WO2014091561A1

WO2014091561A1 - Method for renewing chemical solution used for device for etching liquid crystal glass, nozzle for chemical solution renewal, and chemical solution for renewal

Info

Publication number: WO2014091561A1
Application number: PCT/JP2012/082088
Authority: WO
Inventors: 木内丈司
Original assignee: 富士技研工業株式会社
Priority date: 2012-12-11
Filing date: 2012-12-11
Publication date: 2014-06-19
Also published as: JP5986223B2; KR20150083909A; CN104837784A; JPWO2014091561A1; HK1208855A1; CN104837784B; KR101681441B1

Abstract

To promote the renewing of a chemical solution used for a device for etching liquid crystal glass, in order to maintain an optimum environment when etching liquid crystal glass, and thereby make it possible to obtain a high-quality liquid crystal glass component. A method for renewing a chemical solution used for a device for etching liquid crystal glass, wherein a chemical solution discharge nozzle and a suction nozzle are disposed in an etching solution tank for containing the chemical solution, the chemical solution is discharged and suctioned in a state in which the nozzles are immersed in the chemical solution, the discharging and the suctioning using the above nozzles are performed simultaneously, and a uniform stress is applied to the chemical solution, whereby the renewing of the chemical solution is promoted.

Description

Method of renewing chemical solution used for liquid crystal glass etching apparatus, nozzle for renewing chemical solution, and chemical solution for renewal

The present invention relates to a chemical solution renewal method used in a liquid crystal glass etching apparatus, a chemical solution renewal nozzle, and a renewal chemical solution.

Liquid crystal glass is etched by chemical treatment, and the treatment methods applied for this purpose can be broadly divided into a slimming method for thin plate and light weight and a patterning method for product shape processing. . Here, one of the problems that cannot be avoided in the chemical treatment is a solid material generated by a reaction between the material to be processed and the etching solution. The obstruction of liquid flow and the progress of contamination due to the deposition of this solid substance have made it difficult to manage the etching liquid by the continuous filtration method and to cope with high-precision manufacturing equipment.

Also, as a nozzle for discharging the etchant, that is, the etching liquid for the liquid crystal glass component to the liquid crystal glass or the like, a relatively small nozzle is used for the etching apparatus due to various circumstances. The use of small nozzles means that a large number of small nozzles are required for one liquid crystal glass component, and inevitably raises the problem of uniform etching solution discharge conditions for a large number of nozzles. Variation in etching inside liquid crystal glass parts also affects product standards, so it is difficult to achieve uniform uniformity inside liquid crystal glass parts by combining small nozzles, and drastic measures are required. .

Examining the prior art, there is a photoresist removal apparatus disclosed in Japanese Patent Application Laid-Open No. 2002-251794, which replaces and removes chemicals with a replacement / cleaning liquid ejected from a plurality of spray nozzles, and rotates the glass plate holder. This is an example of the use of a small nozzle, although the purpose is to shake off the replacement / cleaning liquid. Japanese Patent Application Laid-Open No. 2003-91885 is provided with a liquid discharge nozzle for dripping a photoresist removing chemical solution onto the surface of a glass substrate as a means for removing the photoresist layer by ultrasonically vibrating the glass substrate while rotating the glass substrate. The nozzle used for this is also small. As described above, a small nozzle is generally used for discharging the etching solution.

JP 2002-251794 A JP 2003-91885 A

The present invention has been made in view of the above circumstances, and its object is to promote the renewal of the chemical solution used in the liquid crystal glass etching apparatus in order to perform the etching of the liquid crystal glass while maintaining the optimum environment. In this way, high quality liquid crystal glass parts can be obtained. Another object of the present invention is to enable high-precision glass etching by discharging the chemical used for the etching apparatus to the entire liquid crystal glass part at one time and sucking the chemical.

In order to solve the above-mentioned problems, the present invention relates to a method for renewing a chemical used in an etching apparatus for liquid crystal glass, and arranges a nozzle for discharging a chemical and a nozzle for suction in an etching liquid tank that fills the chemical, The chemical solution is discharged and sucked while the nozzle is immersed in the nozzle, and the discharge and suction are simultaneously performed using the nozzle, and the uniform chemical stress is applied to the chemical solution to promote the update of the chemical solution. This is a measure taken.

The present invention relates to etching of liquid crystal glass, and the chemical used is mainly an etchant for etching treatment, that is, an etching solution, or a solid component generated by a reaction between a glass component and an etching solution is washed. For example, a cleaning solution for cleaning the etching apparatus.

The etching apparatus consists of a conveyor that carries liquid crystal glass into the etching liquid tank of the apparatus, a nozzle that discharges the etching liquid to the liquid crystal glass on the conveyor, piping that supplies the etching liquid, and various valve devices. The contact portion with the etching solution is always wet with the solution. On the other hand, the flow does not flow when not in operation, and sometimes the etching solution is withdrawn, so that the liquid components are dried in the non-operation state. As described above, when the etching solution is repeatedly wetted and dried, the solid component is repeatedly deposited as a layer on the surface of the etching apparatus, and as a result, the solid component is deposited on the portion in contact with the etching solution. As a result, the flow of the etching solution is hindered, and the precise performance of the precise etching apparatus tends to hardly be exhibited. Thus, the etching solution used for etching the liquid crystal glass creates a cause that has an undesirable effect on the etching apparatus, and thus corresponds to the chemical solution in the present invention. However, it is also essential to clean the solid components brought about by the etching solution. Therefore, the cleaning solution for cleaning the etching apparatus and the like is also very important as a chemical solution in the present invention. By properly updating the chemicals such as the above etchant and cleaning solution, precise etching processing is guaranteed, and the etching equipment is always maintained in an optimal state by cleaning, so that precise etching processing is stable. Can be implemented.

Further, the present invention relates to a method for renewing a chemical used in a liquid crystal glass etching apparatus, in order to eject and suck a chemical at a time on the entire liquid crystal glass component to be etched with respect to a nozzle used for the discharge and suction of the chemical. And a slit-like opening having a length equal to or longer than that of the liquid crystal glass component. Here, the significance of the nozzle in the present invention will be specifically described. In FIG. 1, 11 is a nozzle of the present invention, 12 is an etching solution level, 13 is a resist imaged by a photosensitive material, 14 is an opening formed therein, 15 is a liquid crystal glass, and 16 is an adhesive. It is a protective material made of a sheet, and protects the metal vapor deposition film 17 that becomes a sensor driving circuit in the patterning method. The above is only an example of the structure of the liquid crystal glass 15. At the start of the etching shown in FIG. 1, the depth J1 is shallow with respect to the width K of the opening 14, and a sufficient action of discharging the etching liquid in the opening by the discharge stress from the nozzle 11 can be obtained. It can be considered that there is virtually no trouble.

In contrast, when the etching reaction proceeds and the opening 14 increases to the depth J2, as shown in FIG. 2, the distance until the etching solution reaches the bottom of the opening from the nozzle 11 increases. The resistance R in the discharge direction received from the fuel tends to increase. The resistance R is represented by R = J / K (J is the depth J1 or J2). Therefore, the renewal efficiency of the chemical solution (in this case, the etching solution) is reduced inside the opening 14, and the etching characteristics in the vertical direction are deteriorated. In addition, when the reaction product adheres and accumulates in the small nozzle, The effect is noticeable.

Therefore, in FIG. 2, when a suction stress is applied from the nozzle 11 to the resist opening 14, the stress is applied in the J2 direction. Therefore, the contact distance (length) between the nozzle 11 and the corresponding resist opening 14 is set as follows. It can be seen that L is a product obtained by multiplying the cross section of action J2 (depth) × K (width): a chemical solution corresponding to a volume of J2 × K × L. By renewing the chemical liquid, if the liquid is in the same system, the total volume of the chemical liquid sucked by the nozzle 11 can be supplied to the bottom of the liquid tank, for example, within the same time, thereby promoting the chemical liquid renewal. In particular, the vertical etching characteristics are optimally maintained.

As described above, the nozzle 20 of the present invention improves an unfavorable situation related to the etching process. However, the nozzle 20 is effective not only for the etching process but also for discharging a cleaning liquid to an etching apparatus or the like. In addition, as shown in FIG. 3, in order to discharge the chemical liquid to the entire liquid crystal glass component 22 at a time, a slit-shaped opening 21 having a length M equal to or longer than the length N of the liquid crystal glass component is provided. It is what. FIG. 3 shows a liquid crystal glass component 22 for picking up a large number of products 23, and there is a margin (margin) between each product 23. FIG. 3 shows the concept until it gets tired, and should not be taken realistically.

Here, if it is possible to discharge the chemical liquid to the entire liquid crystal glass component 22 at a time, for example, a slit shorter than the above length may be used even if the liquid crystal glass component 22 does not have a length N or longer. A nozzle can be configured by connecting a plurality of apertures. That is, it can be considered that the nozzles are divided into about two or three nozzles, and the total amount of them can be discharged at once. However, when a plurality of nozzles are combined, it is inevitable that Kalman excess occurs at the boundary portion between the plurality of liquid flows, and that the influence is not limited to the glass parts. For this reason, profits are likely to be small unless there are circumstances that must be done or if there are significant benefits to doing so. Although it is such a situation, it will be clear from the above description that the requirement of the present invention can be satisfied even if it is divided into several slits instead of one slit-like opening.

FIG. 4 is a schematic view of an immersion type etching apparatus to which the present invention is applied (the above-mentioned FIGS. 1, 2 and 3 may be considered as a part of FIG. 4). In the figure, the liquid crystal glass component 22 is subjected to an etching solution discharge action and a suction action in an etching solution tank 25 of the apparatus while being moved by a conveyor 24. 26 is an ejector, 27 is a discharge circuit, and 28 is a suction circuit, each having a valve whose flow rate can be adjusted. At the tube ends of these circuits 27 and 28,

nozzles

27a and 28a having the function of the nozzle 11 are provided above and below the liquid crystal glass component 22, and the pumping fluid is used so that the suction fluid has a uniform stress. Thus, the liquid is recirculated into the liquid tank through the recirculation circuit 29, and the chemical solution is renewed.

In the present invention, as a chemical solution used in an etching apparatus for liquid crystal glass, for cleaning a solid component generated by a reaction between a glass component adhering to liquid crystal glass parts, an apparatus used for the etching process, and accessories and an etching liquid. The presence of the cleaning liquid is as described above. This cleaning liquid is composed of nitric acid, hydrogen peroxide, halogen acid salt and its acid salt as essential components.

The same material as before can be used for the liquid crystal glass component that is the subject of the present invention. In general, white plate glass used for thin film transistors (TFTs), blue plate glass used for touch panels (white plate glass is also used) and the like are applicable, but the present invention also applies to the above glass materials and various other glass materials. Applicable.

As an etchant for a liquid crystal glass component made of various glass materials as described above, that is, hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, acidic ammonium fluoride, neutral ammonium fluoride, etc. are generally used. In the glass component composition, for example, an oxide of aluminum or potassium is present as a stabilizer. For this reason, there arises a problem that a reaction product of the etching solution and the component added as a stabilizer is produced, which precipitates as a hydrophobic salt having low solubility.

Examples of precipitated substances include Na ₂ O, K ₂ O, Ca ₂ O, MgO, and Al ₂ O ₃ in soda-based blue plate glass, and in addition to BaO · ZrO in white plate glass. The reaction between the solid component cation and the etching component F 2 ⁻ produces the above-described hydrophobic salt having a low solubility (hereinafter simply referred to as “salt”).

As liquid crystal products become higher in definition, the accuracy of equipment and instruments involved in glass etching manufacturing is also required, and highly accurate submerged slit nozzles are also affected by “salt”. If it remains, it will be difficult to maintain accuracy. In this way, when the “salt” remains in the liquid crystal product, that is, the liquid crystal glass part, the quality of the product is adversely affected.

Therefore, in the present invention, the washing of the “salt” is another important factor. Under the present inventors, the development of the above-mentioned cleaning liquid was advanced, and as a result of trial and error, it was found that the cleaning liquid containing nitric acid, hydrogen peroxide, halogen acid salt and its acid salt as the main component was optimal. . The inventor recognizes that nitric acid, hydrogen peroxide, halogen acid or acid salts thereof are combinations of these components that produce an optimal cleaning effect, and the present invention has found this combination in part. It is established based on what has been done. It has not yet been clarified how the above components act. The technique itself for dissolving the “salt” with the above components is not yet known.

The composition of the cleaning liquid for the solid component in the present invention contains nitric acid 0.5 to 3.0 mol, hydrogen peroxide 0.2 to 2.5 mol, halogen acid salt or its acid salt 0.2 to 7.0 mol. Is desirable. More preferable numerical values are in a range of 0.5 to 2.0 mol of nitric acid, 0.5 to 2.0 mol of hydrogen peroxide, and 0.5 to 3.0 mol of a halogenate salt and an acid salt thereof. The lower limit in the case of nitric acid is 0.5 mol, and the lower limit in the case of hydrogen peroxide is 0.2 mol. Below this, the oxidation reaction and cleaning reaction become too slow. Also, in the case of nitric acid, if it exceeds 3.0 mol, the nitric acid decomposition reaction starts, and in the case of hydrogen peroxide, if it exceeds 2.5 mol, a rapid invalidation decomposition reaction starts, which is not preferable. If the halogen acid salt or its acid salt is less than 0.2 mol, the chelate reactivity becomes slow, and even if it is added in excess of 7.0 mol, it does not melt, so that it falls within the above range. In the present invention, using such a cleaning liquid, cleaning of liquid crystal glass parts after etching and equipment, instruments, etc. involved in glass etching manufacturing are contributed to improving the quality of liquid crystal products that are becoming more precise. can do.

The present invention also provides a nozzle for use in discharging and sucking a chemical solution in an etching apparatus for liquid crystal glass. The nozzle includes a slit-like opening having a length equal to or longer than the length of the liquid crystal glass component in order to discharge the chemical at once to the entire liquid crystal glass component to be etched. In order to promote chemical solution renewal, it is desirable to provide a suction port for sucking the chemical solution in the solution. The reason for this is that the chemical liquid can be discharged and sucked at a time to avoid mutual interference due to the flow of a plurality of chemical liquids. Although a smooth flow of the chemical solution cannot be obtained, the rectified flow along the length direction of the opening 14 in FIGS. 1 and 2 is obtained for the first time by performing suction, and the opening formed by etching. The reason that the effect | action which shapes the fine unevenness | corrugation of a side surface is acquired can be mentioned. The flow may be laminar or turbulent.

The chemical solution nozzle of the present invention is not only used for performing a cleaning method using a cleaning liquid for a solid component generated in an etching apparatus for liquid crystal glass, but is also used for an etching process. That is, the chemical liquid in the present invention is an etchant, that is, an etching liquid and a cleaning liquid containing a solid component. In both of these processing operations, the nozzle of the present invention is used to promote the replacement of the chemical solution.

The cleaning liquid according to the present invention is configured and operates as described above, and the updating of the chemical liquid used in the liquid crystal glass etching apparatus is promoted in order to perform the etching of the liquid crystal glass while maintaining the optimum environment. As a result, there is an effect that a high-quality liquid crystal glass component can be obtained. Further, according to the present invention, the chemical liquid is discharged to the entire liquid crystal glass part at the same time, and at the same time, the chemical liquid is sucked to remove the reaction product of the glass component and the etching liquid as completely as possible. This makes it possible to perform accurate glass etching and to obtain a high-quality liquid crystal glass component. In addition, the chemical liquid nozzle according to the present invention is configured as described above, and discharges the chemical liquid to the entire liquid crystal glass part at one time and acts to suck the chemical liquid. By cleaning this solid component, it is possible to maintain high accuracy of devices, instruments, etc. involved in the production of glass etching and realize high quality glass etching.

It is sectional explanatory drawing which shows the relationship between the nozzle for chemical | medical solutions which concerns on this invention, and progress of an etching reaction. It is sectional explanatory drawing which similarly shows the state which reaction advanced more. It is a top view which shows an example of the nozzle of this invention provided with the slit-shaped opening part which has a liquid crystal glass component and the length more than the length. It is sectional explanatory drawing which shows an example of the apparatus directly used for implementation of the etching method which concerns on this invention.

DESCRIPTION OF SYMBOLS 11 Nozzle 12 Liquid level 13 Resist 14 Opening part 15 Liquid crystal glass 16 Protection material 17 Metal vapor deposition film 20 Nozzle 21 Example of slit-shaped opening part 22 Liquid crystal glass component 23 Product 24 Conveyor 25 Etching liquid tank 26 Ejector

<Example>
Hereinafter, the present invention will be described in more detail with reference to examples. The above-described etching apparatus shown in FIG. 4 is used in the method for renewing the chemical used in the liquid crystal glass etching apparatus according to the present invention. Specifically, a chemical solution discharge nozzle 27a and a suction nozzle 28a are vertically arranged in an etching solution tank 25 filled with a chemical solution, with the liquid crystal glass part 22 interposed therebetween, and the nozzle 27a, In the state where 28a is immersed, the chemical solution is discharged and sucked, and the discharge and suction using the

nozzles

27a and 28a are simultaneously performed to apply uniform stress to the chemical solution, so that the update of the chemical solution is promoted. It is configured.

The liquid crystal glass component 22 is moved by the conveyor 24 and is subjected to an etching solution discharge action and a suction action in the etching solution tank 25. Moreover, all the above description with reference to FIG. 4 is an example. Of course, the etching apparatus can constitute the cleaning apparatus as it is. For confirming the cleaning effect, the liquid crystal glass is etched using the etching apparatus of FIG. 4, and as a result, a pipe formed by the reaction between the glass component and the etching solution and having a solid component deposited thereon is used. It was immersed in the cleaning liquid.

Etching was performed by a normal etching method in which blue glass was used as the liquid crystal glass and this was immersed in an etching solution composed of hydrofluoric acid and hydrochloric acid at 35 ° C. Accordingly, the solid components deposited on the inner wall of the pipe are presumed to be cations, fluorine, anions and the like. A part of the pipe is cut and immersed in the cleaning liquid of the present invention, and the liquid containing the cleaned components is treated as described later to obtain sludge, and the effect of the cleaning liquid by renewing the chemical liquid of the present invention is used as a sample. An experiment to confirm was conducted.

Table 1 relates to a solid component cleaning liquid in the liquid crystal glass etching apparatus according to the present invention.
Table 1

Concentration is expressed in mol and water other than components is water.

Add 1 g of dried scale of white glass plate to 100 g of cleaning solution 1-7 above, stir at 30 ° C. for 1 hour, filter, burn filter paper, and irradiate the remaining sludge with light using a lamp. Then, the weight of the “salt” in the reduced-rate dry state was measured, and the decay rate was considered. The results are shown in Table 2.
Table 2

When the pipe with the reaction product deposited on the cleaning agent 3 having the greatest attenuation rate is immersed at a liquid temperature of 25 ° C. for 1 hour, the deposited solid component does not stop the trace. It was possible to confirm a remarkable cleaning effect by the cleaning liquid of the present invention. Further, when the same experiment was performed on the cleaning liquid 4, the precipitated solid component remained in an area of about 40%, but the cleaning liquids 5 to 7 were significantly improved in comparison with the comparative examples. It was confirmed. Thereby, it was confirmed that the cleaning liquids 1 to 4 have the effect of the cleaning liquid targeted by the present invention.

Next, an experiment was conducted to confirm the strength of the liquid crystal glass obtained by the present invention. In the configuration of FIG. 1, a 0.55 mm liquid crystal glass component formed by a resist on a 100 mm × 150 mm soda glass with a conical spray pattern nozzle from a distance of 150 mm above, with an internal pressure of 0.15 mpa. Irradiation was performed, and the glass was moved by +80 mm at a rotation speed of 6 rpm, and the obtained glass was used as one sample glass part. Further, using a similar sample, a 120 mm long slit nozzle is sucked from the sample at a pump discharge flow rate of 150 liters / min from a distance of 20 mm above, and the glass is moved +80 mm at a speed of 6 rpm, The obtained one was used as another test glass part.

The above-mentioned two kinds of samples were subjected to a fracture strength tester as test parts, and the strength at the time when fracture occurred due to the stress applied to the surface of each glass part was measured. The test results are shown in Table 3 as the breaking strength.
Table 3

According to Table 3, the slit nozzle according to the present invention has a 33% increase in the maximum example 2 and a 26% increase in the minimum example 3 than the conical spray pattern nozzle. I understand that

Furthermore, an experiment was performed to confirm the smoothness of the etched surface of the liquid crystal glass obtained by the present invention. Using a white plate glass of 340 mm × 460 mm × 0.7 mm as a sample, this is etched using the immersion type etching apparatus shown in FIG. 4 until the plate thickness becomes 0.4 mm, and then from the above etching apparatus. The sample taken out was mechanically polished to 0.38 mm using an abrasive made of cerium oxide. The number of scratches of 100 μm or more in the glass caused by the polishing was compared with a sample washed with water after etching and a sample washed with water, immersed in chemical solution No. 3 for 60 seconds and then washed with water.

The results are shown in Table 4.
Table 4

According to Table 4, the sample treated with the cleaning liquid of the present invention had only about 20 scratches left in the case of only mechanical polishing and not cleaned with the chemical liquid (the cleaning liquid of the present invention). Since the number of remaining scratches did not exceed two, it can be seen that the effect of the chemical cleaning is remarkable.

The above chemical cleaning demonstrates that the cleaning liquid of the present invention has a remarkable effect for eliminating scratches and restoring smoothness, which means that the liquid crystal glass obtained by the etching technique of the present invention is This means that the occurrence of cracks due to scratches can be significantly reduced. Moreover, it can be seen from the measurement of the breaking strength of the liquid crystal glass in Table 3 that the breaking strength of the liquid crystal glass is remarkably improved. However, it is judged that the disappearance of the scratches contributed to the breaking strength. On the other hand, the chemical solution updating nozzle having a slit-like opening having a length longer than that of the liquid crystal glass component according to the present invention uses a discharge and suction force that is 30% stronger than a conical spray pattern. It turns out that it will be possible. Therefore, according to the present invention, a highly accurate liquid crystal glass component can be efficiently manufactured by synergy of the above effects.

According to the present invention configured as described above, glass etching can be performed under ideal conditions. In addition, by using the cleaning liquid and the chemical nozzle according to the present invention, it is possible to almost completely clean devices, instruments, etc. involved in the manufacture of glass etching, and their accuracy is maintained with high accuracy. Therefore, the cleaning liquid and chemical nozzle of the present invention makes it possible to always maintain the best performance of equipment, instruments, etc. involved in glass etching production, and the glass material is cleaned by the cleaning liquid and chemical nozzle of the present invention. By washing, it becomes possible to manufacture high-quality liquid crystal glass parts.

Claims

A method for renewing a chemical used in a liquid crystal glass etching apparatus,
In the etchant tank that fills the chemical, a chemical discharge nozzle and a suction nozzle are placed.
In the state where the nozzle is immersed in the chemical solution, discharge and suction the chemical solution,
A method for renewing a chemical used in an etching apparatus for liquid crystal glass, characterized in that the renewal of the chemical is promoted by simultaneously performing discharge and suction using the nozzle and applying a uniform stress to the chemical.
A method for renewing a chemical used in a liquid crystal glass etching apparatus,
A nozzle used for discharging and sucking a chemical solution,
A liquid crystal glass comprising a slit-like opening having a length equal to or longer than the length of the liquid crystal glass component in order to discharge and suck a chemical solution at once to the entire liquid crystal glass component to be etched. Nozzle for chemical solution update used for etching equipment.
The liquid chemical used for the liquid crystal glass etching apparatus is a cleaning liquid for cleaning the solid component produced by the reaction between the glass component and the etching liquid, which is attached to the liquid crystal glass parts, the apparatus used for the etching process and accessories. ,
A chemical solution for renewal used in an etching apparatus for liquid crystal glass containing nitric acid, hydrogen peroxide, halogen acid salt or an acid salt thereof as essential components.
The renewal for use in an etching apparatus for liquid crystal glass according to claim 3, containing 0.5 to 3.0 mol of nitric acid, 0.2 to 2.5 mol of hydrogen peroxide, and 0.2 to 7.0 mol of a halogen acid salt or an acid salt thereof. Chemical solution.