CN114644446A - Float glass manufacturing device, float glass manufacturing method, and float glass - Google Patents
Float glass manufacturing device, float glass manufacturing method, and float glass Download PDFInfo
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- CN114644446A CN114644446A CN202111551493.4A CN202111551493A CN114644446A CN 114644446 A CN114644446 A CN 114644446A CN 202111551493 A CN202111551493 A CN 202111551493A CN 114644446 A CN114644446 A CN 114644446A
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- 239000005329 float glass Substances 0.000 title claims abstract description 97
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 41
- 239000011521 glass Substances 0.000 claims abstract description 167
- 238000011144 upstream manufacturing Methods 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims description 52
- 239000002184 metal Substances 0.000 claims description 52
- 238000001816 cooling Methods 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 2
- 229910052681 coesite Inorganic materials 0.000 claims 1
- 229910052906 cristobalite Inorganic materials 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 229910052682 stishovite Inorganic materials 0.000 claims 1
- 229910052905 tridymite Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 16
- 239000000758 substrate Substances 0.000 description 21
- 238000000465 moulding Methods 0.000 description 11
- 230000003287 optical effect Effects 0.000 description 10
- 239000006060 molten glass Substances 0.000 description 9
- 238000010583 slow cooling Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 239000011449 brick Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000007517 polishing process Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000005354 aluminosilicate glass Substances 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 238000012217 deletion Methods 0.000 description 1
- 230000037430 deletion Effects 0.000 description 1
- 238000002438 flame photometric detection Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000075 oxide glass Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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Classifications
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- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
Provided is a technique for obtaining float glass having a large plan view size and a small curvature. A float glass manufacturing apparatus is provided with a bath, a plurality of upper rolls, a ceiling, a plurality of heaters, and a plurality of controllers. The bath has a narrow region, a middle region, and a wide region in this order from the downstream end toward the upstream side. The narrow region has a deep bottom portion, a shallow bottom portion, and a pocket portion in this order from the downstream end toward the upstream side. The ceiling is divided into sections in the flow direction and the width direction of the glass ribbon, and a plurality of heaters are provided for collective control by one controller selected for each of the sections. And a distance in the flow direction between a1 st dividing line that divides two adjacent rows in the flow direction and a downstream end of the pocket, the 1 st dividing line being closest to the downstream end of the pocket, is 0% to 15% of a length of the pocket in the flow direction.
Description
Technical Field
The present disclosure relates to a float glass manufacturing apparatus, a float glass manufacturing method, and float glass.
Background
The float glass manufacturing apparatus forms molten glass into a glass ribbon in a ribbon shape by continuously supplying molten glass onto molten metal in a bath and causing the molten glass to flow over the molten metal. After the glass ribbon was gradually cooled, both widthwise ends of the glass ribbon were cut off to obtain float glass. Float glass is used for a glass substrate of a Flat Panel Display (FPD) or the like.
Patent document 1: international publication No. 2012/066889
With the enlargement of FPDs, the float glass is required to have a large plan view size. However, as the plan view size of the float glass is larger, the plane strain of the float glass is more likely to be larger, and the curvature of the float glass is more likely to be larger.
Disclosure of Invention
An aspect of the present disclosure provides a technique for obtaining float glass having a large plan view size and a small curvature.
A float glass manufacturing apparatus according to one aspect of the present disclosure includes: a bath tank for containing molten metal; a plurality of upper rollers for pressing the widthwise ends of the sheet-like glass ribbon against the surface of the molten metal; a ceiling provided above the glass ribbon; a plurality of heaters suspended from the ceiling; and a plurality of controllers for controlling the plurality of heaters. The bath includes, in order from a downstream end to an upstream side: a narrow region in which the liquid surface has a constant dimension in the width direction, an intermediate region in which the liquid surface has a gradually increasing dimension in the width direction, and a wide region in which the liquid surface has a constant dimension in the width direction that is larger than the narrow region. The narrow region includes, in order from the downstream end toward the upstream side: the molten metal container includes a deep bottom portion, a shallow bottom portion having a depth of the molten metal shallower than the deep bottom portion, and a pocket portion having a depth of the molten metal deeper than the shallow bottom portion. The ceiling is divided into a plurality of rows in the flow direction of the glass ribbon, and each of the rows is divided in the width direction of the glass ribbon, and a plurality of heaters are provided for collective control by one controller selected for each of the plurality of the sections. The distance in the flow direction between the 1 st dividing line that divides two adjacent rows in the flow direction and the downstream end of the pocket closest to the 1 st dividing line at the downstream end of the pocket is 0% to 15% of the length of the pocket in the flow direction.
A float glass according to one aspect of the present disclosure is a float glass having a rectangular shape in plan view with a longitudinal dimension of 2900mm or more, a lateral dimension of 3200mm or more, and an average plate thickness of 0.75mm or less, and is an alkali-free glass having a strain point of 650 ℃ or more, and has a residual stress of 2.0MPa or less in a plane direction parallel to the main surface over the entire main surface.
According to one aspect of the present disclosure, the temperature distribution of the glass ribbon can be appropriately controlled above the molten metal, and float glass having a large plan view size and a small curvature can be obtained.
Drawings
Fig. 1 is a sectional view of a float glass manufacturing apparatus according to an embodiment.
Fig. 2 is a graph showing the flow of the glass ribbon and the depth distribution of the molten metal in the flow direction of the glass ribbon.
Fig. 3 is a plan view showing an example of a ceiling section.
Fig. 4 is a cross-sectional view showing an example of the most downstream section in the glass ribbon flowing direction.
Fig. 5 is a graph showing an example of a relationship between the linear expansion coefficient of glass and temperature.
Fig. 6 (a) is a plan view showing an example of stress generated in the glass ribbon in a process in which the linear expansion coefficient of the glass increases, and fig. 6 (B) is a plan view showing an example of stress generated in the glass ribbon in a process in which the linear expansion coefficient of the glass decreases.
Fig. 7 (a) is a cross-sectional view showing an example of the structure of the narrow region of the bath and the section of the heater, and fig. 7 (B) is a view showing an example of the temperature change of the glass ribbon in the narrow region.
Fig. 8 is a schematic view of collecting float glass according to an embodiment.
Fig. 9 is a plan view of a float glass according to an embodiment.
Description of the reference numerals
A float glass manufacturing apparatus; a bath; an upper roller; a ceiling; a heater; a controller; melting a metal; melting glass; GR..
Detailed Description
Hereinafter, a mode for carrying out the present disclosure will be described with reference to the drawings. In the drawings, the same or corresponding components are denoted by the same reference numerals, and description thereof may be omitted. In each drawing, the X-axis direction, the Y-axis direction, and the Z-axis direction are perpendicular to each other, the X-axis direction and the Y-axis direction are horizontal, and the Z-axis direction is vertical. The X-axis direction is a flow direction of the glass ribbon GR, and the Y-axis direction is a width direction of the glass ribbon GR. In the specification, "to" indicating a numerical range means that numerical values described before and after the range are included as a lower limit value and an upper limit value.
A float glass manufacturing apparatus 1 according to the present embodiment will be described with reference to fig. 1. The float glass manufacturing apparatus 1 includes: a forming apparatus 2 for forming molten glass G into a glass ribbon GR having a ribbon plate shape; a slow cooling device 3 for slowly cooling the glass ribbon GR molded by the molding device 2; and a connecting device 4 for connecting the forming device 2 and the slow cooling device 3. The connecting device 4 includes a slag box 41 and a plurality of lift rollers 42 arranged inside the slag box 41. The glass ribbon GR is conveyed obliquely upward over the plurality of lift rollers 42. The slow cooling device 3 includes a slow cooling furnace 31 and a plurality of conveying rollers 32 arranged inside the slow cooling furnace 31. The glass ribbon GR is conveyed in the horizontal direction on the plurality of conveying rollers 32. After passing through the annealing furnace 31, the glass ribbon GR is cut into a desired size by a processing apparatus not shown. As a result, a float glass is obtained as a product.
When the application of the float glass is a glass substrate for an FPD described later, the float glass is further subjected to cutting, chamfering, and polishing in this order. In the polishing process, at least one of both main surfaces of the float glass is polished to remove fine irregularities and waviness existing in the main surface of the float glass. The glass substrate obtained by the polishing process is a so-called mother glass (mother glass), and is further divided in the middle of the manufacturing process of the FPD.
Examples of the glass type of the float glass include alkali-free glass, aluminosilicate glass, borosilicate glass, and soda-lime glass. The alkali-free glass means that Na is not substantially contained2O、K2And alkali metal oxide glasses such as O. Here, the substantial absence of the alkali metal oxide means that the total content of the alkali metal oxide is 0.1 mass% or less.
The float glass is not particularly limited in its application, and is, for example, a Flat Panel Display (FPD) such as a Liquid Crystal Display (LCD) and an organic EL display, and is, for example, a glass substrate for FPD. When the float glass is used as a glass substrate for an FPD, the float glass is alkali-free glass.
For example, the alkali-free glass contains SiO in mass% based on the oxide2：54％～68％、Al2O3：10％～23％、B2O3: 0% -12%, MgO: 0% -12%, CaO: 0% -15%, SrO: 0% -16%, BaO: 0% -15%, MgO + CaO + SrO + BaO: 8 to 26 percent. In order to obtain a high strain point, the alkali-free glass is preferably expressed in mass% on an oxide basis, B2O3The content of (B) is 5% or less.
In order to obtain a low thermal shrinkage, the strain point of the alkali-free glass is 650 ℃ or higher, for example. Strain point is equal to 1014.5A temperature corresponding to the viscosity of dPa · s in accordance with JIS R3103-02: 2001, respectively. The strain point of the alkali-free glass is preferably 670 ℃ or higher, more preferably 690 ℃ or higher, and still more preferably 700 ℃ or higher. The strain point of the alkali-free glass is preferably 750 ℃ or lower in order to prevent the temperature in the molding apparatus 2 from becoming too high.
Next, a molding apparatus 2 according to the present embodiment will be described with reference to fig. 1 to 4. As shown in fig. 1, the molding apparatus 2 includes a bath 20. The bath 20 contains molten metal M. As the molten metal M, for example, molten tin is used. In addition to the molten tin, a molten tin alloy or the like can be used as long as the density of the molten metal M is higher than that of the molten glass G. The bath 20 includes a box-shaped bottom case 20a opened upward, side bricks 20b protecting the side walls of the bottom case 20a from the molten metal M, and bottom bricks 20c provided on the bottom wall of the bottom case 20 a.
The molding device 2 includes a runner outlet lip 21 and a runner control gate 22. The spout lip 21 continuously supplies the molten glass G onto the molten metal M in the bath 20. The flow path control gate 22 is movable up and down with respect to the flow path outlet lip, and adjusts the flow rate of the molten glass G flowing over the flow path outlet lip 21. The narrower the interval between the flow path control gate 22 and the flow path outlet lip 21, the smaller the flow rate of the molten glass G flowing over the flow path outlet lip 21. The flow path control gate 22 is made of refractory. The flow path control gate plate 22 may be provided with a protective film for preventing the flow path control gate plate 22 from coming into contact with the molten glass G. The protective film is formed of platinum or a platinum alloy, for example.
As shown in fig. 2, the bath 20 has a narrow region X1, a middle region X2, and a wide region X3 in this order from the downstream end toward the upstream side. The narrow region X1 is a region where the width-directional dimension of the liquid surface of the molten metal M is constant. The intermediate region X2 is a region in which the width-directional dimension of the liquid surface gradually increases from the narrow region X1 to the wide region X3. The wide region X3 is a region in which the width-directional dimension of the liquid surface is larger and constant than the narrow region X1.
The molding device 2 includes an upper roller 23. The upper roller 23 is provided in the wide region X3. The upper roller 23 rotates while pressing the end portion of the glass ribbon GR in the width direction against the liquid surface of the molten metal M, and feeds the glass ribbon GR in the X-axis direction. The glass ribbon GR is gradually cooled and solidified while moving in the X-axis direction.
The pair of upper rollers 23 is provided on both sides of the glass ribbon GR in the width direction, and suppresses shrinkage of the glass ribbon GR in the width direction. The sheet thickness of the glass ribbon GR can be made thinner than the equilibrium thickness. Equilibrium thickness refers to the thickness that is naturally achieved due to the balance of gravity and surface tension. The pair of upper rollers 23 is provided in plurality at intervals in the flow direction of the glass ribbon GR.
The upper roller 23 has a rotating member 23a and a rotating shaft 23 b. The rotary member 23a is, for example, disk-shaped, and presses the end portion of the glass ribbon GR in the width direction with its outer periphery to feed out the glass ribbon GR in the flow direction of the glass ribbon GR. The glass ribbon GR is gradually cooled and solidified while moving in the X-axis direction. The rotary shaft 23b is rotationally driven by a drive device, not shown, to rotate the rotary member 23 a.
As shown in fig. 4, the glass ribbon GR has a flat portion GR1 to be cut into float glass at the center portion in the width direction, and has ear portions GR2 having a wall thickness thicker than the flat portion GR1 at both end portions in the width direction. The ear portions GR2 are formed in the process of reducing the thickness of the glass ribbon GR by using the pair of upper rollers 23. The glass ribbon GR is cut into a desired size by a processing apparatus not shown after passing through the annealing furnace 31. The processing apparatus cuts off the ear portions GR2 of the glass ribbon GR. As a result, a float glass having a uniform thickness is obtained.
As shown in fig. 1, the molding apparatus 2 includes a ceiling 24 provided above the glass ribbon GR. The ceiling 24 forms an upper surface of the space S above the bath 20. The upper space S is filled with a reducing gas to prevent oxidation of the molten metal M. The reducing gas is, for example, a mixed gas of nitrogen and hydrogen, and contains 85 to 98.5 vol% of nitrogen and 1.5 to 15 vol% of hydrogen. The reducing gas is supplied from the space above the ceiling 24 to the upper space S through the joints between the bricks of the ceiling 24 and the insertion holes of the heater 25 provided in the ceiling 24.
The molding device 2 includes a heater 25. The heater 25 is suspended from the ceiling 24 and heats the glass ribbon GR passing thereunder. The heater 25 is an electric heater and is heated by energization. The heater 25 is, for example, a SiC heater. A plurality of heaters 25 are arranged in a matrix in the flow direction and the width direction of the glass ribbon GR.
By controlling the outputs of the plurality of heaters 25, the temperature distribution of the glass ribbon GR can be controlled, and the sheet thickness distribution of the glass ribbon GR can be controlled. The output of the heater 25 means the amount of heat per unit time (unit: kW). The outputs of the heaters 25 are controlled for each zone. One controller 26 is used for each zone.
Next, an example of the partition of the ceiling 24 will be described with reference to fig. 3 and 4. Fig. 3 shows only a region overlapping the narrow region X1 in a plan view, but there may be a region overlapping the middle region X2 or the wide region X3 in a plan view. In fig. 3, the open arrows indicate the flow direction of the glass ribbon GR.
As shown in fig. 3, the ceiling 24 is divided into a plurality of rows A, B in the flow direction of the glass ribbon GR. Each row A, B is divided into a plurality of sections a1 to a7 and B1 to B3 in the width direction of the glass ribbon GR. Each row A, B is preferably divided into left and right symmetrical sections around the center line CL in the width direction of the glass ribbon GR. The temperature distribution of the glass ribbon GR can be controlled to be bilaterally symmetric.
The sections a1 to a7 and B1 to B3 are provided with a plurality of heaters 25 collectively controlled by one controller 26 selected for each of the sections a1 to a7 and B1 to B3. The one-time control includes controlling to the same output. By collectively controlling the plurality of heaters 25 by one controller 26, the number of controllers 26 can be reduced. The controller 26 is, for example, a microcomputer.
The boundary D1 between two columns A, B adjacent to each other in the flow direction of the glass ribbon GR is referred to as a1 st dividing line D1. The boundary D2 between two adjacent sections in the width direction of the glass ribbon GR is referred to as a2 nd dividing line D2. Preferably, the 2 nd dividing line D2 is shifted in the width direction of the glass ribbon GR in the row a and the row B with the 1 st dividing line D1 interposed therebetween.
For example, a boundary D2 between the section B1 and the section B2 and a boundary D2 between the section a2 and the section A3 are shifted in the width direction of the glass ribbon GR by a1 st dividing line D1. Therefore, in the upstream row B, the portion of the glass ribbon GR passing below the boundary D2 between the section B1 and the section B2 passes below the section A3 in the downstream row a.
In the upstream row B, the output (unit: kW/m) of the heater 25 per unit area in the sections B1 and B22) On the other hand, a temperature difference occurs between the section B1 and the section B2. The temperature difference also occurs between the glass ribbon GR at the section B1 and the sectionThe line B2 passes below the boundary D2. This portion passes below the section a3 in the downstream row a, and the temperature difference is alleviated.
In the present embodiment, the ceiling 24 overlapping the narrow region X1 in a plan view is divided into 2 rows (row A, B), but may be divided into 3 rows or more.
Next, the plane strain of the float glass will be described. The plane strain is a residual stress generated by a thermal history of the glass substrate, and is a residual stress in a plane direction parallel to the main surface of the glass substrate. The planar strain can be estimated by measuring the optical birefringence, i.e., the optical path difference between two orthogonally polarized light waves. The optical axis of each linearly polarized light wave is perpendicular to the main surface of the glass substrate.
When the optical path difference between two orthogonal linearly polarized light waves is denoted by R (nm), the planar strain F (mpa) is denoted by F ═ R/(C × D). D is the distance (cm) passed by the linearly polarized light wave, and is the thickness of the glass substrate. C is a proportionality constant determined by the chemical composition of the glass substrate and is called the photoelastic constant. C is usually 20 to 40 (nm/cm)/(MPa).
In the case where the stress applied to the glass substrate in the plane direction is zero or isotropic, two orthogonal linearly polarized light waves pass through the glass substrate at the same speed. On the other hand, when the stress in the plane direction applied to the glass substrate is anisotropic, the linearly polarized light wave passes through rapidly in the compressive stress direction and slowly in the tensile stress direction. That is, optical path differences are created between two orthogonal linearly polarized light waves. By measuring the direction and the magnitude of the maximum optical path difference, the anisotropy (direction and magnitude) of the stress can be measured.
The plane strain F is an index indicating anisotropy of stress, and is calculated as a direction in which a stress difference becomes maximum in a plane perpendicular to the optical axis and a stress difference thereof. When a compressive stress remains in a certain direction (for example, the X-axis direction) and a tensile stress of the same magnitude remains in a direction perpendicular thereto (for example, the Y-axis direction), the value of the plane strain F becomes the same. When the same amount of compressive stress or tensile stress remains in two orthogonal axial directions (for example, the X-axis direction and the Y-axis direction), the value of the plane strain F becomes zero.
As described above, the plane strain F is a stress difference in two directions orthogonal to the plane perpendicular to the optical axis. In the vicinity of each side of a rectangular glass substrate in a plan view, since the glass is cut at each side, stress does not remain in a direction perpendicular to each side, but only in a direction parallel to each side. Therefore, the plane strain and the residual stress in the vicinity of each side are almost equal. On the other hand, in the vicinity of the center of the rectangular glass substrate in a plan view, stress is applied from all directions in the plane, and the stresses cancel each other out, so that the plane strain has a small value.
The plane strain F is measured using, for example, an ABR-10A birefringence measuring instrument manufactured by Uniopt. An ABR-10A birefringence measurement device is a device that measures the optical path difference and the main axis orientation of birefringence by irradiating a transverse zeeman laser beam and detecting the phase difference of an orthogonal linearly polarized light wave. The resolution was 0.01nm in optical path difference and 0.1 degree in spindle azimuth. Unlike the method using the Senarmont method as a measuring method, the planar strain of about 0.1MPa to 5MPa can be measured. The planar strain is measured at a plurality of points arranged in a matrix at intervals of, for example, 50mm in the vertical and horizontal directions over the entire main surface of the glass substrate. The maximum value of the plane strain at all the measurement points is referred to as the maximum plane strain. The plane strain is measured in a state where the annealing treatment is not performed after the ear portions GR2 of the glass ribbon GR are cut.
Next, the cause of the plane strain of the float glass will be described with reference to fig. 5 and 6. As shown in fig. 5, the linear expansion coefficient of glass generally has a peak at high temperature. The glass ribbon GR passes through the peak of the linear expansion coefficient of the glass during its cooling as indicated by the arrow in fig. 5. The location where the peak passes is near the outlet 2a (see fig. 1) of the molding device 2. In addition, the temperature of the glass ribbon GR near the exit 2a is a temperature near the glass transition point.
While the glass ribbon GR is being cooled inside the forming apparatus 2, the linear expansion coefficient of the glass gradually increases toward the peak. In this process, as shown by the arrow in fig. 6 (a), tensile stress acts on the ear portions GR2 of the glass ribbon GR. The glass ribbon GR has an ear GR2 thicker than a flat GR1, and a large tensile stress acts on the ear GR 2.
On the other hand, in the process in which the glass ribbon GR is cooled inside the connection device 4 or the slow cooling device 3, the linear expansion coefficient of the glass gradually decreases from the peak. In this process, as shown by the arrow in fig. 6 (B), a compressive stress acts on the ear portions GR2 of the glass ribbon GR. The glass ribbon GR has an ear GR2 thicker than a flat GR1, and a large compressive stress acts on the ear GR 2.
The plane strain of the float glass is mainly determined by the magnitude of the tensile stress indicated by an arrow in fig. 6 (a), the time during which the tensile stress acts, the magnitude of the compressive stress indicated by an arrow in fig. 6 (B), and the time during which the compressive stress acts. The longer the tensile stress is applied, the more likely the tensile stress remains. Further, the longer the time for which the compressive stress acts, the more likely the compressive stress remains.
Compressive stress is generally left in the ear portions GR2 of the glass ribbon GR. Therefore, in the present embodiment, in order to reduce the compressive stress remaining in the ear portion GR2 of the glass ribbon GR, the time during which the tensile stress acts on the ear portion GR2 of the glass ribbon GR is lengthened. Specifically, the structure of the narrow region X1 of the bath 20 and the division of the heater 25 shown in fig. 7 (a) are employed.
First, with reference to fig. 7 (a), a structure of the narrow region X1 of the bath 20 will be described. As shown in fig. 7 (a), the narrow region X1 of the bath 20 has, in order from the downstream end toward the upstream side, a deep bottom portion X1a, a shallow bottom portion X1b in which the depth of the molten metal M is shallower than that of the deep bottom portion X1a, and a pocket portion X1c in which the depth of the molten metal M is deeper than that of the shallow bottom portion X1 b. The entire pocket X1c is provided in the narrow region X1, and as long as the pocket X1c does not extend to the wide region X3, the temperature of the glass ribbon GR is high to such an extent that the glass ribbon GR can be sufficiently sandwiched by the upper rollers 23 even in the downstream region of the wide region X3, and the formability of the glass ribbon GR is good.
In the present embodiment, the pocket X1c is provided entirely in the narrow region X1 as shown in fig. 2, but a part of the pocket may be provided in the middle region X2 and the remaining part may be provided in the narrow region X1. The bath 20 of the present embodiment has the narrow region X1, the intermediate region X2, and the wide region X3, but the technique of the present disclosure is not limited thereto. For example, the bath 20 may not have the intermediate region X2 between the narrow region X1 and the wide region X3, or may have a liquid surface whose width-directional dimension changes discontinuously between the narrow region X1 and the wide region X3. The number of the regions having a constant dimension in the width direction of the liquid surface is not limited to 2, and may be 1, or 3 or more. The dimension of the liquid surface in the width direction may be continuously changed from the upstream end to the downstream end of the bath 20.
The deep bottom X1a has, for example, a horizontal bottom surface and two vertical step surfaces. The step surface of the deep bottom portion X1a is vertically raised from the bottom surface, but may be inclined. The pocket X1c also has, for example, a horizontal bottom surface and two vertical step surfaces. The step surface of the pocket portion X1c is vertically raised from the bottom surface, but may be inclined. The shallow bottom X1b has a top surface that is higher in level than the bottom surface of the deep bottom X1a and the bottom surface of the pocket X1 c.
The depth Dc of the molten metal M in the pocket X1c is deep, the heat capacity of the molten metal M is large, and the molten metal M easily absorbs heat from the glass ribbon GR. Therefore, as shown in fig. 7 (B), the cooling rate of the glass ribbon GR at the pocket X1c can be increased. Further, the cooling speed of the glass ribbon GR at the deep bottom portion X1a can be reduced while maintaining the length L in the flow direction of the narrow region X1. As a result, the glass ribbon GR can be cooled slowly at a position immediately before the outlet 2a of the forming apparatus 2, and the time during which the tensile stress acts on the ear portions GR2 of the glass ribbon GR can be lengthened, thereby reducing the plane strain of the float glass.
The average cooling rate of the center line CL in the width direction of the glass ribbon GR passing through the pocket X1c is, for example, 60 deg.C/min to 120 deg.C/min, preferably 70 deg.C/min to 110 deg.C/min, more preferably 80 deg.C/min to 100 deg.C/min, and still more preferably 88 deg.C/min to 100 deg.C/min. When the average cooling rate is 60 ℃/min to 120 ℃/min, the conveyance rate of the glass ribbon GR can be increased, the productivity of the float glass can be improved, and the cooling rate of the glass ribbon GR at the deep bottom portion X1a can be reduced, whereby the plane strain of the float glass can be reduced.
The depth Db of the molten metal M at the shallow bottom portion X1b is shallower than both the depth Dc of the molten metal M at the pocket portion X1c and the depth Da of the molten metal M at the deep bottom portion X1 a. In other words, the relationship "Db < Dc" holds true for "Db < Da". As shown in fig. 7 (B), the shallow bottom portion X1B acts to generate a difference in cooling rate between the pocket portion X1c and the deep bottom portion X1a of the glass ribbon GR. In the pocket portion X1c, the glass ribbon GR cools at a faster rate than the deep bottom portion X1 a.
The depth Da of the molten metal M at the deep bottom X1a is deeper than the depth Db of the molten metal M at the shallow bottom X1 b. In other words, the relationship "Da > Db" holds. Therefore, the heat capacity of the molten metal M is large, and the temperature change of the glass ribbon GR due to the output variation of the heater 25 and the like can be suppressed.
The depth Dc of the molten metal M in the pocket X1c may be deeper than the depth Da of the molten metal M in the deep bottom X1 a. In other words, the relationship "Dc > Da > Db" may also hold. The heat capacity of the molten metal M at the pocket X1c is larger than that in the case where Dc is smaller than Da, and the molten metal M easily absorbs heat of the glass ribbon GR. Therefore, the cooling rate of the glass ribbon GR at the pocket X1c can be increased. Further, the cooling speed of the glass ribbon GR at the deep bottom portion X1a can be reduced while maintaining the length L in the flow direction of the narrow region X1.
The depth Dc of the molten metal M in the pocket X1c is, for example, 1.5 to 2.5 times the depth Db of the molten metal M in the shallow bottom X1 b. In other words, Dc/Db is 1.5 to 2.5. Dc/Db is preferably 1.5 to 2.0, more preferably 1.7 to 1.8.
The depth Da of the molten metal M at the deep bottom portion X1a is, for example, 1.5 to 2.5 times the depth Db of the molten metal M at the shallow bottom portion X1 b. In other words, Da/Db is 1.5-2.5. Da/Db is preferably 1.5 to 2.0, more preferably 1.7 to 1.8.
The length Lc in the flow direction of the pocket X1c is, for example, 15% to 35% of the length L in the flow direction of the narrow region X1. Lc is preferably 20% to 30% of L. When the length Lc is 15% to 35% of the length L, the cooling rate of the glass ribbon GR at the pocket X1c can be increased.
The length La in the flow direction of the deep bottom X1a is 40% to 60% of the length L in the flow direction of the narrow region X1. La is preferably 49% to 56%. If the length La is 40% to 60% of the length L, the cooling rate of the glass ribbon GR at the deep bottom portion X1a can be reduced.
Next, the zones of the heater 25 will be described with reference to fig. 3 and 4 in addition to fig. 7 (a). As shown in fig. 7 (a), the distance E in the flow direction between the 1 st dividing line D1 that divides the two rows A, B adjacent in the flow direction and the 1 st dividing line D1 closest to the downstream end X1D of the pocket X1c and the downstream end X1D of the pocket X1c is 0% to 15% of the length Lc in the flow direction of the pocket X1 c.
When the distance E is 0% to 15% of the length Lc, the 1 st dividing line D1 substantially coincides with the downstream end X1D of the pocket X1c in plan view. Therefore, a difference in cooling rate between the pocket portion X1c and the deep bottom portion X1a is likely to occur in the glass ribbon GR. The interval E is preferably 0% to 10% of the length Lc, more preferably 0% to 5% of the length Lc.
The forming apparatus 2 increases the output of the heater 25 on the downstream side as compared with the output of the heater 25 on the upstream side in order to quickly cool the glass ribbon GR at the pocket X1c on the upstream side and slowly cool the glass ribbon GR at the deep bottom X1a on the downstream side. If the interval E is out of the range of 0% to 15% of the length Lc, the amount of heating of the glass ribbon GR at the upstream-side pocket X1c by the downstream-side heater 25 is large, and it is difficult to impart a difference in cooling rate to the glass ribbon GR at the pocket X1c and the deep bottom portion X1 a.
The smaller the interval E, the more preferable. The interval E is, for example, 0mm to 500mm, preferably 0mm to 250mm, and more preferably 0mm to 125 mm.
In the present embodiment, the 1 st dividing line D1 is provided upstream of the downstream end X1D of the pocket X1c, but may be provided downstream of the downstream end X1D of the pocket X1 c.
As shown in fig. 3, the row a most downstream in the flow direction includes 5 or more (for example, 7) sections a1 to a7 in the width direction. If the number of sections included in the row a is 5 or more, a temperature difference is easily applied in the width direction of the glass ribbon GR at a position immediately before the outlet 2a of the forming apparatus 2. The number of segments included in the row a is preferably 7 or more. In view of the number of controllers 26, the number of sections included in the row a is preferably 11 or less.
In a plan view, the 2 nd dividing line D2 dividing two sections adjacent in the width direction in the most downstream row a overlaps the ear portion GR2 of the glass ribbon GR. A temperature difference is easily applied to the ear portions GR2 and the flat portions GR1 of the glass ribbon GR at a position immediately before the outlet 2a of the molding apparatus 2, and the flat portions GR1 can be cooled to a temperature lower than the ear portions GR 2.
As a result, the flat portion GR1 can be hardened at a position immediately before the outlet 2a of the molding device 2. Further, the ear portion GR2 can be cooled slowly, the time during which tensile stress acts on the ear portion GR2 can be lengthened, and the plane strain of the float glass can be reduced.
As shown in fig. 8, the float glass manufacturing apparatus and the float glass manufacturing method according to the present disclosure are suitable for collecting two (site L and site R) pieces of float glass having a substrate size of 11 th generation (G11) or more from the glass ribbon GR in the width direction of the glass ribbon GR. This is because, in this case, the width-direction dimension of the glass ribbon GR in the narrow region X1 is 6m or more, and it is not easy to reduce the plane strain of the float glass.
The substrate sizes of the 11 th generation (G11) were 2972mm in the vertical (short) direction and 3404mm in the horizontal (long) direction before the dicing process, and 2940mm in the vertical (short) direction and 3370mm in the horizontal (long) direction after the dicing process. The substrate size of the 6 th generation (G6) was 1524mm in the vertical direction (short side) and 1880mm in the horizontal direction (long side) before the cutting process.
Next, a float glass 10 according to the present embodiment will be described with reference to fig. 9. The float glass 10 is manufactured using the float glass manufacturing apparatus 1 described above. The float glass 10 is a so-called mother glass, and is cut into two pieces at positions indicated by broken lines in fig. 9, for example, in the middle of the FPD manufacturing process. The float glass 10 may be cut into four or more pieces in the middle of the FPD manufacturing process, and may be cut into a plurality of pieces. The production efficiency of the FPD can be improved.
The float glass 10 has a rectangular shape in plan view. The rectangle is a rectangle in which the length of 2 sides of one group is different from the length of 2 sides of the other group, but may be a square in which the lengths of 4 sides are equal. In addition, the rectangle includes a shape in which corners of 4 sides are chamfered.
The maximum plane strain of the float glass 10 is, for example, 2.0MPa or less. If the maximum plane strain is 2.0MPa or less, the glass can be prevented from being deformed before and after cutting even when the plane view size is large and the average plate thickness is small. Therefore, it is possible to suppress the pattern of the color filter or the Thin Film Transistor (TFT) from being deviated by cutting the glass substrate.
The maximum plane strain of the float glass 10 is preferably 1.5MPa or less. If the maximum plane strain is 1.5MPa or less, the bending of the float glass 10 is small even when the plane view size is large and the average plate thickness is small. Therefore, in the manufacturing process of the FPD, the vacuum adsorption failure of the float glass 10 (glass substrate) can be suppressed.
The present inventors investigated the cause of the vacuum adsorption failure of mother glass in the FPD manufacturing process. As a result, the present inventors found that: when the maximum plane strain of the mother glass having a vertical dimension T1 of 2900mm or more, a lateral dimension T2 of 3200mm or more and an average plate thickness of 0.75mm or less exceeds 1.5MPa, the bending of the mother glass is large, and a vacuum suction failure occurs. Thus, by using the float glass manufacturing apparatus 1 described above, the maximum plane strain of the mother glass can be reduced.
The maximum plane strain of the float glass 10 is more preferably 1.0MPa or less. The maximum plane strain of the float glass 10 is preferably 0.1MPa or more.
Examples
The experimental data will be described below. In examples 1 to 3, using the float glass manufacturing apparatus 1 according to the above embodiment, under the same conditions except for the "cooling rate" shown in table 1, a rectangular float glass having a vertical dimension of 2972mm, a horizontal dimension of 3404mm, and an average plate thickness of 0.5mm in a plan view was manufactured. The float glass is alkali-free glass having a strain point of 670 ℃ and contains SiO in mass% based on oxides2：60％、Al2O3：17％、B2O3：8％、MgO：3％、CaO：4％、SrO：8％。
In examples 1 to 3, the distance E in the flow direction between the 1 st dividing line D1 closest to the downstream end X1D of the pocket X1c and the downstream end X1D of the pocket X1c is 0% of the length Lc in the flow direction of the pocket X1c (see fig. 7 (a)). Examples 1 to 3 are all examples. Table 1 shows the experimental conditions and the experimental results.
Table 1:
| example 1 | Example 2 | Example 3 | |
| Cooling Rate (. degree. C./min) | 86.5 | 89.1 | 93.7 |
| log10η1 | 13.2 | 13.2 | 13.2 |
| log10η2 | 13.5 | 13.5 | 13.5 |
| Maximum plane strain (MPa) | 1.78 | 1.14 | 0.99 |
In table 1, "cooling rate" is an average cooling rate of the widthwise center line CL of the glass ribbon GR when passing through the pocket X1 c. In table 1, "η 1" is the viscosity ([ dPa · s ]) of the widthwise center line CL of the glass ribbon GR in the downstream region of the slag box 41, and "η 2" is the viscosity ([ dPa · s ]) of the widthwise center line CL of the glass ribbon GR at a position separated by 3m from the most upstream end toward the downstream side of the quenching furnace 31.
As is clear from Table 1, float glasses having a maximum plane strain of 2.0MPa or less were obtained in examples 1 to 3.
In examples 2 to 3, the cooling rate of the glass ribbon GR at the pocket X1c was higher and the cooling rate of the glass ribbon GR at the deep bottom X1a was lower than in example 1. As a result, compared to example 1, the glass ribbon GR can be cooled slowly at a position immediately before the outlet 2a of the forming apparatus 2, and the time during which the tensile stress acts on the lug portions GR2 of the glass ribbon GR can be made longer, thereby obtaining float glass having a maximum plane strain of 1.5MPa or less.
The float glass production apparatus, the float glass production method, and the float glass according to the present disclosure have been described above, but the present disclosure is not limited to the above embodiments and the like. Various changes, modifications, substitutions, additions, deletions, and combinations may be made within the scope of the claims. These are of course also within the technical scope of the present disclosure.
Claims (19)
1. A float glass manufacturing device is provided with: a bath tank for containing molten metal; a plurality of upper rollers that press the widthwise ends of the glass ribbon in the form of a band plate against the surface of the molten metal; a ceiling disposed above the glass ribbon; a plurality of heaters suspended from the ceiling; and a plurality of controllers controlling the plurality of heaters,
it is characterized in that the preparation method is characterized in that,
the bath has, in order from the downstream end to the upstream side: a narrow region in which the dimension of the liquid surface in the width direction is constant, a middle region in which the dimension of the liquid surface in the width direction gradually increases, and a wide region in which the dimension of the liquid surface in the width direction is larger than and constant than the narrow region,
the narrow region has, in order from the downstream end toward the upstream side: a deep bottom portion, a shallow bottom portion in which a depth of the molten metal is shallower than the deep bottom portion, and a pocket portion in which a depth of the molten metal is deeper than the shallow bottom portion,
a plurality of heaters collectively controlled by one controller selected for each of the sections are provided in each section in which the ceiling is divided into a plurality of rows in the flow direction of the glass ribbon and each row is divided in the width direction of the glass ribbon,
a distance in the flow direction between a1 st dividing line that divides two adjacent rows in the flow direction and a downstream end of the pocket, the 1 st dividing line being closest to the downstream end of the pocket, is 0% to 15% of a length of the pocket in the flow direction.
2. The float glass manufacturing apparatus of claim 1,
a depth of the molten metal at the pocket is deeper than a depth of the molten metal at the deep bottom.
3. The float glass manufacturing apparatus according to claim 1 or 2,
the depth of the molten metal at the pocket is 1.5 to 2.5 times the depth of the molten metal at the shallow bottom.
4. The float glass manufacturing apparatus according to any one of claims 1 to 3,
the length of the pocket in the flow direction is 15% to 35% of the length of the narrow region in the flow direction.
5. The float glass manufacturing apparatus according to any one of claims 1 to 4,
the depth of the molten metal at the deep bottom is 1.5 to 2.5 times the depth of the molten metal at the shallow bottom.
6. The float glass manufacturing apparatus according to any one of claims 1 to 5,
the length of the deep bottom in the flow direction is 40% to 60% of the length of the narrow region in the flow direction.
7. The float glass manufacturing apparatus according to any one of claims 1 to 6,
the glass ribbon has a flat portion to be cut into float glass at a central portion in the width direction, and has lug portions having a wall thickness thicker than that of the flat portion at both end portions in the width direction,
the column most downstream in the flow direction includes 5 or more of the sections in the width direction,
a2 nd dividing line that divides two sections adjacent in the width direction in the most downstream row overlaps with the ear portion of the glass ribbon in a plan view.
8. The float glass manufacturing apparatus according to any one of claims 1 to 7,
the 1 st dividing line is provided upstream of the downstream end of the pocket.
9. The float glass manufacturing apparatus according to any one of claims 1 to 7,
the 1 st dividing line is provided on a downstream side of the downstream end of the pocket.
10. The float glass manufacturing apparatus according to any one of claims 1 to 9,
the pocket is entirely disposed in the narrow region.
11. A float glass manufacturing device is provided with: a bath tank for containing molten metal; a plurality of upper rollers that press the widthwise ends of the glass ribbon in a ribbon shape against the surface of the molten metal; a ceiling disposed above the glass ribbon; a plurality of heaters suspended from the ceiling; and a plurality of controllers controlling the plurality of heaters,
it is characterized in that the preparation method is characterized in that,
the bath has, in order from the downstream end to the upstream side: a deep bottom portion, a shallow bottom portion in which a depth of the molten metal is shallower than the deep bottom portion, and a pocket portion in which a depth of the molten metal is deeper than the shallow bottom portion,
a plurality of heaters collectively controlled by one controller selected for each of the sections are provided in each section in which the ceiling is divided into a plurality of rows in the flow direction of the glass ribbon and each row is divided in the width direction of the glass ribbon,
a distance in the flow direction between a1 st dividing line that divides two adjacent rows in the flow direction and a downstream end of the pocket closest to the 1 st dividing line and the downstream end of the pocket is 0% to 15% of a length of the pocket in the flow direction.
12. A float glass production method using the float glass production apparatus according to any one of claims 1 to 11,
it is characterized in that the preparation method is characterized in that,
comprises the following steps:
forming the glass ribbon in a ribbon shape over the molten metal; and
heating the glass ribbon passing under the heater with the heater.
13. The float glass manufacturing method according to claim 12,
the average cooling rate of the center line of the glass ribbon in the width direction is 60 to 120 ℃/min when the glass ribbon passes through the pocket.
14. A float glass which is rectangular in plan view, has a longitudinal dimension of 2900mm or more, a lateral dimension of 3200mm or more and an average plate thickness of 0.75mm or less,
it is characterized in that the preparation method is characterized in that,
the float glass is alkali-free glass with a strain point above 650 ℃,
the residual stress in a plane direction parallel to the main surface is 2.0MPa or less over the entire main surface.
15. The float glass of claim 14,
the residual stress in a plane direction parallel to the main surface is 1.5MPa or less over the entire main surface.
16. The float glass of claim 14 or 15,
the average thickness is 0.55mm or less.
17. The float glass of any one of claims 14 to 16,
the alkali-free glass contains, in mass% on an oxide basis:
SiO2：54％～68％；
Al2O3：10％～23％；
B2O3：0％～12％；
MgO：0％～12％；
CaO：0％～15％；
SrO：0％～16％；
BaO：0％～15％；
MgO+CaO+SrO+BaO：8％～26％。
18. the float glass of claim 17,
b in the alkali-free glass is represented by mass% based on oxides2O3The content of (A) is less than 5%.
19. A float glass produced by the float glass production method according to claim 12 or 13.
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2021
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- 2021-12-17 CN CN202111551493.4A patent/CN114644446B/en active Active
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| JP2000016825A (en) * | 1998-06-29 | 2000-01-18 | Nippon Electric Glass Co Ltd | Production of glass substrate for flat panel display |
| CN101229953A (en) * | 2007-06-13 | 2008-07-30 | 河南安彩高科股份有限公司 | Annealing method for ultra-thin flat glass |
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