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WO2019178076A1 - Procédés et appareil de production de surfaces antireflets - Google Patents

Procédés et appareil de production de surfaces antireflets Download PDF

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Publication number
WO2019178076A1
WO2019178076A1 PCT/US2019/021819 US2019021819W WO2019178076A1 WO 2019178076 A1 WO2019178076 A1 WO 2019178076A1 US 2019021819 W US2019021819 W US 2019021819W WO 2019178076 A1 WO2019178076 A1 WO 2019178076A1
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WO
WIPO (PCT)
Prior art keywords
article
dispensing
dipping tank
tank
circuit
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/US2019/021819
Other languages
English (en)
Inventor
Haixing CHEN
Ling Chen
Chenglong Dai
Liping HONG
Jianqiang Zhu
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.)
Corning Inc
Original Assignee
Corning Inc
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 Corning Inc filed Critical Corning Inc
Publication of WO2019178076A1 publication Critical patent/WO2019178076A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching

Definitions

  • the present disclosure relates generally to methods and apparatus for surface roughening and, more particularly, to methods and apparatus for production of anti-glare glass.
  • Anti-glare glass has attracted more interest recently due to the wide application of touch screen, especially for large-size interactive TV, electronic whiteboard, outdoor touch screen, and handheld touch panels.
  • Anti-glare properties are typically provided by creating a textured surface on the glass.
  • the textured surface reduces reflection of light through random scattering of the reflected light.
  • Textured surfaces can be produced by various methods, for example sandblasting, surface coating, plasma etching, wet chemical etching, and screen printing. Some methods may be too expensive or difficult to scale up for mass production. Yet, other methods may generate limited surface texture or roughness. Sparkle may also be of concern with textured surfaces produced by some methods. Sparkle is perceived as twinkling of images on a display where the anti-glare glass is used.
  • a plurality of dispensing ports may be arranged in the dipping tank to produce a plurality of etching slurry streams that promote mixing of the etching slurry and thereby provide a better distribution of insoluble material in the slurry that may otherwise settle to the bottom portion of an article reception area of the dipping tank. Due to the even distribution of insoluble material within the etching slurry provided by the plurality of etching slurry streams, uneven etching, pitting and other undesirable attributes that may result in undesired sparkle can be avoided. [0005]
  • Embodiment 1 An apparatus for producing anti-glare surfaces.
  • the apparatus can comprise a dipping tank.
  • the dipping tank can comprise an article reception area extending along an article insertion direction of the dipping tank.
  • a cross-sectional area of the article reception area taken perpendicular to the article insertion direction can comprise at least one peripheral side.
  • a projection of the at least one peripheral side in the article insertion direction circumscribes the article reception area.
  • the apparatus can further comprise a plurality of dispensing ports positioned within the dipping tank and spaced along the projection of the at least one peripheral side.
  • a resultant dispensing direction extending from each dispensing port of the plurality of dispensing ports can comprise a first directional component extending inwardly towards the article reception area.
  • Embodiment 2 The apparatus of embodiment 1, wherein the resultant dispensing direction extends at an angle of from about 30 to about 80 from a plane perpendicular to the article insertion direction.
  • Embodiment 3 The apparatus of any one of embodiments 1 and 2, wherein the plurality of dispensing ports comprises a first circuit of dispensing ports and a second circuit of dispensing ports.
  • Embodiment 4 The apparatus of embodiment 3, wherein the resultant dispensing direction extending from each dispensing port of the first circuit of dispensing ports comprises a second directional component extending in the article insertion direction.
  • Embodiment 5 The apparatus of any one of embodiments 3 and 4, wherein the resultant dispensing direction extending from each dispensing port of the second circuit of dispensing ports comprises a second directional component extending in an article extraction direction opposite the article insertion direction.
  • Embodiment 6 The apparatus of any one of embodiments 3-5, wherein the plurality of dispensing ports comprises a third circuit of dispensing ports.
  • Embodiment 7 The apparatus of embodiment 6, wherein the resultant dispensing direction extending from each dispensing port of the third circuit of dispensing ports comprises a second directional component extending in the article insertion direction.
  • Embodiment 8 The apparatus of any one of embodiments 1-7, further comprising a sub-tank and a pumping unit fluidly coupled to the dipping tank and the sub-tank.
  • Embodiment 9 The apparatus of embodiment 8, further comprising an agitator in the sub-tank.
  • Embodiment 10 The apparatus of any one of embodiments 1-9, further comprising an article carrier sized to be received within the article reception area.
  • the article carrier can be sized to be inserted into the article reception area by moving the article carrier in the article insertion direction.
  • Embodiment 11 A method for producing anti-glare surfaces with a dipping tank comprising an article reception area extending along an article insertion direction of the dipping tank.
  • a cross-sectional area of the article reception area taken perpendicular to the article insertion direction can comprise at least one peripheral side, wherein a projection of the at least one peripheral side in the article insertion direction circumscribes the article reception area.
  • the method can comprise dispensing an etching slurry stream along a resultant dispensing direction from each dispensing port of a plurality of dispensing ports positioned within the dipping tank and spaced along the projection of the at least one peripheral side.
  • Each resultant dispensing direction can comprise a first directional component extending inwardly towards the article reception area.
  • the method can further include inserting an article in the article insertion direction into the article reception area.
  • the article can be submerged beneath a free surface of etching slurry disposed within the dipping tank.
  • the method can further comprise roughening an exposed surface area of the article with the etching slurry while the article is submerged beneath the free surface of the etching slurry.
  • Embodiment 12 The method of embodiment 11, further comprising the step of extracting the article from the article reception area.
  • Embodiment 13 The method of any one of embodiments 11 and 12, wherein the dispensing the etching slurry stream along the resultant dispensing direction from each dispensing port of the plurality of dispensing ports is conducted: prior to inserting the article, while inserting the article, after inserting the article and/or while roughening of the exposed surface area.
  • Embodiment 14 The method of any one of embodiments 11-13, wherein the resultant dispensing direction extends at an angle of from about 30° to about 80° from a plane perpendicular to the article insertion direction.
  • Embodiment 15 The method of any one of embodiments 11-14, wherein the plurality of dispensing ports comprises a first circuit of dispensing ports and a second circuit of dispensing ports.
  • Embodiment 16 The method of embodiment 15, wherein the dispensing port of each of the first circuit of dispensing ports and the second circuit of dispensing ports is disposed below an upper 33% of a depth of the etching slurry within the dipping tank.
  • Embodiment 17 The method of any one of embodiments 15 and 16, wherein the resultant dispensing direction extending from each dispensing port of the first circuit of dispensing ports comprises a second directional component extending in the article insertion direction.
  • Embodiment 18 The method of any one of embodiments 15-17, wherein the resultant dispensing direction extending from each dispensing port of the second circuit of dispensing ports comprises a second directional component extending in an article extraction direction opposite the article insertion direction.
  • Embodiment 19 The method of any one of embodiments 15-18, wherein the plurality of dispensing ports comprises a third circuit of dispensing ports.
  • Embodiment 20 The method of embodiment 19, wherein the resultant dispensing direction extending from each dispensing port of the third circuit of dispensing ports comprises a second directional component extending in the article insertion direction.
  • Embodiment 21 The method of any one of embodiments 11-20, further comprising pumping etching slurry from a sub-tank to the dipping tank.
  • Embodiment 22 The method of embodiment 21, further comprising agitating the etching slurry in the sub-tank.
  • FIG. 1 is a schematic view of an apparatus for producing anti-glare surfaces in accordance with embodiments of the disclosure with an article positioned over a free surface of etching slurry disposed within a dipping tank;
  • FIG. 2 is another schematic view of the apparatus for producing anti glare surfaces of FIG. 1 with the article submerged beneath the free surface of the etching slurry;
  • FIG. 3 is a perspective view of an example dispensing apparatus shown in FIGS. 1 and 2;
  • FIG. 4 is a top view of the dipping tank and dispensing apparatus along line 4-4 of FIG. 1;
  • FIG. 5 is a cross-sectional end view of the dipping tank and dispensing apparatus taken along line 5-5 of FIG. 4;
  • FIG. 6 is a cross-sectional side view of the dipping tank and dispensing apparatus taken along line 6-6 of FIG. 4;
  • FIG. 7 is an example flow chart illustrating methods for producing anti-glare surfaces
  • FIG. 8 is a plot illustrating results from experiments measuring solid content in different areas of the dipping tank with and without use of a dispensing apparatus in the dipping tank.
  • FIG. 9 is a plot illustrating the standard deviation of the experiments of FIG. 8
  • Embodiments of apparatus and methods of the disclosure can produce anti-glare surfaces and can be applicable to materials (e.g., glass) having surfaces affected by glare.
  • materials e.g., glass
  • Other examples of materials that may be processed are glass- ceramics and other crystalline materials, and generally materials whose surfaces can be roughened by etching with an etching slurry. Etching with an etching slurry can be used to create textured surfaces on glass or other material. At least in the case of glass, the textured surfaces can provide the glass with the anti-glare properties.
  • Methods and apparatus of the disclosure are not limited to the production of anti-glare glass and may be applicable to other materials and that can be roughened by etching with an etching slurry.
  • FIG. 1 schematically illustrates an example embodiment of an apparatus 101 for producing anti-glare surfaces for an article 103 (e.g., one or more glass sheets).
  • the apparatus 101 can comprise a dipping tank 105 to hold an etching slurry 121 within an interior area 109 of the dipping tank 105.
  • the apparatus 101 can further include a dispensing apparatus 107 disposed within the interior area 109 of the dipping tank 105 to mix the etching slurry 121 within the dipping tank 105.
  • the apparatus 101 for producing anti-glare surfaces can comprise the dipping tank 105 and the dispensing apparatus 107 without other features illustrated in FIG. 1.
  • the apparatus 101 can be considered as the dipping tank 105, dispensing apparatus 107 and one or more of the additional features whether or not illustrated in FIG. 1.
  • the interior 109 of the dipping tank 105 can include an article reception area 401 represented in phantom lines. As shown in FIGS. 5 and 6, the article reception area 401 can extend in an article insertion direction 501 of the dipping tank 105.
  • the article reception area 401 is considered the area of the interior 109 that can receive an article 103, article carrier 111 and/or article rack 127 while inserting in the article insertion direction 501 (e.g., the illustrated linear article insertion direction 501) without physically contacting the dispensing apparatus 107.
  • the article insertion direction 501 e.g., the illustrated linear article insertion direction 501
  • a cross- sectional area 403 of the article reception area 401 taken perpendicular to the article insertion direction 501 can comprise at least one peripheral side 404a-d.
  • the cross-sectional area 403 of the article reception area 401 can be constant along the length of the article reception area 401 in the article insertion direction 501 and can comprise a footprint that is larger than a maximum footprint of the corresponding cross-sectional area of the article 103, article carrier 111 and/or article rack 127.
  • the article 103, article carrier 111 and/or article rack 127 can be inserted in the article insertion direction 501 without physically contacting the dispensing apparatus 107.
  • a projection 405a-d of the at least one peripheral side 404a-d of the cross-sectional area 403 corresponding to the above-referenced footprint of the cross-sectional area 403 may extend in the article insertion direction 501 and/or an article extraction direction 502 opposite the article insertion direction 501.
  • the projection 405a-d of the at least one peripheral side 404a-d in the article insertion direction 501 can circumscribe the article reception area 401.
  • the peripheral sides 404a-d of the cross-sectional area 403 of the article reception area 401 can define an enclosed area that can include a wide variety of shapes.
  • the peripheral sides can form a curvilinear shape (e.g., oblong shape, circular shape), a polygonal shape (e.g., triangular, rectangular) or other shape.
  • the peripheral sides 404a-d can comprise a rectangular shape including to parallel first and second sides 404a, 404b that are perpendicular to parallel third and fourth sides 404c, 404d.
  • Providing the article reception area 401 with rectangular shaped peripheral sides 404a-d can be designed to accommodate an article carrier 111 and/or article rack 127 designed to support the article 103 (e.g., one or more glass sheets) schematically shown in FIG. 1.
  • the article carrier 111 can be geometrically similar and smaller than the shape defined by the peripheral sides 404a-d of the article reception area 401 to permit a larger number of articles may be dipped by inserting the articles in the article insertion direction 501 without interfering with other components (e.g., dispensing ports) of the dispensing apparatus 107.
  • the dispensing apparatus 107 can further include a plurality of dispensing devices 407 that each include at least one dispensing port 409 such that a plurality of dispensing ports 409 may be positioned within the dipping tank 105 and spaced along the projection 405a-d of the at least one peripheral side 404a-d.
  • the dispensing port can comprise the opening at the end of a tube.
  • each dispensing device 407 can comprise a dispensing tube 410 with the opening at the end of the dispensing tube 410 comprising the dispensing port 409 of the dispensing device 407.
  • the interior cross-section taken perpendicular to a symmetrical longitudinal axis of the dispensing tube 410 can be substantially identical along the length of the dispensing tube 410.
  • the interior path may be shaped to produce a jet stream of fluid passing through the dispensing tube 410 to the opening at the end of the tube.
  • the dispensing tube 410 may include one or more side openings 408. The side openings 408, if provided, can allow mixing of etching slurry from the dipping tank 105 with the etching slurry flowing through the dispensing tube 410.
  • the etching slurry flowing through the dispensing tube 410 can cause a pressure drop at the side openings 408 due to a Venturi effect.
  • the pressure drop draws etching slurry from the dipping tank 105, through the side openings 408, and into the interior of the dispensing tube 410 to be entrained and further mixed prior to exiting the dispensing port 409.
  • the side openings 408 can help further homogenize etching slurry within the dipping tank 105.
  • a set of ports of the plurality of dispensing ports can be spaced along a length of the projection of the at least one peripheral side of the article reception area 401. Although not shown, one or more sides may only include one dispensing port or no dispensing port. In some embodiments, a set of ports of the plurality of dispensing ports can be spaced along a length of every side projection of the article reception area although the plurality of dispensing ports may be spaced along less than all the side projections of the article reception area. For instance, as shown in FIG.
  • the plurality of dispensing ports 409 can include a first set 411 of dispensing ports spaced apart along the length of the projection 405a of the first peripheral side 404a, a second set 413 of dispensing ports spaced apart along the length of the projection 405b of the second peripheral side 404b, a third set 415 of dispensing ports spaced apart along the length of the projection 405c of the third peripheral side 404c, and a fourth set 417 of dispensing ports spaced apart along the length of the projection 405d of the fourth peripheral side 404d.
  • Providing a plurality of dispensing ports that are spaced along a length of every side of the article reception area can help enhance homogenization of the etching slurry 121 and provide etching slurry streams that approach from each side of the article reception area 401.
  • the plurality of dispensing ports 409 can optionally comprise a plurality of circuits of dispensing ports that are connected in parallel with one another. Although two or more circuits of dispensing ports may be provided, a single circuit of dispensing ports may alternatively be provided in further embodiments. In one embodiment, as shown in FIGS. 1, 3, 5 and 6, the plurality of dispensing ports 409 can be arranged as a first circuit 113 of dispensing ports, a second circuit 115 of dispensing ports and a third circuit 117 of dispensing ports. A common fluid supply line 119 may connect the plurality of circuits 113, 115, 117 of dispensing ports in parallel with one another as shown in FIG. 1.
  • etchant slurry passing through the common fluid supply line 119 can be divided such that part of the etchant slurry passes through each of the plurality of circuits 113, 115, 117.
  • Providing multiple circuits can allow targeting of etchant slurry streams to different or overlapping depths of the dipping tank 105.
  • each circuit 113, 115, 117 can provide dispensing ports that are connected to one another by a fluid path that circumscribes the article reception area 401.
  • the first circuit 113 of dispensing ports 409 can be connected by a first conduit 301 that circumscribes the article reception area 401.
  • the second circuit 115 of dispensing ports 409 can be connected by a second conduit 303 that also circumscribes the article reception area 401.
  • the third circuit 117 of dispensing ports 409 can be connected by a third conduit 305 that also circumscribes the article reception area 401.
  • each circuit 113, 115, 117 can be provided with a respective inlet port 307 for fluid connection with the common fluid supply line 119.
  • each dispensing port 409 can contribute to defining a resultant dispensing direction 309 provided by the dispensing device 407.
  • the resultant dispensing direction can be the resultant vector of a laminar flow of water passing through the dispensing port that is submerged below a free surface of a body of water.
  • the flow vectors of each portion of the fluid flowing out of the dispensing port can be added to obtain the resultant flow vector of fluid flowing through the dispensing port, wherein the resultant directional vector of the resultant flow vector can be considered the resultant dispensing direction.
  • the dispensing device 407 comprises a linear circular cylindrical tube 410 with a dispensing port 409 having a cross-section perpendicular to a linear symmetrical axis of the circular cylindrical tube 410
  • the resultant dispensing direction can comprise a direction of the linear symmetrical axis of the tube 410.
  • the resultant dispensing direction 309 extending from each dispensing port 409 of the plurality of dispensing ports can comprise a first directional component 309a extending inwardly towards the article reception area 401.
  • Providing each first directional component 309a extending inwardly toward the article reception area 401 can help direct thorough mixing of etching slurry 121 in a direction toward the article placed within the article reception area 401.
  • inorganic material can be more thoroughly mixed and distributed throughout the etching slurry 121 and introduce the mixed etching slurry 121 to the article 103 within the article reception area 401 to provide consistent etching of the article within the article reception area 401.
  • the resultant dispensing direction 309 extending from each dispensing port 409 of the plurality of dispensing ports can comprise a second directional component 309b extending in either the article insertion direction 501 or an article extraction direction 502 opposite the article insertion direction 501.
  • one or more of the circuits 113, 115, 117 can include at least one dispensing port with a second component extending in the article insertion direction and at least another dispensing port with a second component extending in the article extraction direction.
  • the corresponding second directional component 309b of the dispensing ports 409 of each circuit 113, 115, 117 can all extend in the article insertion direction 501 or all extend in the article extraction direction 502.
  • Extending the second directional component 309b of all dispensing ports of each circuit 113, 115, 117 in the same direction can help target mixing objectives at various depth locations throughout a depth“D” of the etching slurry 121 within the tank. Due to gravity, it is believed that insoluble material tends to settle to the lower portion of the dipping tank 105. To avoid disproportionate accumulation of the insoluble material that the bottom of the dipping tank 105, the second directional component 309b of at least some or all of the dispensing ports of the third circuit 117 of dispensing ports can extend in the article insertion direction 501.
  • the downwardly directed streams of etching slurry from the dispensing ports 409 of the third circuit 117 can be effective to sweep insoluble material off the bottom of the dipping tank 105 and promote etchant slurry currents in the dipping tank 105 that can be effective to lift the insoluble material toward a central depth band“Dl” of the depth“D” of the etching slurry 121 within the dipping tank 105.
  • the dispensing ports 409 can be located within a lower depth band“D2” that may be lowest 25% of the depth“D” of the etching slurry.
  • the second directional component 309b of at least some or all of the dispensing ports of the second circuit 115 of dispensing ports can extend in the article extraction direction 502 that can be opposite the article insertion direction 501.
  • the dispensing ports 409 of the second circuit 115 of dispensing ports can each be located within the central depth band“Dl” below the upper 33% of the depth“D” of the etching slurry 121 within the dipping tank 105.
  • the central depth band“Dl” is located below the upper 33% of the depth“D” and above the lower 33% of the depth“D” of the etching slurry 121 within the dipping tank 105.
  • the upwardly directed streams of etching slurry from the dispensing ports 409 of the second circuit 115 can be effective to promote a current of etching material including insoluble material to the upper 33% of the depth “D” of the etching slurry 121 within the dipping tank 105.
  • the second directional component 309b of at least some or all of the dispensing ports 409 of the first circuit 113 of dispensing ports can extend in the article insertion direction 501.
  • the dispensing ports 409 of the first circuit 113 of dispensing ports can each be located within the central depth band“Dl” below the upper 33% of the depth“D” of the etching slurry 121 within the dipping tank 105.
  • the central depth band “Dl” can be located below the upper 33% of the depth“D” and above the lower 33% of the depth“D” of the etching slurry 121 within the dipping tank 105.
  • the downwardly directed streams of etching slurry from the dispensing ports 409 of the first circuit 113 can be effective to promote a current of etching material including insoluble material from the upper 33% of the depth“D” of the etching slurry 121 toward a lower depth of the dipping tank 105.
  • the dispensing ports 409 from the first circuit 113 can be laterally misaligned with the dispensing ports 409 from the second circuit 115 in a direction perpendicular to the article insertion direction 501.
  • Providing lateral misalignment can avoid direct conflict of oppositely directed streams of etching slurry and thereby promote flows of etching slurry in opposite directions that are laterally disposed with one another, thereby providing circulation of some etching slurry between the opposing flows of etching slurry to provide mixing of insoluble material within the etching slurry.
  • each resultant dispensing direction 309 of each dispensing port 409 of the plurality of dispensing ports can extend at an angle from about 30° to about 80° from a plane 503 perpendicular to the article insertion direction 501.
  • each resultant dispensing direction 309 of each dispensing port 409 of the first set 411 and second set 413 of dispensing ports of the first circuit 113, second circuit 115 and third circuit 117 can extend at an angle“A” within a range of from about 30° to about 80°, for example from about 60° to about 80°, for example about 80°.
  • each resultant dispensing direction 309 of each dispensing port 409 of the first set 411 and second set 413 of dispensing ports can extend at the same angle“A” although different angles may be provided in further embodiments.
  • Increasing the angle“A” to a range of from about 60° to about 80°, for example about 80° can increase the quantity of the etching slurry stream being sent along the second directional component 309b (i.e., the article insertion direction 501 or article extraction direction 502) while also increasing the size of the article reception area 401.
  • each resultant dispensing direction 309 of each dispensing port 409 of the third set 415 and fourth set 417 of dispensing ports of the first circuit 113, second circuit 115 and third circuit 117 can extend at an angle“B” within a range of from about 30° to about 80°, for example from about 30° to about 60°, for example about 45°.
  • the angle“B” of each resultant dispensing direction 309 of each dispensing port 409 of the third set 415 and fourth set 417 of dispensing ports can extend at the same angle“B” although different angles may be provided in further embodiments.
  • Decreasing the angle“B” to a range of from about 30° to about 60°, for example about 45° can increase the quantity of the etching slurry stream being sent along the first directional component 309a (i.e., inwardly towards the article reception area 401).
  • an article carrier 111 is provided and sized to be moved in the article insertion direction 501 to be received within the article reception area 401 as shown in FIG. 2.
  • the outer frame of the article carrier 111 can be smaller than the article reception area 401 as shown in FIG. 4 such that the article carrier 111 can be inserted into the article reception area 401.
  • the article carrier 111 can be moved in the article insertion direction 501 such that a mounting surface 125 of the article carrier 111 is moved from outside of the dipping tank 105 (see FIG. 1), through an opening in the upper portion of the dipping tank 105, beneath a free surface 123 of the etching slurry 121, through an upper opening of the article reception area 401, and into the article reception area 401 as shown in FIG. 2.
  • an article holder for example an article rack 127 may be mounted to the article carrier 111 to allow the article 103 (i.e., one or a plurality of articles) to be carried by the article carrier 111.
  • the article rack 127 can support the article 103 (e.g., one or a plurality of glass sheets) and may optionally be mounted to the mounting surface 125 to move together with the article carrier 111.
  • the apparatus 101 can optionally include a sub-tank 129 that can include etching slurry 121.
  • a pumping unit can be fluidly coupled to the dipping tank 105 and the sub-tank 129 to provide fluid circulation between the dipping tank 105 and the sub-tank 129.
  • the pumping unit can include a single or multiple fluid pumps. For instance, as shown in FIGS.
  • the pumping unit can comprise a first slurry pump 131 that may draw etching slurry from a drain line 135 fluidly connected to a drain of the dipping tank 105 and through the flow line 137 and the common fluid supply line 119 to be dispensed in the dipping tank 105 with the dispensing apparatus 107.
  • the drain line 135 can further return etching slurry 121 from the dipping tank 105 to the sub-tank 129.
  • a valve 139 may be arranged in the drain line 135 to control the amount, if any, of the etching slurry 121 that is drained from the drain line 135 the etching slurry dipping tank 105 into the etching slurry sub-tank 129.
  • the valve 139 may be closed such that all of the etching slurry 121 is self-circulated back to the dipping tank 105 by way of first slurry pump 131 and dispensing apparatus 107.
  • the term "self-circulate" as used relative to the dipping tank 105 means that the etching slurry is pumped from the dipping tank 105 back into the dipping tank 105.
  • the valve 139 may be partially or entirely opened to drain at least a portion of the etching slurry from the drain of the dipping tank 105 to the sub-tank 129.
  • the pumping unit can also include at least one second slurry pump 133. As shown in FIGS. 1 and 2, the at least one second slurry pump 133 can be arranged to pump the etching slurry 121 from the sub-tank 129 to the etching slurry dipping tank 105.
  • the at least one second slurry pump 133 can also self-circulate the slurry of etching slurry 121 in the sub-tank 129.
  • the term "self-circulate" as used relative to the sub-tank 129 means that the etching slurry is pumped from the sub-tank 129 back into the sub-tank 129. Pumping of the etching slurry 121 into the etching slurry dipping tank 105 and self-circulation of the slurry of etching slurry 121 in the sub-tank 129 may or may not occur concurrently.
  • the at least one second slurry pump 133 may have one or more pumps.
  • the at least one second slurry pump 133 is shown with a single second slurry pump 141.
  • a suction end 143 of the second slurry pump 141 is connected to the sub-tank 129 via a flow line 145 and a discharge end 147 of the second slurry pump 141 is connected to the dipping tank 105 and sub-tank 129 via flow lines 149, 151, respectively.
  • Valves 153 may be positioned in the flow lines 149, 151 to determine which of the etching slurry dipping tank 105 and etching slurry sub-tank 129 will receive etching slurry from the pump discharge end 147 at any given time. If more than one pump is included in the at least one second slurry pump 133, then one pump could be dedicated to pumping the etching slurry 121 from the sub-tank 129 to the etching slurry dipping tank 105 while another pump could be dedicated to self-circulating the etching slurry 121 in the sub-tank 129.
  • the flow line 149 can be designed to introduce etching slurry 121 from the sub-tank 129 to the dipping tank 105 without passing through the dispensing apparatus 107.
  • the flow line 149 can be connected to the common fluid supply line 119 to introduce fluid from the sub-tank 129 to the dipping tank 105 by way of the dispensing apparatus 107.
  • a valve may be provided to split the flow or allow selective flow from the sub-tank 129 to the dipping tank 105 to allow selective flow to be introduced directly to the sub-tank 129 (i.e., without the dispensing apparatus 107) or to allow selective flow to be introduced to the sub-tank 129 by the dispensing apparatus 107.
  • the sub-tank 129 may include an agitator 155 to stir the etching slurry 121 in the sub-tank 129.
  • the agitator 155 may be a mechanical device for example a paddle, impeller that may be rotated about a rotation axis to stir and thereby mix the etching slurry 121 in the sub-tank 129.
  • a motor 157 may be coupled to the agitator 155 to provide the rotation of the agitator 155.
  • Both the self-circulation of the etching slurry 121 in the sub-tank 129 and the motion of the agitator 155 can act to homogenize the etching slurry 121 in the sub-tank 129.
  • This homogenized etching slurry 121 can then be transferred to the etching slurry dipping tank 105 at the desired time.
  • the dispensing apparatus 107 can still further homogenize the etching slurry 121 within the dipping tank 105 to provide uniform etching fluid composition acting to uniformly etch surfaces of the article being dipped in the dipping tank 105.
  • a filter 159 may be arranged to remove large particles and agglomerates formed in the circulating etching slurry 121.
  • the filter 159 may include one or more filters made of materials for example nylon or other suitable filter material.
  • a similar filter may be provided in the common fluid supply line 119 to filter material being drained from the dipping tank 105 prior to being dispensed with the dispensing apparatus 107 back into the dipping tank 105.
  • Temperature sensors 161 may be arranged to sense the temperature of the etching slurry 121 in the sub-tank 129.
  • One or more heating devices 163 may be arranged to provide heat to the sub-tank 129 as needed such that the temperature of the etching slurry 121 in the sub-tank 129 is maintained at a desired range suitable for the etching slurry etching of glass.
  • the heating device 163 may be controlled using the output of the temperature sensors 161.
  • a controller unit 165 may receive data from the temperature sensors 161 and then send appropriate commands to the heating device 163 to adjust the output of the heating device 163. Cooling devices may also be used to assist in maintaining the desired temperature range for the etching slurry.
  • FIG. 7 is an example flow chart 701 illustrating methods for producing anti-glare surfaces for the article 103.
  • Various methods can begin at 703, for example with the article 103 (e.g., a single article or a plurality of articles).
  • the article with one or more surface areas to be roughened e.g., to provide an anti-glare surface).
  • the article can comprise a glass article, a glass-ceramic article.
  • the article can comprise a glass sheet or a glass-ceramic sheet.
  • the article can begin at 703 without any substantial anti-glare properties.
  • the article beginning at 703 can optionally begin without having been previously subjected to strengthening with an ion-exchange process since roughening the article surface may reduce the benefits achieved with the ion-exchange process.
  • the method can proceed to the step 705 of producing anti-glare surfaces with the dipping tank 105 as discussed more fully above with respect to FIGS. 1-6.
  • the dipping tank 105 can comprise the article reception area 401 extending along the article insertion direction 501 of the dipping tank 105.
  • the cross-sectional area 403 of the article reception area 401 taken perpendicular to the article insertion direction 501 can comprise the at least one peripheral side 404a-d.
  • the projection 405a-d of the at least one peripheral side 404a-d in the article insertion direction 501 can circumscribe the article reception area 401.
  • Step 705 can include inserting the article 103 in the article insertion direction 501 into the article reception area 401. As shown in FIG. 2, once inserted, the article 103 can be submerged beneath the free surface 123 of etching slurry 121 disposed within the dipping tank 105.
  • Embodiments of the disclosure can provide the article 103 can comprise a single article although the article 103 can comprise the illustrated plurality of articles. In some embodiments, the article can be inserted, for example, with the article carrier 111.
  • Step 705 further includes roughening an exposed surface area of the article 103 with the etching slurry 121 while the article 103 is submerged (i.e., at least partially or entirely submerged) beneath the free surface 123 of the etching slurry.
  • the etching slurry may include various compositions that may depend on the composition of the article 103 to be etched.
  • the etching slurry 121 can include insoluble salts or filler suspended in the etchant.
  • the etching slurry 121 may contain several fluorine salts, some insoluble salts, and some soluble salts. In some embodiments, these salts may be dissolved or suspended in mineral acid to form an etching slurry.
  • the fluorine salts can be the primary etchants in the etching slurry and can act to etch and roughen exposed surface areas of a glass article.
  • an etching slurry 121 is composed of 10-20 wt % ammonium fluoride (NH 4 F) and ammonium hydrogen difluoride (NH4HF2) as fluoride salts, 0-10 wt % potassium nitrite (KNO3) as additional salt, 5-20 wt % barium sulfate (BaS0 4 ) as filler, 1-10 wt % soluble starch, and 0-5 wt % polyacrylamide, with hydrochloric acid (HC1) used as the mineral acid.
  • NH 4 F ammonium fluoride
  • NH4HF2 ammonium hydrogen difluoride
  • KNO3 potassium nitrite
  • BaS0 4 barium sulfate
  • HC1 hydrochloric acid
  • the article 103 may be left submerged beneath the free surface 123 of the etching slurry 121 within the dipping tank 105 for a time period until sufficient surface roughening has occurred (or has expected to have occurred). Once the time period has elapsed, the article 103 may be extracted from the article reception area 401, for example, by moving the article in the article 103 in the article extraction direction 502.
  • the step 705 can further include dispensing an etching slurry stream along the resultant dispensing direction 309 from each dispensing port 409 of the plurality of dispensing ports positioned within the dipping tank 105 and spaced along the projection 405a-d of the at least one peripheral side 404a-d.
  • the resultant dispensing direction of each etching slurry stream can extend at an angle from a plane perpendicular to the article insertion direction with a first directional component 309a that extends inwardly toward the article reception area 401.
  • some embodiments can provide the angle “A”, “B” within a range from about 30° to about 80° from the plane 503 perpendicular to the article insertion direction 501.
  • the directional vector of the resultant dispensing direction 309 of each dispensing port 409 can provide a stream of etching slurry 121 in the direction of the article 103 within the article reception area 401 to enhance flow of homogenized etching slurry toward the surfaces of the article 103 to be roughened. Consequently, due to the streams of etching slurry 121, a more thorough and consistent etching can be achieved across the area of the surface to be roughened.
  • Dispensing the etching slurry stream along the resultant dispensing direction 309 from each dispensing port 409 of the plurality of ports can be conducted during various time periods. For instance, dispensing of the etching slurry streams can be conducted prior to inserting the article 103. In such embodiments, a more homogeneous mixing of etching slurry 121 can be achieved to provide a more even distribution of inorganics prior to inserting the article 103 into the article reception area 401.
  • dispensing the etching slurry streams can be conducted while inserting the article 103 into the article reception area 401, while roughening the exposed surface area of the article within the article reception area 401, and/or while extracting the article 103 from the article reception area 401 to allow a more homogenized etching stream to contact the surfaces to be roughened and also direct homogenized etching streams inwardly toward the article to consistently provide a source of homogenized etching slurry to contact the surfaces of the article to be roughened.
  • enhanced homogenization of etching slurry 121 within the dipping tank 105 and more even exposure of homogenized etching slurry 121 to all surfaces of the article to be roughened can be achieved by arranging the etching slurry streams to be dispensed from a plurality of dispensing ports arranged in a first circuit 113 of dispensing ports, a second circuit 115 of dispensing ports and/or a third 117 circuit of dispensing ports.
  • the circuits 113, 115, 117 of dispensing ports can be located below an upper 33% of the depth of the etching slurry 121 within the dipping tank 105.
  • the depth of the etching slurry 121 is considered the greatest distance between the free surface 123 of the etching slurry 121 within the dipping tank 105 and a lower wall of the dipping tank. Positioning the circuits below the upper 33% of the depth of the etching slurry within the dipping tank can help agitate lower depths of etching slurry to help prevent settling of insoluble material into the lower portions of the dipping tank due to gravity.
  • each resultant dispensing direction 309 can include the first directional component 309a to encourage etching slurry flow in the direction of the article 103 within the article reception area 401.
  • resultant dispensing direction 309 extending from each dispensing port 409 of the third circuit of dispensing ports comprises the second directional component 309b extending in the article insertion direction 501 to help sweep insoluble material from the bottom of the dipping tank 105 that may otherwise accumulate under the influence of gravity.
  • the resultant dispensing direction 309 extending from each dispensing port 409 of the second circuit of dispensing ports comprises the second directional component 309b extending in the article extraction direction 502 to help move insoluble material swept from the bottom of the dipping tank 105 towards the upper 33% of the depth of the etching slurry within the dipping tank 105.
  • the resultant dispensing direction 309 extending from each dispensing port 409 of the first circuit of dispensing ports comprises the second directional component 309b extending in the article insertion direction 501 to help mix the insoluble material and promote movement of the insoluble material from the upper 33% of the depth of the etching slurry to lower depths of the etching solution within the dipping tank 105.
  • the etching slurry streams from the first circuit 113 may be offset laterally from the etching slurry streams of the second circuit 115 to promote a tortuous current flow to further promote random distribution of insoluble material within the etching slurry 121 contained within the dipping tank 105.
  • the dispensing apparatus 107 can help prevent settling of insoluble material at the bottom of the dipping tank 105.
  • further agitation may be achieved by way of a movement device 167.
  • the movement device 167 to provide any combination of vertical, horizontal, rotational, and vibrational motions to the article carrier 111 to provide relative movement between the etching slurry 121 and the article 103 within the article carrier 111 to promote introduction of fresh etching slurry to the surface of the article to be roughened.
  • the movement device 167 may be designed to lift and drop the article carrier 111 in a specialized frequency and amplitude, for example 10 cycles/minute at 100 mm stroke. Similar movement devices may be provided in other processing steps that may be provide in addition to step 705 shown in FIG. 7.
  • the optional sub-tank 129 may be provided, wherein step 705 can include cycling etching slurry 121 from the dipping tank 105, through the sub-tank 129 and then back to the dipping tank 105.
  • the etching slurry 121 within the sub- tank may be agitated (e.g., via agitator 155) to homogenize the etching slurry within the sub-tank 129. Agitating the etching slurry in the sub-tank 129 can provide a homogenized etching slurry that can be reintroduced into the dipping tank 105.
  • the article 103 can comprise a plurality of articles supported by article rack 127.
  • the article 103 can comprise a glass sheet or a plurality of glass sheets.
  • the article carrier 111 carrying the article rack 127 and article 103 can be lowered in article insertion direction 501 until the article rack 127 and article 103 is submerged (e.g., entirely submerged) below the free surface 123 of the etching slurry 121 and positioned within (e.g., entirely within) the article reception area 401.
  • the etching slurry 121 may optionally be allowed to self-circulate in the sub-tank 129 for a predetermined time period.
  • the valve 153 in flow line 151 can be at least partially open while the at least one second slurry pump 133 self-circulates fluid through flow lines 145, 151.
  • the agitator 155 may be activated to agitate etching slurry 121 within the sub-tank 129.
  • valve 153 of flow line 149 may be at least partially opened to allow the at least one second slurry pump 133 to reintroduce homogenized etching slurry 121 from the sub-tank 129 to the dipping tank 105.
  • the article carrier 111 with the article 103 can be dipped or immersed in the etching slurry within the article reception area 401 of the etching slurry dipping tank 105.
  • the etching slurry 121 may optionally be allowed to self-circulate in the dipping tank 105 for a time period.
  • the first slurry pump 131 may self-circulate fluid through the flow line 137 from the drain line 135 and through the dispensing apparatus 107 from the common fluid supply line 119.
  • the self-circulation of etching slurry 121 in the dipping tank 105 can improve homogeneity and prevent settling of insoluble material from the etching slurry 121.
  • the article carrier 111 with the article 103 can be dipped or immersed in the etching slurry with in the article reception area 401 of the etching slurry dipping tank 105.
  • the temperature sensor(s) 161, heating device(s) 163, at least one second slurry pump 133, and valve(s) 153, 139 may receive commands from the controller unit 165.
  • the controller unit 165 may include program instructions which when executed will cause self-circulation and agitation of the etching slurry 121 in the sub-tank 129 for an appropriate period time, followed by transfer of the etching slurry 121 from the sub-tank 129 to the dipping tank 105 at the appropriate time, followed by draining of the etching slurry 121 from the dipping tank 105 to the sub-tank 129 at the appropriate time.
  • the controller unit 165 can send commands to the first slurry pump 131.
  • the controller unit 165 may include program instructions which when executed will cause self-circulation and agitation of the etching slurry 121 in the dipping tank 105 for an appropriate time period.
  • the controller unit 165 may optionally operate a robot (not shown) to carry the article carrier 111 and dip the article carrier 111 including the article 103 into the dipping tank 105 at the appropriate time.
  • the motion of the robot can be synchronized with the self-circulation of the etching slurry 121 in the sub-tank 129 and/or the dipping tank 105 such that the article carrier 111 is dipped in the etching slurry dipping tank 105 at optimum conditions for the etching slurry 121 to etch surfaces of the article 103.
  • FIG. 8 is a plot illustrating results from experiments measuring solid content in different areas of the dipping tank with and without operating a dispensing apparatus in the dipping tank.
  • reference numeral 801U represents a data set of solid content measured in an upper portion of the dipping tank 105 while using the dispensing apparatus
  • 803U represents a data set of solid content measured in the upper portion of the dipping tank 105 without using the dispensing apparatus 107.
  • Reference numeral 801C represents a data set of solid content measured in a central portion of the dipping tank 105 while using the dispensing apparatus while 803C represents a data set of solid content measured in the central portion of the dipping tank 105 without using the dispensing apparatus 107.
  • Reference numeral 801B represents a data set of solid content measured in a bottom portion of the dipping tank 105 while using the dispensing apparatus while 803B represents a data set of solid content measured in the bottom portion of the dipping tank 105 without using the dispensing apparatus 107.
  • The“dash” symbol indicated at reference number 805 represents Ql of the data set (i.e., the middle value in the upper half of the rank-ordered solid content data set) and the“dash” symbol referenced at 807 represents Q3 of the data set (i.e., the middle value in the lower half of the ranked-ordered solid content data set).
  • the dash 805 appears at the upper end of the cross-hatched bar while the dash 807 appears at the lower end of the cross-hatched bar.
  • the upper letter“X” indicates the maximum solid content measured in the data set while the lower letter“X” (see the letter“X” 811 in the key) indicates the minimum solid content measured in the data set.
  • the“+” sign indicates the median solid content measured in the data set.
  • the median value 813 (represented by the“+” symbol), when compared to the data sets 803U, 803C, 80 IB, the median value of the solid content is relatively close together in the data sets 801U, 801C, 801B that was measured while using the dispensing apparatus.
  • the evidence suggests that median value of solid content within the etching slurry can be more evenly distributed between the upper, central and lower areas of the dipping tank when using the dispensing apparatus 107.
  • FIG. 9 is a plot illustrating the standard deviation of the experiments of FIG. 8.
  • reference numbers 901U, 901C, 901B, 903U, 903C, 903B indicate the corresponding standard of deviation of the data sets 801U, 801C, 801B, 803U, 803C, 803B, respectively.
  • the corresponding standard deviation of each of the data sets 801U, 801C, 801B are lower than each standard of deviation of each of the data sets 803U, 803C, 803B.
  • more uniformity is achieved using the dispensing apparatus 107 in the upper, central and bottom areas of the dipping tank 105 than any area of the tank that does not use the dispensing apparatus 107.
  • the uniformity achieved at the bottom area of the tank using the dispensing apparatus 107 is many orders of magnitude greater than uniformity achieved at the bottom area of the tank that does not use the dispensing apparatus. 107.
  • yield can be adversely affected by cosmetic defects, for example stripes, white smudges, pinholes, etc. These cosmetic defects can come from the non-uniformity of the etching slurry 121 during dipping the article 103. These cosmetic defects may lead to non-uniform anti-glare feature size and feature size distribution on the article surface (e.g., glass surface) that may result in a high sparkle level.
  • cosmetic defects for example stripes, white smudges, pinholes, etc.
  • These cosmetic defects can come from the non-uniformity of the etching slurry 121 during dipping the article 103. These cosmetic defects may lead to non-uniform anti-glare feature size and feature size distribution on the article surface (e.g., glass surface) that may result in a high sparkle level.
  • cosmetic defects on the article surface may be significantly reduced, thereby increasing yield and lowering level of undesirable features (e.g., lowering the sparkle level of an anti-glare glass sheet or other article).
  • step 709 of pre-etching the article 103 may be briefly exposed to an acid solution.
  • the acid solution used during step 709 may be, for example, a diluted mixture of hydrofluoric acid (HF) and hydrochloric acid (HC1), or other type of acid solution.
  • HF hydrofluoric acid
  • HC1 hydrochloric acid
  • the method may proceed to a cleaning step 711 as indicated by arrow 712.
  • the cleaning step can include rinsing with deionized water.
  • the cleaning step can include washing the article with a detergent and then cleaning the article in an ultrasonic bath with deionized water.
  • the method may also begin with a cleaning step to pre-clean the article to remove surface contaminants from the article 103.
  • Pre- cleaning of the article 103 may involve a first cleaning of the article with a detergent, followed by a further cleaning of the article in an ultrasonic bath with deionized water. Other suitable methods may optionally be used to pre-clean the article as desired.
  • the method may proceed to step 705 of slurry etching as indicated by arrow 715.
  • the article may alternatively be pre-cleaned prior to the pre-etching step 709.
  • step 705 the article 103 may be dipped by submerging the article (e.g., partially, entirely) underneath the free surface of the etching slurry 121 for a predetermined period (e.g., 30 seconds to 120 seconds). After step 705, as indicated by arrow 706, the process may end at 707.
  • a predetermined period e.g. 30 seconds to 120 seconds
  • the method may proceed to a cleaning step 716 as indicated by arrow 718 to remove the etching slurry from the surfaces of the article.
  • the cleaning step can include dipping the article in a washing tank and/or passing the article through a spray washing tank.
  • the process may end at 707 after cleaning step 716.
  • the process may proceed to a post- etching step 720.
  • the optional post-etching step can include submerging the article 103 in a post-etching acid solution for possibly several minutes.
  • the post-etching acid solution may be, for example, a mixture of hydrofluoric acid (HF) and hydrochloric acid (HC1).
  • the concentration of the acid solution used in the post- etching step 720 may or may not be the same as the concentration of the acid solution used in the pre-etching step 709.
  • the article 103 may optionally be processed to neutralize acid on the article during step 721 as indicated by arrow 722.
  • the article 703 may be submerged in an alkaline solution for a few seconds to neutralize any residual etching slurry on the article 103.
  • the process may then conclude as indicated by arrow 706 or optionally proceed to cleaning step 723 as indicated by arrow 724.
  • the cleaning step 723, if provided, can clean alkaline solution from the surfaces of the article 103 to complete the process as indicated by arrow 706 or proceed to the post-etching step 720 as indicated by arrow 725.
  • the article may be cleaned during step 726 prior to completing the process at 707.
  • the article 103 may be rinsed and cleaned with deionized water thoroughly and then dried (e.g., in air).
  • the resulting article can include anti-glare properties and can be used in applications requiring anti-glare properties.
  • the glass article may be subject to strengthening by way of an ion-exchange process or other technique.
  • portions of the exposed surface of the article may be provided with an acid-resistant film to act as a mask to prevent etching on certain surfaces of the article.
  • acid-resistant films can comprise a polymer (e.g., polyethylene) or other suitable material that will be resistant to the various etchants involved in the etching process.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

La présente invention concerne un appareil de production de surfaces antireflets qui comprennent chacune un réservoir d'immersion et une pluralité d'orifices de distribution positionnés dans le réservoir d'immersion et espacés le long d'une partie saillante d'au moins un côté périphérique d'une zone de réception d'article. Un sens de distribution ainsi obtenu, prenant naissance au niveau de chaque orifice de distribution de la pluralité d'orifices de distribution, peut comprendre un premier élément directionnel s'étendant vers l'intérieur vers la zone de réception d'article. Dans des modes de réalisation supplémentaires, des procédés de production de surfaces antireflets peuvent consister à distribuer un flux de suspension de gravure dans le sens de distribution obtenu comprenant un premier élément directionnel s'étendant vers l'intérieur vers la zone de réception d'article du réservoir d'immersion. Les procédés peuvent en outre consister à mousser une zone de surface à nu de l'article inséré dans la zone de réception d'article avec la suspension de gravure pendant que l'article est immergé sous une surface libre de la suspension de gravure.
PCT/US2019/021819 2018-03-16 2019-03-12 Procédés et appareil de production de surfaces antireflets Ceased WO2019178076A1 (fr)

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CN201810219197.6A CN110272210A (zh) 2018-03-16 2018-03-16 产生防眩光表面的方法和设备
CN201810219197.6 2018-03-16

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CN111499212B (zh) * 2020-05-25 2022-07-12 福建和达玻璃技术有限公司 高效率小尺寸屏幕盖板玻璃防眩处理设备及方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6071374A (en) * 1996-06-26 2000-06-06 Lg Electronics Inc. Apparatus for etching glass substrate
US20030057180A1 (en) * 2001-09-25 2003-03-27 Kim Jong Soo Bubble plate for etching and etching apparatus using the same
US20080135176A1 (en) * 2006-12-08 2008-06-12 Sang-Min Park Apparatus for etching substrate and fabrication line for fabricating liquid crystal display using the same
US20090039054A1 (en) * 2007-04-10 2009-02-12 Samsung Electronics Co., Ltd. Etching apparatus of glass substrate for flat panel display and method of ectching glass substrate for flat panel display using the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6071374A (en) * 1996-06-26 2000-06-06 Lg Electronics Inc. Apparatus for etching glass substrate
US20030057180A1 (en) * 2001-09-25 2003-03-27 Kim Jong Soo Bubble plate for etching and etching apparatus using the same
US20080135176A1 (en) * 2006-12-08 2008-06-12 Sang-Min Park Apparatus for etching substrate and fabrication line for fabricating liquid crystal display using the same
US20090039054A1 (en) * 2007-04-10 2009-02-12 Samsung Electronics Co., Ltd. Etching apparatus of glass substrate for flat panel display and method of ectching glass substrate for flat panel display using the same

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