JP2019006621A - Glass surface treatment device - Google Patents

Abstract

To provide a glass surface treatment device capable of performing surface treatment of a glass substrate with a simple method and capable of being produced in a continuous production.SOLUTION: A spray etching device 10 comprises: a frosting processing chamber 18; a first cleaning chamber 20; an etching chamber 22; and a second cleaning chamber 24. The frosting processing chamber 18 brings a processing mixed liquor obtained by mixing at least any one of a granular silicofluoride salt and fluoride salt which are insoluble to an etchant and the etchant including hydrofluoric acid, into contact with a transported glass substrate 1100, for forming irregularities on a surface of the glass. An etching chamber 22 brings an etchant including hydrofluoric acid into contact with the glass substrate 100 which passed the frosting processing chamber 18, for performing etching processing to the glass substrate 100.SELECTED DRAWING: Figure 7

Description

  The present invention relates to a glass surface treatment apparatus configured to roughen the surface of a glass substrate.

  Conventionally, in an image display device such as a liquid crystal display or an organic EL display, a film having an antireflection characteristic has been used in order to prevent reflection or reflection of external light on a display surface. Such a film has irregularities formed on the surface so that reflected light can be diffused. In recent years, in order to improve light transmittance, there is an increasing demand for processing directly on a glass substrate without using a film. Those directly processed on a glass substrate are used not only for image display devices but also for solar panels and the like.

  Examples of the method of directly processing the glass substrate include a method of making the surface uneven by physical force, a method of adjusting the haze of the surface by etching, and the like. Among conventional techniques, there is one that forms irregularities by roughening the surface by sandblasting and etching with an etching solution such as hydrofluoric acid (see, for example, Patent Document 1).

JP 2004-82285 A

  However, it is considered that the method of processing by sandblasting as in Patent Document 1 is difficult to cope with a large glass substrate. The reason for this is that in order to uniformly process a large glass substrate, it is necessary to control so that the nozzles for injecting the blasting material are sequentially scanned over the glass substrate so that uniform processing is performed on the entire area of the glass substrate. Because there is. Furthermore, there is a disadvantage that the processing time becomes longer as the substrate size increases.

  In addition, it is considered difficult to use the sandblasting apparatus in combination with an apparatus that performs continuous processing. The reason for this is that if dust such as blast material enters the transport gear portion of a transport mechanism such as a transport roller or a belt conveyor, there is a high possibility of causing a transport trouble. Further, it may be necessary to provide a large cleaning process for preventing dust from adversely affecting the subsequent process.

  An object of the present invention is to provide a glass surface treatment apparatus capable of continuous production and capable of surface treatment of a glass substrate by a simple method.

  The glass surface treatment apparatus according to the present invention is configured to perform a surface treatment on plate-like glass that is sequentially conveyed between a carry-in portion and a discharge portion. The surface processing apparatus includes at least a first processing chamber, a first cleaning chamber, a second processing chamber, and a second cleaning chamber.

  The first processing chamber includes a processing liquid mixture in which at least one of an etching solution containing hydrofluoric acid and a granular silicofluoride salt or a fluoride salt insoluble in the etching solution is mixed with the glass to be conveyed. It is comprised so that an unevenness | corrugation may be formed in the surface of glass by making it contact. In an etching process using only a normal etching solution, it is difficult to form sufficiently large irregularities on the glass surface, but a processing mixed solution in which granular silicofluoride salt insoluble in the etching solution is mixed is used. As a result, the silicofluoride salt covering the glass surface provides a masking effect, and the glass surface is etched unevenly. And sufficiently large unevenness is formed on the glass surface.

  The first cleaning chamber is configured to clean the glass that has passed through the first processing chamber. The purpose of cleaning in this first cleaning chamber is to remove silicofluoride and fluoride salts covering the glass surface.

  The second processing chamber is configured to etch the glass by bringing an etching solution containing hydrofluoric acid into contact with the glass that has passed through the first cleaning chamber. By further etching the glass on which the unevenness is formed in the first processing chamber, the uneven shape on the glass surface can be appropriately adjusted to a desired shape, or the glass can be thinned.

  The second cleaning chamber is configured to clean the glass that has passed through the second processing chamber. In the second processing chamber, all the chemical solution adhering to the glass discharged to the outside of the apparatus is washed away.

  In this configuration, irregularities are formed on the surface of the glass by the processing liquid mixture in the first processing chamber, and the adjustment of the irregularities and the adjustment of the glass thickness are continued in the second processing chamber located at the subsequent stage. Done. For this reason, it becomes possible to perform the surface treatment of glass efficiently in a single apparatus.

  In the above-described configuration, it is preferable to further include means for recovering at least one of the silicofluoride salt or the fluoride salt generated in the second processing chamber and supplying the recovered salt to the first cleaning chamber. By adopting this configuration, it is possible to effectively utilize silicic fluoride salt, which is an unnecessary substance, in the first cleaning chamber in the etching process of the second processing chamber. In particular, since the silicofluoride salt can be recovered and transported through a path in a single apparatus, it is easy to save resources, reduce the acid atmosphere isolation range, save space, and the like.

  Moreover, it is preferable to further include an adding means for adding potassium fluoride and sodium fluoride to the processing mixture. By performing etching in the presence of sodium silicofluoride and potassium silicofluoride, the siliceous fluoride salt and fluoride salt that easily adhere to the glass surface with a sticky mochi will cover the glass surface. Applicants' experiments have shown that deposits are less likely to detach from the glass surface. Therefore, the unevenness forming process is more suitably performed in the first processing chamber.

  Furthermore, it is preferable to further include means for regenerating sodium fluoride from the etching process waste liquid generated in the second processing chamber. For example, when sodium chloride is added to the etching treatment waste liquid, sodium silicofluoride is obtained, and sodium fluoride can be obtained by adding sodium hydroxide thereto. By adopting a configuration for performing such processing, it is possible to effectively utilize the drainage generated in the second processing chamber.

  According to the present invention, continuous production is possible in a single glass surface treatment apparatus, and the surface treatment of a glass substrate can be performed by a simple method.

It is a figure which shows schematic structure of the spray etching apparatus which concerns on one Embodiment of this invention. It is a figure which shows schematic structure of the etching chamber which concerns on one Embodiment of this invention. It is a figure which shows schematic structure of the etching chamber which concerns on one Embodiment of this invention. It is a figure which shows schematic structure of the drive unit of a spray etching apparatus. It is a figure which shows an example of a structure of the spray piping unit of a spray etching apparatus. It is a figure which shows an example of a structure of the spray piping unit of a spray etching apparatus. It is a figure explaining the uneven | corrugated formation process with respect to a glass substrate. It is a figure which shows schematic structure of the spray etching apparatus which concerns on one Embodiment of this invention. It is a figure which shows schematic structure of the spray etching apparatus which concerns on other embodiment of this invention.

  Hereinafter, a spray etching apparatus 10 according to an embodiment of the present invention will be described with reference to the drawings. The spray etching apparatus 10 is configured to perform a surface treatment on a glass substrate that is sequentially transported between a carry-in part and a discharge part, and corresponds to the glass surface treatment apparatus of the present invention.

  FIG. 1A and FIG. 1B show a schematic configuration of the spray etching apparatus 10. The spray etching apparatus 10 includes an introduction unit 12, a pretreatment chamber 14, a precleaning chamber 16, a frost processing chamber 18, a first cleaning chamber 20, an etching chamber 22, a second cleaning chamber 24, and a discharge unit 26. Each of the pretreatment chamber 14, the precleaning chamber 16, the frost processing chamber 18, the first cleaning chamber 20, the etching chamber 22, and the second cleaning chamber 24 has a slit shape through which the glass substrate 100 can pass through a part of the partition wall. The opening is formed.

  The spray etching apparatus 10 includes a plurality of conveying rollers 30 arranged from the introduction section 12 at the most upstream position to the discharge section 26 at the most downstream position. The transport roller 30 is configured to load (load) the glass substrate 100 on the introduction unit 12 into the preprocessing chamber 14, the precleaning chamber 16, the frost processing chamber 18, the first cleaning chamber 20, the etching chamber 22, and the second cleaning chamber. It is comprised so that it may convey to the discharge part 26, passing 24 sequentially.

  The pretreatment chamber 14 uses an acid solution or an alkaline solution such as dilute hydrofluoric acid, dilute hydrochloric acid, dilute potassium hydroxide, or dilute sodium hydroxide to perform acid cleaning or alkali cleaning on the glass substrate 100 before frost processing. Is configured to perform the pre-processing.

  The pre-cleaning chamber 16 is configured to wash away the acidic solution or alkaline solution sprayed onto the glass substrate 100 in the pre-processing chamber 14 with cleaning water. In the pre-cleaning chamber 16, the glass substrate 100 is dried by an air knife or the like after being sprayed with cleaning water and before being discharged from the pre-cleaning chamber 16.

  In the frost processing chamber 18, one or both of an etching solution containing hydrofluoric acid and a granular silicofluoride salt or fluoride salt insoluble in this etching solution is applied to the glass substrate 100 to be transferred. By bringing the mixed frost processing liquid (corresponding to the mixed liquid for processing of the present invention) into contact, irregularities are formed on the surface of the glass substrate 100. In this embodiment, the frost processing chamber 18 corresponds to the first processing chamber of the present invention.

  In the frost processing chamber 18, for example, the frost processing is performed with a frost processing liquid containing at least a fluoride salt or a silicofluoride salt that is insoluble in hydrofluoric acid and hydrofluoric acid. In this embodiment, a mixed solution for frost processing containing 5 to 10% by weight of hydrofluoric acid and a fluoride salt (sodium fluoride, potassium fluoride, etc.) is used, but is not limited thereto. .

  The first cleaning chamber 20 is configured to clean the glass substrate 100 that has passed through the frost processing chamber 18. In the first cleaning chamber 20, the mixed liquid for frosting and the like adhering to the glass substrate 100 is washed away.

  The etching chamber 22 corresponds to the second processing chamber of the present invention. In the etching chamber 22, an etching process is performed on the glass substrate 100 by bringing an etching solution containing hydrofluoric acid into contact with the glass substrate 100 that has passed through the first cleaning chamber 20. In this embodiment, 1 to 10% by weight of hydrofluoric acid and 1 to 10% by weight of hydrochloric acid are used as the etching solution, but the present invention is not limited to this.

  The second cleaning chamber 24 is configured to clean the glass substrate that has passed through the etching chamber 22. In the second cleaning chamber 24, the glass substrate 100 is washed with water by spraying cleaning water from above and below on the glass substrate 100. However, the cleaning method is not limited to this.

  The glass substrate 100 that has been surface-treated and cleaned in the spray etching apparatus 10 is discharged to the discharge unit 26. In the discharge unit 26, the glass substrate 100 is taken out (unloaded).

  As shown in FIG. 1 (B), each chamber is provided with a drying means (eg, an air knife, a dehydrating roller, etc.) for removing the liquid on the glass substrate 100. Etching solution and cleaning water are removed. The spray etching apparatus 10 is connected to an exhaust system (not shown) including a scrubber and a drainage system (not shown) including a filter press and the like, and exhaust and drainage are appropriately performed.

  Next, the configuration of the etching chamber 22 will be described with reference to FIG. The treatment chambers other than the etching chamber 22 (the pretreatment chamber 14, the precleaning chamber 16, the frosting chamber 18, the first cleaning chamber 20, and the second cleaning chamber 24), in principle, exclude differences in the processing liquids used. Since the configuration is almost the same, the etching chamber 22 will be described here, and the description of the other processing chambers will be omitted.

  The etching chamber 22 includes at least an upper spray piping unit 222, a lower spray piping unit 224, an upper hose unit 226, a lower hose unit 227 (see FIG. 3), and a guide shaft 58.

  The upper spray piping unit 222 is disposed at a predetermined distance above the glass substrate 100 conveyed on the conveying roller 30. The upper spray pipe unit 222 is configured to arrange a plurality of pipes having a plurality of discharge nozzles for discharging the etching solution in parallel. In this embodiment, an example in which six discharge nozzles are provided in each pipe arranged in parallel is described, but the number of pipes and discharge nozzles is not limited to this.

 Here, the frame member, the discharge nozzle, and the piping of the upper spray piping unit 222 are made of a composite transparent resin material based on polyvinyl chloride, details of which will be described later. The lower spray piping unit 224 is disposed at a predetermined distance below the glass substrate 100 that is transported on the transport roller 30. Since the basic configuration of the lower spray piping unit 224 is the same as that of the upper spray piping unit 222, description thereof is omitted.

  The upper spray piping unit 222 and the lower spray piping unit 224 are each provided with base members 230 serving as legs at four locations (four corners in this embodiment) at the bottom. The base member 230 is slidably supported by eight guide members 232 provided at predetermined positions in the etching chamber 22. The base member 230 has a tapered bottom, and the guide member 232 has a groove that fits the bottom of the base member 230. When the base member 230 reciprocates linearly along the groove of the guide member 232, the upper spray piping unit 222 and the lower spray piping unit 224 reciprocate linearly in the width direction orthogonal to the conveyance direction of the glass substrate 100. become.

  Since the base member 230 and the guide member 232 always rub against each other, it is preferable to use a material having acid resistance and high sliding characteristics and wear resistance. In this embodiment, polytetrafluoroethylene is used for the base member 230, and ultrahigh molecular weight polyethylene resin (U-PE) is used for the guide member 232, but the material is not limited thereto. For example, it is also possible to use a composite transparent resin material adopted for the frame member, the discharge nozzle, and the piping.

  The upper hose unit 226 is configured by a bundle of acid-resistant hoses having flexibility, and is configured to connect the upper spray piping unit 222 and the liquid feeding unit 40. The lower hose unit 227 is configured by a bundle of acid-resistant hoses having flexibility, and is configured to connect the lower spray piping unit 224 and the liquid feeding unit 40 (see FIG. 5). . The guide shaft 58 is configured to transmit the driving force from the driving unit 50 to the upper spray piping unit 222 and the lower spray piping unit 224.

  As shown in FIG. 3, the drive unit 50 is configured to transmit a driving force to the upper spray piping unit 222 and the lower spray piping unit 224 via the guide shaft 56. Since the guide shaft 58 penetrates the side wall of the etching chamber 22, a seal mechanism such as a seal bearing 58 is used to maintain water tightness and air tightness. The seal bearing 58 is configured to slidably support the guide shaft 56. One end of the guide shaft 56 is connected to the upper spray piping unit 222 or the lower spray piping unit 224. The other end of the guide shaft 56 is connected to a movable frame 60 slidably supported by an LM guide (Linear Motion Guide) 64.

  The drive unit 50 includes a motor unit 52 having a motor as a drive source, a drive circuit thereof, and the like. A rotation shaft 54 is connected to the motor unit 52. A rotating disk 70 is attached to both ends of the rotating shaft 54.

  As shown in FIG. 4A, a cam follower 72 is attached to the rotating disk 70. On the other hand, the movable frame 60 is attached with a guide member 62 in which a groove of a size that fits the cam follower 72 is formed. 4A shows a state in which the cam follower 72 of the rotating disk 70 and the guide member 62 of the movable frame are separated for convenience of explanation, but the cam follower 72 becomes a guide member 62 in actual use. Fits in a slidable state.

  When the rotating shaft 54 is rotated by the driving force of the motor unit 52, the rotating force of the rotating disk 70 is transmitted to the movable frame 60 as a driving force for reciprocating the movable frame 60. The driving force transmitted to the movable frame 60 is transmitted to the upper spray piping unit 222 and the lower spray piping unit 224 via the guide shaft 56.

  The configuration of the drive unit 50 described above is an example, and the present invention is not limited to this. For example, as shown in FIG. 4B, a cam plate 74 having a difference between a desired major axis and a minor axis can be used instead of the rotating disc 70. In this case, when a configuration is adopted in which a force is constantly applied to the movable frame 60 in a predetermined direction (an urging force by an elastic member, a magnetic member, or the like) and the cam plate 74 presses the movable frame 60 against this force. good. In addition, an optimal cam mechanism can be selected as appropriate.

  The upper hose unit 226 is configured to supply the etching liquid from the liquid feeding unit 40 to the upper spray piping unit 222. The lower hose unit 227 is configured to supply the etching liquid from the liquid feeding unit 40 to the lower spray piping unit 224. The upper hose unit 226 and the lower hose unit 227 are made of an acid-resistant member such as tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA). As the upper hose unit 226 and the lower hose unit 227, the above composite transparent resin material can be used, and other acid-resistant flexible materials may be used. In the upper hose unit 226 and the lower hose unit 227, the distance between the liquid feeding unit 40 and the upper spray piping unit 222 and the lower spray piping unit 224 is changed by the sliding operation of the upper spray piping unit 222 and the lower spray piping unit 224. Even in such a case, it is designed to be sufficiently longer than necessary so as to have sufficient deflection to absorb this change (see FIGS. 5 and 6).

  In this embodiment, the upper hose unit 226 connects the lower part of the liquid feeding unit 40 and the upper spray piping unit 222, while the lower hose unit 227 connects the upper part of the liquid feeding unit 40 and the lower spray piping unit 224. It is configured as follows. The reason is that the length of the upper hose unit 226 and the lower hose unit 227 can be increased, and when the upper spray pipe unit 222 and the lower spray pipe unit 224 are reciprocally slid, This is because the lower hose unit 227 is easily bent.

  As a result, even when a relatively hard fluororesin is used, the upper hose unit 226 and the lower hose unit 227 can easily perform their original functions. Further, the lengths of the upper hose unit 226 and the lower hose unit 227 (particularly, the lengths of the portions located outside the upper spray piping unit 222 and the lower spray piping unit 224) can be increased. And it becomes possible to reliably prevent the upper hose unit 226 and the lower hose unit 227 from dripping into the spray area of the etching solution.

  In the spray etching apparatus 10 described above, the glass substrate 100 is loaded into the introduction unit 12 by an operator or a robot. The glass substrate 100 is sequentially loaded onto the introduction unit 12 with an appropriate interval. The glass substrate 100 is introduced into the pretreatment chamber 14 from the introducing portion 12 through the slit-shaped opening, and the entire surface is cleaned with cleaning water. Subsequently, the glass substrate 100 is introduced from the pretreatment chamber 14 through the slit-shaped opening to the precleaning chamber 16 and the frosting chamber 18.

  In a normal etching process made of hydrofluoric acid, hydrochloric acid, or the like, it is difficult to process unevenness on the surface of the glass substrate 100 so as to exhibit an antireflection function, an antiglare function, or the like. For this reason, in the frost processing chamber 18, the surface of the glass substrate 100 is etched unevenly while the masking function is exerted by attaching a silicofluoride salt to the surface of the glass substrate 100. Concavities and convexities are formed.

  The mixed liquid for frost processing used in the frost processing chamber 18 contains hydrofluoric acid and at least one of a silicofluoride salt or a fluoride salt. It is preferable to add a fluoride salt (sodium fluoride, potassium fluoride, ammonium fluoride, etc.) as required. At this time, a mixed solution for frost processing may be prepared by mixing hydrofluoric acid and an aqueous fluoride salt solution.

  The treatment in the frost processing chamber 18 is preferably performed in the presence of sodium silicofluoride and potassium silicofluoride. Since sodium silicofluoride and potassium silicofluoride have a sticky shape, they tend to adhere to the surface of the glass substrate 100 and become the core of sludge groups generated during frost processing. Here, it is a figure explaining the uneven | corrugated formation process with respect to the glass substrate 100 using FIG. 7 (A)-FIG.7 (D). As shown in FIG. 7A, innumerable precipitates (including sludge such as fluoride salt and silicofluoride salt) adhere to the surface of the glass substrate 100 in the frost processing chamber 18 so as to cover it. .

  Among the innumerable precipitates, as shown in FIG. 7 (B), sodium fluoride salt or silicofluoride salt 102 (in the figure, schematically shown by hatched diamonds) and The adhering substance 104 (shown schematically in the figure as a hexagon) is included. The sodium fluoride salt or silicofluoride salt 102 easily adheres to the glass substrate 100 and also easily adheres to other deposits 104. Therefore, the role of attracting the deposits and the deposit and the glass substrate 100 are separated. Play the role of attracting. Therefore, the presence of the sodium fluoride salt or silicofluoride salt 102 such as sodium silicofluoride and potassium silicofluoride improves the performance of the uneven processing in the frost processing chamber 18.

  In the region where the sodium fluoride salt or silicofluoride salt 102 and the deposit 104 are adhered on the surface of the glass substrate 100, these exhibit a masking function, so that the etching process proceeds as shown in FIG. 7B. do not do. For this reason, irregular irregular shapes are formed on the surface of the glass substrate 100.

  Fluoride salt, silicofluoride salt, and other deposits adhering to the surface of the glass substrate 100 in the frost processing chamber 18 are washed away with cleaning water in the first cleaning chamber 20 as shown in FIG. 7C. Removed. Normally, the deposits can be removed by adjusting the spray pressure of the washing water as appropriate, but if sufficient washing is not possible with water alone, acid washing with hydrochloric acid, nitric acid, sulfuric acid, etc. should be performed. It is also possible to make it.

  In the etching chamber 22 subsequent to the first cleaning chamber 20, the etching solution is sprayed from the upper spray piping unit 222 and the lower spray piping unit 224 to the upper surface and the lower surface of the glass substrate 100, respectively. At the time of this etching process, as shown in FIGS. 6A and 6B, the upper spray piping unit 222 and the lower spray piping unit 224 repeat reciprocation in the width direction. It will change from time to time. As a result, it is difficult for the sprayed etchant to stay on the upper surface of the glass substrate 100.

  As shown in FIG. 7D, the glass substrate 100 is thinned and the uneven shape is adjusted in the etching chamber 22. Thereafter, the liquid is drained by an air knife or the like and then introduced into the second cleaning chamber 24. The glass substrate 100 is cleaned with cleaning water in the second cleaning chamber 24. Then, after dehydration processing by an air knife or the like, it is discharged to the discharge unit 26. The glass substrate 100 discharged to the discharge unit 26 is collected by an operator or a robot and transferred to a subsequent process.

  In the above-described procedure, in the spray etching apparatus 10, the frost processing and the etching process for the glass substrate 100 are performed on a continuous transport path. For this reason, the work efficiency of the surface treatment (AG (anti-glare) treatment, AR (anti-reflection) treatment, decoration treatment, thinning treatment, etc.) on the glass substrate 100 is improved. In particular, since it is possible to process the glass substrate 100 conveyed continuously by a single wafer method, it is easy to deal with a large amount of processing of the glass substrate 100.

  The spray etching apparatus 10 can easily handle larger glass substrates (for example, G4.5 size or more) as compared with batch processing in which a plurality of glass substrates stored in a processing cassette are immersed in a processing liquid tank. In addition, it is easy to improve the in-plane uniformity of characteristics such as HAZE and Gloss. In particular, when the frost processing is immersed in the frost processing liquid, the processing amount is likely to vary between the top and bottom of the glass substrate. However, in the single wafer type spray etching apparatus 10, such inconvenience is unlikely to occur.

  Means for recovering at least one of granular fluoride salt and silicic fluoride salt insoluble in the etching solution generated in the etching chamber 22 and supplying the spray etching apparatus 10 to the frost processing chamber 18. It is preferable to further provide.

  This will be described with reference to FIG. The spray etching apparatus 10 includes a pretreatment liquid storage unit 142 for storing a chemical solution to be supplied to each chamber, cleaning water storage units 162, 202, and 242, a frost processing liquid storage unit 182, and an etching processing liquid storage unit 223. ing. Further, the spray etching apparatus 10 has a configuration in which the liquid used in each chamber is discharged, such as the cleaning water discharge unit 400, the frost processing liquid discharge unit 184, and the etching processing liquid discharge unit 225.

  In the etching chamber 22, a fluoride salt and a silicofluoride salt are precipitated and precipitated. Therefore, a precipitate recovery unit 204 is provided for separating and recovering the fluoride salt and the silicofluoride salt from the liquid. It is preferable to adopt a configuration in which one or both of the chloride salt and the silicofluoride salt are supplied to the frost treatment liquid storage unit 182. Examples of the configuration included in the precipitate collection unit 204 include solid-liquid separation means such as a filter press, but are not limited thereto.

  It is preferable to further include an adding means for adding sodium fluoride and potassium fluoride to the frost processing solution. As shown in FIG. 9, the spray etching apparatus 10 may be provided with at least one fluoride salt storage unit 186 that stores, for example, sodium fluoride and potassium fluoride. Then, sodium fluoride and potassium fluoride can be supplied from the fluoride salt storage unit 186 to the frost processing chamber 18 via the frost treatment liquid storage unit 182. By adopting such a configuration, the precipitates in the frost processing chamber 18 are easily solidified and attached to the surface of the glass substrate 100, and the uneven processing on the glass substrate 100 can be suitably performed easily.

  Furthermore, it is preferable to further include means for regenerating sodium fluoride from the etching process waste liquid generated in the second processing chamber. For example, it is good to provide the precipitation part collection | recovery part 206 which adds sodium chloride to the etching process waste liquid in the 2nd process liquid discharge part 225, and collect | recovers sodium silicofluoride. Sodium fluoride can be obtained by adding sodium hydroxide to the sodium silicofluoride collected in the precipitation part collecting part 206. By supplying the obtained regenerated sodium fluoride to the frost treatment liquid storage unit 182, it becomes possible to effectively utilize the drainage generated in the etching chamber 22.

  The above description of the embodiment is to be considered in all respects as illustrative and not restrictive. The scope of the present invention is shown not by the above embodiments but by the claims. Furthermore, the scope of the present invention is intended to include all modifications within the meaning and scope equivalent to the scope of the claims.

DESCRIPTION OF SYMBOLS 10- Spray etching apparatus 12- Introduction part 14- Pre-processing chamber 16- Pre-cleaning chamber 18- Frost processing chamber 20- First cleaning chamber 22- Etching chamber 24-Second cleaning chamber 26- Discharge part 30- Conveyance roller 40-Liquid feeding unit 50-Drive unit

Claims (4)

A glass surface treatment apparatus configured to perform surface treatment on plate-like glass that is sequentially conveyed between a carry-in part and a discharge part,
By bringing the etching liquid containing hydrofluoric acid and a processing liquid mixture in which at least one of granular silicofluoride salt or fluoride salt insoluble in the etching liquid is mixed with the glass to be conveyed A first processing chamber configured to form irregularities on the surface of the glass;
A first cleaning chamber configured to clean the glass that has passed through the first processing chamber;
A second processing chamber configured to etch the glass by contacting an etchant containing hydrofluoric acid with the glass that has passed through the first cleaning chamber;
A second cleaning chamber configured to clean the glass that has passed through the second processing chamber;
A glass surface treatment apparatus comprising at least   The glass surface according to claim 1, further comprising means for recovering at least one of a fluoride salt and a silicofluoride salt generated in the second processing chamber and supplying the recovered salt to the first cleaning chamber. Processing equipment.   The glass surface treatment apparatus according to claim 1, further comprising addition means for adding potassium fluoride and sodium fluoride to the treatment liquid mixture.   The glass surface treatment apparatus according to claim 3, further comprising means for regenerating the sodium fluoride from the etching treatment waste liquid generated in the second treatment chamber.

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