glass, soda lime glass, alkali silicate glass, alkali aluminosilicate glass, alkali aluminogermanate glass, etc. can be applied. it can.
  • the glass applicable to the present invention is not limited to the above.
  • Glass composition 1 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 40 to 70%, Al 2 O 3 : 2 to 25%, B 2 O 3 : 0 to 20%, MgO: 0 to 10%, CaO: 0 to 15%, SrO: 0 to 10%, BaO: 0 to 15%, ZnO: 0 to 10%, ZrO 2 : 0 to 10%, Refiner: 0-2%, It is an alkali-free glass.
  • Glass composition 2 (Glass composition 2) Moreover, the alkali free glass of the following composition is also illustrated.
  • the indications in parentheses below are the preferred contents of each component, and the ones described later are more preferred.
  • SiO 2 50 to 70% (55 to 65%, 57 to 64%, 58 to 62%), Al 2 O 3 : 2 to 25% (10 to 20%, 12 to 18%, 15 to 18%), B 2 O 3 : 0 to 20% (5 to 15%, 6 to 13%, 7 to 12%).
  • the following components may be included as optional components.
  • MgO 0 to 10% (lower limit is 0.01%, lower limit is 0.5%, upper limit is 5%, upper limit is 4%, upper limit is 2%), CaO: 0 to 20% (lower limit is 1%, lower limit is 3%, lower limit is 4%, upper limit is 9%, upper limit is 8%, Upper limit is 7%, upper limit is 6%), SrO: 0 to 20% (lower limit is 0.5%, lower limit is 3%, upper limit is 9%, upper limit is 8%, upper limit is 7 %%, upper limit is 6%), BaO: 0 to 10% (upper limit is 8%, upper limit is 3%, upper limit is 1%, upper limit is 0.2%), ZrO 2 : 0 to 10% (0 to 5%, 0 to 4%, 0 to 1%, 0 to 0.1%).
  • Glass composition 3 SiO 2 : 50 to 70%, B 2 O 3 : 5 to 18%, Al 2 O 3 : 0 to 25%, MgO: 0 to 10%, CaO: 0-20%, SrO: 0 to 20%, BaO: 0 to 10%, RO: 5 to 20% (where R is at least one selected from Mg, Ca, Sr and Ba, and the glass plate contains), It is preferable to contain. Furthermore, 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. Further, it is preferable that the total amount of fining agents is 0.05 to 1.5% and substantially free of As 2 O 3 , Sb 2 O 3 and PbO. More preferably, the iron oxide content in the glass is 0.01 to 0.2%.
  • Glass composition 4 examples of the glass composition of the other glass plate used in the present embodiment include the following.
  • the strain point temperature can be increased, and the thermal contraction of the glass plate can be further reduced.
  • the glass plate of the following composition is suitable for the glass substrate for liquid crystal displays and the glass substrate for organic EL displays, and is especially suitable for the glass substrate to which a polysilicon TFT is applied.
  • the content rate display of the composition shown below is mass%.
  • the indications in parentheses below are the preferred contents of each component, and the ones described later are more preferred.
  • SiO 2 57 to 75%, Al 2 O 3 : 8 to 25%, B 2 O 3 : 3 to less than 11%, CaO: 0-20%, MgO: 0 to 15%, Non-alkali glass.
  • 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. Further, it is preferable that the total amount of fining agents is 0.05 to 1.5% and substantially free of As 2 O 3 , Sb 2 O 3 and PbO.
  • the content of iron oxide in the glass is more preferably 0.01 to 0.2% from the viewpoint of reducing the specific resistance.
  • Glass composition 5 Glass composition 5
  • the glass plate applied to the cover glass or the glass plate for solar cell after chemical strengthening include those in which the glass plate is in mass% and contains the following components.
  • SiO 2 50 to 70% (55 to 65%, 57 to 64%, 57 to 62%), Al 2 O 3 : 5 to 20% (9 to 18%, 12 to 17%), Na 2 O: 6-30% (7-20%, 8-18%, 10-15%).
  • the following composition may be included as an optional component.
  • MgO 0 to 10% (lower limit is 1%, lower limit is 2%, lower limit is 3%, lower limit is 4%, upper limit is 9%, upper limit is 8%, upper limit is 7%), CaO: 0 to 20% (lower limit is 0.1%, lower limit is 1%, lower limit is 2%, upper limit is 10%, upper limit is 5%, upper limit is 4%, upper limit is 3%), ZrO 2 : 0 to 10% (0 to 5%, 0 to 4%, 0 to 1%, 0 to 0.1%).
  • a glass plate having a glass strain point temperature of 675 ° C. or higher (strain point temperature of 675 ° C. to 750 ° C.) is preferable, and a strain point temperature of 680 ° C. or higher (strain point temperature of 680 ° C.).
  • a glass plate having a strain point temperature of 690 ° C. or higher (a strain point temperature of 690 ° C. to 750 ° C.) is particularly preferable.
  • a glass plate is a mass% display and includes the following components.
  • the total content of SrO and BaO is less than 8% by mass in terms of reducing weight and reducing the thermal expansion coefficient.
  • the total content of SrO and BaO is preferably 0 to 7%, more preferably 0 to 5%, still more preferably 0 to 3%, still more preferably 0 to 1%.
  • the mass ratio (SiO 2 + Al 2 O 3 ) / RO is preferably 7.5 or more.
  • the ⁇ -OH value is preferably set to 0.1 to 0.3 [mm ⁇ 1 ].
  • the glass plate is made of R 2 O (where R 2 O is Li 2 O, Na 2 O and K 2 O).
  • the total amount of all components contained in the glass plate is preferably 0.01 to 0.8% by mass from the viewpoint of reducing the specific resistance of the glass.
  • the glass plate preferably has a CaO / RO of 0.65 or more in order to prevent an increase in the devitrification temperature while realizing a high strain point temperature. By setting the devitrification temperature to 1250 ° C. or lower, the overflow downdraw method can be applied.
  • the total content of SrO and BaO is preferably 0% or more and less than 2% from the viewpoint of weight reduction.
  • SiO 2 is a component constituting the glass skeleton of the glass plate, and has the effect of increasing the chemical durability and strain point temperature of the glass.
  • the content of SiO 2 is too low, the effects of chemical durability and heat resistance cannot be obtained sufficiently.
  • the strain point temperature decreases and the thermal expansion coefficient increases, the thermal contraction rate increases. If the content of SiO 2 is too high, the glass tends to be devitrified, making molding difficult, and increasing the viscosity, making it difficult to homogenize the glass. Moreover, since the specific resistance of glass is increased, melting becomes difficult.
  • Al 2 O 3 is a component forming a glass skeleton, and has an effect of increasing the chemical durability and strain point temperature of the glass. It also has the effect of increasing the etching rate. When the content of Al 2 O 3 is too low, the effects of chemical durability and heat resistance of the glass cannot be obtained sufficiently. In addition, the strain point temperature and Young's modulus are reduced. On the other hand, when the content ratio of Al 2 O 3 is too high, the viscosity of the glass increases to make it difficult to dissolve, and the acid resistance decreases. Moreover, since the specific resistance of glass is increased, melting becomes difficult.
  • B 2 O 3 is a component that lowers the viscosity of the glass and promotes melting and clarification of the glass. If the content of B 2 O 3 is too low, melting becomes difficult, and the acid resistance of the glass decreases. Moreover, devitrification resistance falls and a thermal expansion coefficient increases. On the other hand, if the content of B 2 O 3 is too high, the strain point temperature is lowered, so that the heat resistance is lowered. In addition, Young's modulus decreases. Moreover, due to the volatilization of B 2 O 3 during glass melting, glass non-uniformity becomes prominent and striae are likely to occur.
  • MgO and CaO are components that lower the viscosity of the glass and promote glass melting and fining. Further, Mg and Ca are advantageous components for improving the meltability while reducing the weight of the obtained glass because the ratio of increasing the density of the glass is small in the alkaline earth metal. However, if the content of MgO and CaO becomes too high, the strain point temperature is lowered. Furthermore, the chemical durability of the glass is reduced. CaO is an effective component for reducing the specific resistance and improving the meltability of the glass without rapidly increasing the devitrification temperature of the glass. Therefore, it is preferable to contain in the glass of high strain point temperature. Moreover, since MgO raises the devitrification temperature of glass, when reducing a devitrification temperature, it is preferable not to contain substantially.
  • SrO and BaO are components that lower the viscosity of the glass and promote glass melting and fining. Moreover, it is also a component which improves the oxidizability of a glass raw material and improves clarity. However, if the content of SrO and BaO becomes too high, the density of the glass increases, the weight of the glass plate cannot be reduced, and the chemical durability of the glass decreases.
  • BaO is preferably not substantially contained. In the present specification, “substantially free of BaO” means less than 0.01% by mass and is not intentionally contained except for impurities.
  • Li 2 O, Na 2 O, and K 2 O are components that reduce the viscosity of the glass and improve the meltability and moldability of the glass.
  • Li 2 O, Na 2 O and K 2 O content is too low it reduces the melting properties of the glass, the higher the cost for the melting.
  • the content of Li 2 O, Na 2 O, or K 2 O becomes too high, devitrification resistance decreases due to deterioration of the glass balance.
  • Li 2 O, Na 2 O, and K 2 O are components that may be eluted from the glass to deteriorate the TFT characteristics, and may increase the thermal expansion coefficient of the glass and damage the substrate during heat treatment. Therefore, when applied as a glass substrate for a liquid crystal display or a glass substrate for an organic EL display, it is preferably substantially not contained. However, by deliberately containing the above-mentioned components in the glass, the basicity of the glass is increased while the deterioration of the TFT characteristics and the thermal expansion of the glass are suppressed within a certain range, and the oxidation of the metal whose valence fluctuates. It is possible to make clear and exhibit clarity.
  • 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, without Na 2 O is allowed to contain, 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%.
  • ZrO 2 is a component that increases the viscosity near the devitrification temperature of glass and the strain point temperature. ZrO 2 is also a component that improves the heat resistance of the glass. However, if the content of ZrO 2 becomes too high, the devitrification temperature increases and the devitrification resistance decreases.
  • TiO 2 is a component that lowers the high temperature viscosity of the glass. However, when the content of TiO 2 becomes too high, the devitrification resistance is lowered. Furthermore, since the glass is colored, application to a cover glass of a display screen of an electronic device is not preferable. Further, since the glass is colored, the ultraviolet transmittance is reduced, and therefore, when the treatment using the ultraviolet curable resin is performed, there is a disadvantage that the ultraviolet curable resin cannot be sufficiently cured.
  • a clarifier can be added as a component for defoaming bubbles in the glass.
  • the fining agent is not particularly limited as long as it has a small environmental burden and excellent glass fining properties.
  • a metal oxide such as tin oxide, iron oxide, cerium oxide, terbium oxide, molybdenum oxide and tungsten oxide. There may be mentioned at least one selected.
  • Sb 2 O 3 and PbO are substances having an effect of clarifying the glass by causing a reaction with valence fluctuation in the molten glass, but As 2 O 3 , Sb 2 O 3 and Since PbO is a substance having a large environmental load, it is preferable that PbO is not substantially contained.
  • substantially not containing As 2 O 3 , Sb 2 O 3 and PbO means less than 0.01% by mass and intentionally not containing impurities.
  • the thickness of the glass plate of this embodiment is, for example, 0.1 mm to 1.5 mm.
  • the thickness is preferably 0.1 to 1.2 mm, more preferably 0.3 to 1.0 mm, even more preferably 0.3 to 0.8 mm, and particularly preferably 0.3 to 0.5 mm.
  • the thinner the glass plate the smaller the amount of heat held by the glass, making it difficult to control the glass temperature distribution in the forming furnace 40 and the slow cooling furnace 50. Therefore, a glass plate having a thickness of 0.5 mm or less is applied to the method of the present embodiment, which can stabilize the temperature of the furnace internal space, so that the glass plate is deformed, warped, and variations in plane distortion and heat shrinkage. This has a great effect of suppressing the variation of the image.
  • the length in the width direction of the glass plate of the present embodiment is, for example, 500 mm to 3500 mm, preferably 1000 mm to 3500 mm, and more preferably 2000 mm to 3500 mm.
  • the length of the glass plate in the vertical direction is, for example, 500 mm to 3500 mm, preferably 1000 mm to 3500 mm, and more preferably 2000 mm to 3500 mm.
  • a glass manufacturing apparatus will also be enlarged corresponding to the magnitude
  • the furnace internal space is widened, and when low-temperature air flows from the furnace external space into the furnace internal space, the influence on the cooling of the glass ribbon G differs in the width direction of the glass ribbon G. Accordingly, the region corresponding to the annealing point temperature to the strain point temperature of the glass ribbon G varies in the width direction of the glass ribbon G, and the time for the glass ribbon G to pass the annealing point temperature to the strain point temperature may vary. . As a result, the thermal contraction of the glass ribbon G also varies in the width direction.
  • the effect of the present embodiment that is, the effect of suppressing the deformation, warpage, plane distortion variation, and thermal shrinkage variation of the glass plate is increased. Furthermore, the effect of this embodiment becomes remarkable, so that the length of the glass plate in the width direction is 2500 mm or more and 3000 mm or more.
  • the thermal shrinkage rate when left in a temperature atmosphere at 550 ° C. for 2 hours is 110 ppm or less, 80 ppm or less, 50 ppm or less, preferably 40 ppm or less, more preferably 35 ppm or less. Yes, more preferably 30 ppm or less, particularly preferably 20 ppm or less.
  • the heat shrinkage rate is calculated by heat shrinkage / initial length ⁇ 10 6 (ppm). The following methods are exemplified as a method for measuring the heat shrinkage rate. 1.
  • the glass plate is cut in half in a direction perpendicular to the marking line, and one of them is heat-treated (in the above, 550 ° C. for 2 hours). 3. The glass plate after the heat treatment and the other glass plate are put together to measure the amount of deviation of the marking line.
  • the variation in the heat shrinkage rate is more likely to cause a display defect in the display panel than when the heat shrinkage rate is high or low, particularly when a TFT is formed on a glass plate in the production of a display. In this respect, it is important to suppress variations in the heat shrinkage rate. In addition, it is preferable that the dispersion
  • the variation in the heat shrinkage rate means that when the heat shrinkage rate is measured by the above method at three positions in the width direction of the glass plate (for example, the position of the central portion and the position in the vicinity of both end portions in the width direction).
  • the variation in thermal shrinkage of the glass plate is preferably ⁇ 3.0% or less, more preferably ⁇ 2.85% or less, still more preferably ⁇ 2.7% or less, and further preferably ⁇ 2.65% or less. .
  • the variation in the thermal shrinkage rate is preferably ⁇ 3.0% or less.
  • it is ⁇ 2.8% or less, more preferably ⁇ 2.7% or less, and further preferably ⁇ 2.6% or less.
  • high strain point glass refers to glass having a strain point temperature of 680 ° C. or higher.
  • the maximum value (flat value of retardation value) of the plane distortion of a glass plate is 1.7 nm or less.
  • it is 1.3 nm or less, More preferably, it is 1.0 nm or less, More preferably, it is 0.7 nm or less.
  • the plane strain is measured by, for example, a birefringence measuring device manufactured by UNIOPT.
  • the method of the present embodiment capable of reducing the plane distortion of the glass plate is particularly preferably used for manufacturing a glass substrate for a liquid crystal display.
  • the warpage of the glass plate when measured by the following method, has a maximum warpage in the range of 0 to 0.2 mm, preferably 0 to 0.15 mm, more preferably 0 to 0.1 mm. Or less, more preferably 0 to 0.05 mm or less, and particularly preferably 0 to 0.05 mm or less.
  • the measurement of warpage is 1. First, a plurality of small plates (about 400 mm square plates) are cut out from a glass plate. 2. Next, for each of the small plates, the warpage of the four corners and the four central portions is measured on each of the front and back sides (that is, a total of 16 warpages are measured).
  • the glass plate is manufactured by variously changing the manufacturing method of the glass plate, and further heat treatment is performed under the same conditions as when the liquid crystal display is manufactured, and the heat shrinkage rate is obtained by the method described above In addition, the plane strain was measured, and the variation of the thermal shrinkage rate was obtained.
  • Example 1 In the inner space of the furnace, the pressure difference between the region where the temperature of the glass ribbon G is the annealing point temperature to the strain point temperature and the outer space corresponding to the same position in the height direction of this region is 5 Pa (in detail) Was adjusted to 3 to 7 Pa).
  • 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% SrO 5% SnO 2 0.5%
  • Example 2 As in Example 1, the pressure difference between the region in the furnace internal space where the temperature of the glass ribbon G is between the annealing point temperature and the strain point temperature and the space outside the furnace corresponding to the height position of this region is The pressure in the external space of the furnace was adjusted so as to be 5 Pa (specifically, 3 to 7 Pa).
  • glass composition is as follows (a content rate is a mass% display).
  • size of a glass plate is 1100 mm x 1300 mm. This glass plate is used as a glass substrate for a liquid crystal display for forming a polysilicon TFT. SiO 2 66% Al 2 O 3 17.5% B 2 O 3 7.5% CaO 8.5% SnO 2 0.5%
  • Example 3 In the inner space of the furnace, the pressure difference between the region where the temperature of the glass ribbon G is the annealing point temperature to the strain point temperature and the outer space of the furnace corresponding to the height position of this region is 20 Pa (specifically, 18 to A glass substrate for a liquid crystal display was produced in the same manner as in Example 1 except that the pressure was 22 Pa).
  • Example 4 In the inner space of the furnace, the pressure difference between the region where the temperature of the glass ribbon G is the annealing point temperature to the strain point temperature and the outer space of the furnace corresponding to the height position of this region is 20 Pa (specifically, 18 to The glass substrate for liquid crystal display which forms a polysilicon TFT was manufactured by the method similar to Example 2 except being 22Pa).
  • Example 5 In the interior space of the furnace, the pressure difference between the region where the temperature of the glass ribbon G is the annealing point temperature to the strain point temperature and the space outside the furnace corresponding to the height position of this region is 35 Pa (specifically 33 to A glass substrate for a liquid crystal display was produced in the same manner as in Example 1 except that the pressure was 37 Pa).
  • Example 6 In the interior space of the furnace, the pressure difference between the region where the temperature of the glass ribbon G is the annealing point temperature to the strain point temperature and the space outside the furnace corresponding to the height position of this region is 35 Pa (specifically 33 to The glass substrate for liquid crystal display which forms a polysilicon TFT by the method similar to Example 2 except having been 37 Pa) was manufactured.
  • Example 7 In the inner space of the furnace, the pressure difference between the region where the temperature of the glass ribbon G is the annealing point temperature to the strain point temperature and the outer space of the furnace corresponding to the height position of this region is 60 Pa (specifically 55 to A glass substrate for a liquid crystal display was produced in the same manner as in Example 1 except that the pressure was 65 Pa).
  • Table 1 below shows the evaluation results of Examples 1 to 7 and Comparative Example.
  • the molten glass was supplied to the forming apparatus 200, and a glass plate was produced by the overflow down draw method. Thereafter, the glass plate was cut to produce a glass plate having a longitudinal direction of 1100 mm, a width direction of 1300 mm, and a thickness of 0.5 mm.
  • the atmospheric pressure in the furnace outer space was controlled to be higher toward the upstream side as shown in Table 2 below.
  • the content rate of each component contained in a molten glass is as follows.
  • the maximum strain (maximum value of retardation) of the glass plates produced in Examples 8 to 12 was 1.6 nm or less. Moreover, the curvature of the glass plate was 0.18 mm or less. In particular, the maximum strain (maximum retardation value) of the glass plates produced in Examples 9 to 11 was 1.0 nm or less. Moreover, the curvature of the glass plate was 0.15 mm or less.
  • Example 8 to 12 the furnace external spaces S3a and S3b shown in FIG. 3 were connected to control the atmospheric pressure as one space. At that time, the pressure difference between the region where the temperature of the glass ribbon G is the annealing point temperature to the strain point temperature and the furnace external space S3a, S3b corresponding to the height position of this region is 10 to 20 Pa. The pressure in the space outside the furnace was adjusted. The air pressure in the furnace external space S3c was adjusted so that the difference between the air pressure in the furnace external space S3c and the pressure in the corresponding position in the furnace internal space was 5 Pa (specifically, 3 to 7 Pa). Table 2 below shows the conditions and evaluation results of Examples 8 to 12.
  • P1 Air pressure [Pa] in the upper space S1 outside the forming furnace
  • P2 Pressure in the furnace outer space S2 [Pa]
  • P3 Pressure in the furnace outer space S3a, S3b [Pa]
  • P4 Pressure in space S4 [Pa]
  • (Disclosure 1) A method for producing a glass plate by a downdraw method, A melting step of 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 forming a flow of the glass ribbon; 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; Cutting the cooled glass ribbon in a cutting space, and
  • the internal space of the molding furnace provided with the molded body and the internal space of the slow cooling furnace provided with the roller are furnace internal spaces, and the external space of the molding furnace and the slow cooling furnace is a furnace external space, the furnace The external space is a space partitioned by a partition with respect to the atmospheric pressure atmosphere, and the atmospheric pressure of at least a part of the furnace external space is relative to the atmospheric pressure of the furnace internal space at the same position in the flow direction of the glass ribbon.
  • a method for producing a glass plate wherein the atmospheric pressure is adjusted so as to be low.
  • the pressure in the outer space of the furnace is in the region between the position in the slow cooling furnace corresponding to the slow cooling point temperature of the glass ribbon and the position in the slow cooling furnace corresponding to the strain point temperature of the glass ribbon.
  • the furnace outer space has an upper space located above the ceiling surface of the inner space of the molding furnace, and the upper space does not allow air to flow from the upper space into the furnace inner space.
  • the flow direction of the glass ribbon is a vertical direction
  • the molding furnace is provided vertically above the slow cooling furnace
  • the furnace outer space is divided into a plurality of partial spaces in the vertical direction,
  • the difference between each atmospheric pressure in the partial space and the atmospheric pressure in the furnace internal space at the same position in the vertical direction of the partial space is compared between the uppermost partial space and the lowermost partial space.
  • the furnace outer space includes a second partial space located at the same position as the slow cooling furnace in the flow direction of the glass ribbon, and the difference between the atmospheric pressure of the furnace internal space of the slow cooling furnace and the atmospheric pressure of the second partial space is 0
  • the furnace external space includes a first partial space located at the same position as the formed body and a second partial space located at the same position as the slow cooling furnace in the flow direction of the glass ribbon, and the first partial space and the first When two partial spaces are separated by a wall and adjacent to each other, the atmospheric pressure in the first partial space of the furnace external space is larger than the atmospheric pressure in the second partial space, and the atmospheric pressure in the first partial space and the second
  • the furnace exterior space includes a plurality of second partial spaces at the same position as the slow cooling furnace, and the plurality of the second partial spaces have a higher atmospheric pressure toward the upstream side in the flow direction of the molten glass. 12.
  • the slow cooling step includes In the central part of the width direction of the glass ribbon, so that a tensile stress works in the flow direction of the glass ribbon, At least in a temperature range from a temperature obtained by adding 150 ° C. to the annealing point temperature of the glass ribbon to a temperature obtained by subtracting 200 ° C. from the strain point temperature of the glass ribbon, The cooling rate of the central part in the width direction of the glass ribbon is faster than the cooling rate of the both end parts, The disclosure 1 to 12, wherein the glass ribbon is changed from a state in which a temperature in a central portion in the width direction of the glass ribbon is higher than the both end portions to a state in which the temperature in the central portion is lower than the both end portions. Manufacturing method of glass plate.
  • the slow cooling step includes a first cooling step, a second cooling step, and a third cooling step
  • the first cooling step is a step of cooling at the first average cooling rate until the temperature of the central portion in the width direction of the glass ribbon reaches the annealing point temperature
  • the second cooling step is a step of cooling at the second average cooling rate until the temperature of the central portion in the width direction of the glass ribbon reaches the strain point temperature of ⁇ 50 ° C. from the annealing point temperature
  • the third cooling step is a step of cooling at a third average cooling rate until the temperature of the central portion in the width direction of the glass ribbon becomes a strain point temperature of ⁇ 50 ° C. to a strain point temperature of ⁇ 200 ° C.
  • the first average cooling rate is 5.0 ° C./second or more, the first average cooling rate is faster than the third average cooling rate, and the third average cooling rate is the second 14.
  • An apparatus for producing a glass plate by a downdraw method A melting apparatus for melting glass raw material to obtain molten glass; The molten glass is supplied to a molded body provided in a molding furnace to form a glass ribbon, the flow of the glass ribbon is created, and the glass ribbon is pulled by a roller provided in the slow cooling furnace, and the slow cooling furnace A molding device for cooling inside, A cutting device for cutting the cooled glass ribbon in a cutting space,
  • the furnace The external space is a space partitioned by a partition with respect to the atmospheric pressure atmosphere, and the atmospheric pressure of at least a part of the furnace external space is relative to the atmospheric pressure of the furnace internal space at the same position in the flow direction of the glass ribbon.
  • An apparatus for producing a glass plate characterized in that an atmospheric pressure control device for adjusting the atmospheric pressure
  • the atmospheric pressure control device is a device that adjusts the inflow of air to and from the atmosphere in order to control the atmospheric pressure in the furnace exterior space.
  • cooling roller 340 Cooling units 350a to 350h Conveying rollers 355, 360a, 360b, 360c, 415, 416, 417a, 417b, 417c, 418 Pressure sensor 400 Cutting devices 411, 412, 413a, 413b, 413c, 414 Floor surfaces 421, 422, 423a, 423b, 423c, 424 Blower 500 Controller 510 Drive unit

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Re-Forming, After-Treatment, Cutting And Transporting Of Glass Products (AREA)
PCT/JP2012/004231 2011-06-30 2012-06-29 ガラス板の製造方法及びガラス板の製造装置 Ceased WO2013001834A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
KR1020127034182A KR101442384B1 (ko) 2011-06-30 2012-06-29 유리판의 제조 방법 및 유리판의 제조 장치
JP2012530008A JP5235249B1 (ja) 2011-06-30 2012-06-29 ガラス板の製造方法及びガラス板の製造装置
CN201280002970.4A CN103108840B (zh) 2011-06-30 2012-06-29 玻璃板的制造方法及玻璃板的制造装置
KR1020127020852A KR101300934B1 (ko) 2011-06-30 2012-06-29 유리판의 제조 방법 및 유리판의 제조 장치

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011-146719 2011-06-30
JP2011146719 2011-06-30

Publications (1)

Publication Number Publication Date
WO2013001834A1 true WO2013001834A1 (ja) 2013-01-03

Family

ID=47423751

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/004231 Ceased WO2013001834A1 (ja) 2011-06-30 2012-06-29 ガラス板の製造方法及びガラス板の製造装置

Country Status (5)

Country Link
JP (3) JP5235249B1 (https=)
KR (2) KR101442384B1 (https=)
CN (2) CN103108840B (https=)
TW (2) TW201328997A (https=)
WO (1) WO2013001834A1 (https=)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104395253A (zh) * 2013-03-29 2015-03-04 安瀚视特控股株式会社 玻璃基板制造方法及玻璃基板制造装置
WO2017079546A1 (en) * 2015-11-05 2017-05-11 Corning Incorporated Glass manufacturing method for reduced particle adhesion
WO2021124801A1 (ja) * 2019-12-18 2021-06-24 日本電気硝子株式会社 ガラス物品の製造方法及びガラス物品の製造装置

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6007277B2 (ja) * 2014-03-31 2016-10-12 ＡｖａｎＳｔｒａｔｅ株式会社 ガラス基板の製造方法、及び、ガラス基板の製造装置
CN104944748B (zh) * 2014-03-31 2017-10-20 安瀚视特控股株式会社 玻璃基板的制造方法、及玻璃基板的制造装置
WO2015166972A1 (ja) * 2014-04-30 2015-11-05 ＡｖａｎＳｔｒａｔｅ株式会社 ガラス板の製造方法、及び、ガラス板の製造装置
JP2016210630A (ja) * 2015-04-28 2016-12-15 旭硝子株式会社 支持ロール、ガラス板の製造方法
JP6623836B2 (ja) * 2016-02-29 2019-12-25 日本電気硝子株式会社 ガラス板製造設備およびガラス板の製造方法
US9758418B1 (en) * 2016-04-06 2017-09-12 Corning Incorporated Methods of producing glass ribbon
JP6834379B2 (ja) * 2016-11-11 2021-02-24 日本電気硝子株式会社 板ガラス製造方法及び板ガラス製造装置
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
KR102139863B1 (ko) * 2017-09-29 2020-07-31 아반스트레이트 가부시키가이샤 유리판의 제조 방법
JP7265553B2 (ja) * 2017-10-30 2023-04-26 コーニング インコーポレイテッド 薄いガラスリボンの処理システムおよび方法
WO2019124271A1 (ja) 2017-12-20 2019-06-27 日本電気硝子株式会社 ガラス板の製造方法
WO2020129907A1 (ja) * 2018-12-21 2020-06-25 日本電気硝子株式会社 ガラス板製造方法及びその製造装置

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11171567A (ja) * 1997-07-31 1999-06-29 Owens Brockway Glass Container Inc ケースガラス流送出方法及び装置
JP2008266098A (ja) * 2007-04-24 2008-11-06 Nippon Electric Glass Co Ltd ガラス板製造方法およびガラス板製造設備
JP2009173525A (ja) * 2007-12-25 2009-08-06 Nippon Electric Glass Co Ltd ガラス板の製造方法及び製造設備

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE757057A (fr) * 1969-10-06 1971-04-05 Corning Glass Works Procede et appareil de controle d'epaisseur d'une feuille de verre nouvellement etiree
JPH02149438A (ja) * 1988-11-30 1990-06-08 Hoya Corp ガラス板の製造装置
CN101374778B (zh) * 2005-12-15 2012-12-12 康宁股份有限公司 溢流下拉玻璃形成方法和装置
JP5428287B2 (ja) * 2007-12-25 2014-02-26 日本電気硝子株式会社 ガラス板の製造方法及び製造設備
US20110094267A1 (en) * 2009-10-28 2011-04-28 Kenneth William Aniolek Methods of producing glass sheets
US8707737B2 (en) * 2009-11-30 2014-04-29 Corning Incorporated Method and apparatus for pressure control of glass-making thickness-control zone

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11171567A (ja) * 1997-07-31 1999-06-29 Owens Brockway Glass Container Inc ケースガラス流送出方法及び装置
JP2008266098A (ja) * 2007-04-24 2008-11-06 Nippon Electric Glass Co Ltd ガラス板製造方法およびガラス板製造設備
JP2009173525A (ja) * 2007-12-25 2009-08-06 Nippon Electric Glass Co Ltd ガラス板の製造方法及び製造設備

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104395253A (zh) * 2013-03-29 2015-03-04 安瀚视特控股株式会社 玻璃基板制造方法及玻璃基板制造装置
CN104395253B (zh) * 2013-03-29 2016-12-14 安瀚视特控股株式会社 玻璃基板制造方法及玻璃基板制造装置
WO2017079546A1 (en) * 2015-11-05 2017-05-11 Corning Incorporated Glass manufacturing method for reduced particle adhesion
WO2021124801A1 (ja) * 2019-12-18 2021-06-24 日本電気硝子株式会社 ガラス物品の製造方法及びガラス物品の製造装置

Also Published As

Publication number Publication date
CN103253848B (zh) 2016-08-17
JP6125572B2 (ja) 2017-05-10
TWI417255B (zh) 2013-12-01
JP2016006007A (ja) 2016-01-14
KR20130035252A (ko) 2013-04-08
CN103253848A (zh) 2013-08-21
JP2013126946A (ja) 2013-06-27
JP5235249B1 (ja) 2013-07-10
TW201305069A (zh) 2013-02-01
CN103108840B (zh) 2015-02-25
KR101300934B1 (ko) 2013-08-27
KR101442384B1 (ko) 2014-09-22
CN103108840A (zh) 2013-05-15
JPWO2013001834A1 (ja) 2015-02-23
TWI561482B (https=) 2016-12-11
JP5778196B2 (ja) 2015-09-16
TW201328997A (zh) 2013-07-16
KR20140017417A (ko) 2014-02-11

Similar Documents

Publication Publication Date Title
JP6125572B2 (ja) ガラス板の製造方法及びガラス板の製造装置
JP5189224B2 (ja) ガラス板の製造方法及びガラス板製造装置
CN101821209B (zh) 玻璃板的制造方法及制造设备
JP5288388B1 (ja) ガラス板の製造方法及びガラス板製造装置
TWI422539B (zh) 玻璃板製造方法以及玻璃板製造設備
US10822264B2 (en) Alkali-free glass substrate and method for manufacturing alkali-free glass substrate
WO2012132309A1 (ja) ガラス板の製造方法及びガラス板製造装置
JP5848329B2 (ja) ガラス板の製造方法及びガラス板製造装置
JP5508466B2 (ja) ガラス基板の製造方法

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2012530008

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 201280002970.4

Country of ref document: CN

ENP Entry into the national phase

Ref document number: 20127020852

Country of ref document: KR

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12803593

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12803593

Country of ref document: EP

Kind code of ref document: A1