JP2006163148A - Developing device and developing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a developing device and a developing method which achieve both of reduction in a flow amount of a developing solution and regeneration and usage of a used developing solution. <P>SOLUTION: The developing device is equipped with: a developing unit having a means to apply ultrasonic vibration to a developing solution, in which an object to be developed is developed with a developing solution with the above ultrasonic vibration applied; an ultrafiltration device having an ultrafiltration filter to filter the developing solution after used in the above development; and a means to return the filtrate passing the ultrafiltration filter as a developing solution to the developing unit. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a developing device and a developing method, and more particularly, to a developing device and a developing method suitable for manufacturing a color filter for a liquid crystal display.

  A color filter used in a liquid crystal display or the like is an optical element having a fine red, green, blue pattern or the like. The manufacturing process of such a color filter includes steps of applying a photosensitive resist to a transparent substrate such as glass, exposing, and developing, and the same steps are repeated for each color. Hereinafter, a conventional development process in manufacturing a color filter will be described.

  When developing the exposed photosensitive resist by the automatic development processing method, as the developing process is repeated many times, the elution component dissolves in the developing solution from the photosensitive resist and greatly affects the performance of the developing solution. Dissolved components adhere to the substrate to be developed, greatly affecting the quality of the color filter.

  In order to remove photosensitive resist components dissolved in the developer, such as pigments, acrylic resins, monomers, etc., automatic developing devices equipped with a filter have become widespread. Since clogging occurs, there is a problem of frequent replacement of the filter.

  Proposals for regenerating the developer by removing the photosensitive resist eluate in the developer have been made in the past, and in fact, a method for regenerating the developer using an ultrafiltration filter has been proposed. (For example, refer to Patent Document 1).

  However, this developer regeneration method is not suitable for manufacturing color filters that perform continuous processing at a high throughput because the amount of developer used in the conventional development method is increased.

The photolithographic production line has been increasing year by year, and accordingly, the development apparatus has also increased in size. With conventional development methods such as the shower development method and the dip development method, the photosensitive resist as described above is used. In the developer in which the components are dissolved, there is a problem that maintenance work of the developing tank is difficult.
JP-A-11-212275

  An object of the present invention is to provide a developing device and a developing method that are made under the circumstances as described above and that can simultaneously reduce the amount of developer used and recycle and use a used developer. And

  In order to solve the above-described problems, a first aspect of the present invention includes a developing unit that includes means for applying ultrasonic vibration to a developer, and the development target is developed with the developer that has been subjected to ultrasonic vibration. And an ultrafiltration device comprising an ultrafiltration filter for filtering the developer after being used for the development, and means for returning the filtrate that has passed through the ultrafiltration filter to the development unit as a developer. A developing device is provided.

  According to a second aspect of the present invention, there is provided a developing unit including means for applying ultrasonic vibration to the developer, wherein the developing process is performed by the developer applied with the ultrasonic vibration, and the developer after being used for development. An ultrafiltration circulation tank that contains the ultrafiltration filter, an ultrafiltration device that filters the developer after being used for development, and the developer in the ultrafiltration circulation tank from the development unit. Means for supplying to the ultrafiltration device; a filtrate circulation tank for storing the filtrate that has passed through the ultrafiltration filter in the ultrafiltration device; and returning the filtrate as a developer from the filtrate circulation tank to the developing unit. And a developing device.

  According to a third aspect of the present invention, there is provided a developing method in which the developing apparatus described above is used, and the developing unit is subjected to a developing process using a filtrate that has passed through an ultrafiltration filter in a developing unit.

  According to the developing device and the developing method configured as described above, since the developing solution to which ultrasonic vibration is applied is used, it is possible to perform continuous development efficiently even with a low flow rate developing solution. As a result, the entire amount of the used developer can be processed by an ultrafiltration filter, and the developer can be recycled.

  Hereinafter, the developing device and the developing method of the present invention will be described in more detail.

  The present invention is characterized in that development processing is performed using a developer to which ultrasonic vibration is applied by irradiating ultrasonic waves. In this way, by applying ultrasonic vibration to the developer, a physical force due to fine vibration is added to the developer, thereby promoting development processing capability.

  The frequency of the ultrasonic wave is preferably in the range of 0.8 to 1.2 MHz. Further, the time during which the developer is irradiated with ultrasonic waves is preferably 5% to 70% of the development time required for the entire development process, and the number of development units is thereby determined. For example, when the development time is 120 seconds, the time during which the ultrasonic waves are actually irradiated is 6 seconds to 84 seconds.

The developing unit is preferably such that the flow rate of the developing solution per unit area of the cross section perpendicular to the substrate to be processed is about 15 to 150 L / min · m ^{2 in the} developing chamber in which development is performed.

  In the present invention, an ultrafiltration filter is used to remove the photosensitive resist component dissolved in the developer by the development process and regenerate the developer. Here, the ultrafiltration filter to be used preferably has a filtrate permeability of 5% to 30% with respect to the amount of developer supplied to the ultrafiltration filter. The molecular weight cut off and the material of the ultrafiltration filter are not particularly limited.

  In order to perform continuous circulation use of the developer, such as development processing by the development unit, regeneration of the developer by the ultrafiltration filter, and supply of the filtrate to the development unit, the ultrafiltration device uses an ultrafiltration filter. Means are provided for regular backwashing.

  In order to simultaneously realize development processing at a low flow rate and resist component removal by ultrafiltration, in the present invention, the relationship between the filtrate flow rate of the ultrafiltration filter, the area of the ultrafiltration filter, and the developer flow rate required for development, It is desirable to maintain a flow rate balance so as to satisfy the relationship of [ultrafiltration filtrate flow rate] × [ultrafiltration filter area] × A = [developer flow rate required for development]. In this case, A is 0.1-30.

  Further, the developer flow rate required for development satisfies the relationship [developer flow rate supplied to the development unit] = [developer flow rate per unit area of the development chamber of the development unit] × [nozzle area] × B. Is preferably a value of 1-20.

  Furthermore, in order to simultaneously realize development processing with a low flow rate developer and removal of resist components by ultrafiltration, the ultrafiltration circulation tank is designed to prevent continuous deterioration due to development processing of the developer. Can have a means for periodically discarding a fixed amount of the developer during continuous operation, and the filtrate circulation tank can have a means for regularly taking in a constant amount of the new developer.

 FIG. 3 shows a comparison between the conventional method and the method of the present invention. A is a case where all the developing solutions are drained and a new developing solution is supplied after developing a predetermined number of substrates to be developed, and B is a new developing solution supply and a developing solution drain in the developing solution tank. The correlation between the time and the developing solution contamination is shown in the case where the developing solution is exchanged after developing a predetermined number of substrates to be developed, continuously. On the other hand, C shows a correlation between time and developer contamination degree in which the method of the present invention is adopted.

 In the method A, since the regular drain of the developer in the developer tank and the regular supply of the new developer are not performed, the degree of contamination deteriorates almost linearly. On the contrary, since B does this, the degree of contamination reaches a steady state with a certain number of development processing sheets, but the amount of drainage taking into consideration the running cost is still high in the degree of contamination of the developing solution, which hinders product quality. There are many. C can suppress the degree of contamination of the developing solution to a considerably low level even when the amount of new developing solution supplied is the same as that of B. As shown in FIG. 3, the interval until all the developing solution in the developing solution tank is drained. Can be set long enough.

 As described above, according to the present invention, it is possible to provide a developing device and a developing method in which workability is not deteriorated even when a product is enlarged and process management is extremely easy.

  According to the present invention, since the developer to which ultrasonic vibration is applied is used, it is possible to efficiently perform the development continuously with a low flow rate developer, thereby reducing the total amount of the used developer. It is possible to circulate and use the developer by processing with an ultrafiltration filter. As a result, high-quality products can be manufactured at low cost, and maintenance can be improved.

  The best mode for carrying out the invention will be described below with reference to the drawings.

  FIG. 1 is a flowchart showing a developing device according to an embodiment of the present invention. Reference numeral 1 schematically indicates a developing unit in which three developing units 2 each including an ultrasonic vibrator are arranged. In the developing unit 2, the developing solution is supplied to the substrate coated with the photosensitive resist and exposed in a state where ultrasonic vibration is applied by the ultrasonic vibrator. As a result, the developing unit 2 performs the developing process. Done.

  The processed developer after being subjected to the development processing is introduced into the ultrafiltration circulation tank 3 through the pipe 4. The processed developer in the ultrafiltration circulation tank 3 is supplied to the five ultrafiltration filters 5 of the ultrafiltration unit 6 surrounded by a broken line in the drawing through the pump 7 and the pipe 8.

  The processed developer supplied to the ultrafiltration filter 5 is separated into a filtrate that has passed through the ultrafiltration filter 5 and a concentrate that does not pass through. The concentrated liquid is returned to the ultrafiltration circulation tank 3 via the pipe 9. On the other hand, the filtrate that has passed through the ultrafiltration filter is supplied to the filtrate circulation tank 10 via the three-way valve 17 and the pipe line 11.

  At least one filtrate in the ultrafiltration filter 5 is supplied to the backwash tank 12 via the three-way valve 17 and the pipe line 14. When the amount of liquid in the backwash tank 12 becomes constant, the filtrate in the backwash tank 12 is supplied to one of the selected ultrafiltration filters 5 via the pump 13 and the conduit 14, and the ultrafiltration filter 5 Back wash. The developer (filtrate) in the filtrate circulation tank 10 is supplied to the developing unit 1 via the pump 15 and the pipe line 16.

  An example of a specific structure of the developing unit 2 in the developing unit 1 is shown in FIG. As shown in FIG. 2, the developing unit 2 includes an upper ultrasonic unit 22 having a vibrator 21 inside and a lower unit 23, and a developing chamber 24 is disposed between these units 22 and 23. . In the developing chamber 24, the developer is introduced from the developer introduction port 25, and the processed developer is discharged from the developer discharge port 26. In the developing chamber 24, the developing substrate 27 is transported from the left to the right, contrary to the direction in which the developing solution flows, and a developing process is performed in the process.

  As for the cross-sectional size of the developing chamber 24, the width in the direction perpendicular to the substrate surface is preferably 30 to 100 mm, and the width in the direction parallel to the substrate surface is preferably substrate size +30 to 100 mm. If the cross-sectional size of the developing chamber 24 is too small, the flow rate of the developing solution becomes high and it becomes difficult to perform uniform development, and if it is too large, the flow rate of the developing solution becomes slow and the development process takes time. In addition, the flow rate increases and the developer is wasted.

  The frequency of the ultrasonic vibration to be used is preferably 0.8 to 1.2 MHz. If the frequency is less than 0.8 MHz, film peeling occurs in the developing portion due to the influence of cavitation, and if it exceeds 1.2 MHz, the effect of applying ultrasonic vibration cannot be obtained.

The flow rate of the developing solution flowing developing chamber 24 is preferably a unit area per 15~150L / min · ^{m 2} of cross section perpendicular to the flow of the developing chamber 24, a 30~70L / min · ^{m 2} Is more preferable. If it is less than 15 L / min · m ² , a uniform film surface (liquid level) cannot be maintained, and if it exceeds 150 L / min · m ² , the effect of applying ultrasonic vibration is reduced.

  As the ultrafiltration filter 5 of the ultrafiltration device part, it is preferable to select one having a filtrate permeability of 5 to 30%. In order to maintain the liquid permeability at 5 to 30%, it is effective to have a system for regularly back-washing the ultrafiltration filter 5 automatically and manually. When the filtrate permeability is less than 5%, the flux decreases, and when it exceeds 30%, film peeling occurs due to the influence (pressure resistance) on the film.

  Examples of the developer to be used include alkaline ones such as sodium hydroxide and potassium hydroxide, and it is desirable to use a developer having a pH of 10 to 13.

  In the developing device according to the present embodiment, in order to prevent continuous deterioration of the developer component that is continuously subjected to the development processing, means 18 for automatically and manually draining the ultrafiltration circulating liquid periodically; Means 19 is provided for periodically or automatically supplying a developing solution of the same amount as the amount of the developer required for the drain + the amount of the developer taken out by the substrate to the filtrate circulation tank.

  According to the developing device according to the present embodiment described above, since the developing solution to which ultrasonic vibration is applied is used, the developing can be performed very efficiently, and therefore, the developing is continuously performed with the low flow rate developing solution. Can be done.

  On the other hand, in order to circulate and use the developer, it has been attempted to treat the entire amount of the used developer with an ultrafiltration filter, but when the amount of filtrate obtained is small and an attempt is made to obtain a large amount of filtrate. However, there is a problem that high pressure must be applied to the ultrafiltration filter, which deteriorates the life of the ultrafiltration filter.

  On the other hand, according to the developing device according to the present embodiment, as described above, since the amount of the used developer is small, the entire amount of the used developer can be processed by an ultrafiltration filter and reused. It has become possible.

  Hereinafter, examples in which development processing is performed using the developing device according to an embodiment of the present invention described above will be described.

  A photosensitive resist in which a pigment is dispersed is applied to a glass substrate having a size of 680 × 880 mm by a coating device, and then exposed to about 100 mJ with an exposure machine, and the developing device shown in FIG. 1 having the developing unit shown in FIG. Then, the development processing was continuously performed.

  At this time, as a developing unit 2 to be used, a developing chamber 24 having a cross-sectional size of 90 mm × 700 mm is selected, and an ultrasonic vibrator 21 for irradiating an ultrasonic vibration of 950 kHz is disposed on an upper portion of a glass substrate 27 to be developed. It was assumed. In order to develop the glass substrate 27 to be developed, three developing units 2 are arranged.

The flow rate of the developing solution flowing in the developing chamber of the developing unit 2 is 3.5 L / min per developing unit (flow rate per unit area: 55.56 L / min · m ² ), and the liquid flow rate required for development is 21 L / min. Conducted in min.

As the ultrafiltration filter 5 for filtering the developer after being subjected to the development processing, one having a filtrate permeability of 10% to 15% and a membrane area of 7.8 m ² is selected, and ultrafiltration is performed. The number of filters 5 was three.

  At this time, the amount of the filtrate of the ultrafiltration filter 5 was 12 to 14 L / min, and one was used for backwashing, and the one supplied to the filtrate tank 10 was used in two configurations.

  The molecular weight cutoff of the ultrafiltration filter 5 was 30,000.

  In the developing process by this developing apparatus, the amount of the developer taken out by the substrate 27 is set to 0.4 L, the periodic drain amount is set to 0.6 L per sheet of the substrate, and the periodic new liquid supply amount is set to the substrate 1. Set to 1 L per sheet.

  Under the above conditions, the development time was 60 seconds, of which the time during which ultrasonic vibration was applied to the developer was 25 seconds, and when 10 sheets were continuously developed, the developability equivalent to that of the conventional shower development method was obtained. It was confirmed that

  In addition, it was confirmed that no foreign matter was reattached due to the contamination of the developing solution, and that the inside of the developing unit 21 was clean.

 As described above, in the developing apparatus according to the present embodiment, the three ultrafiltration filters 5 can efficiently perform the developing process with the developer without contamination, but the conventional ultrasonic vibration is not applied. In order to obtain a developing solution having the same degree of contamination by the developing device, 26 ultrafiltration filters were required.

Next, the present inventors are a conventional developing device in which ultrasonic vibration is not applied to the amount of developer used per developer substrate when developing for color filter production. And an experiment comparing the apparatus according to this example. The results are shown in the table below.

 In Table 1 above, BM is a black matrix, R is a red pattern, G is a green pattern, B is a blue pattern, and PS is the amount of developer used for the post spacer.

 From Table 1 above, it can be seen that when the amount of developer used in the case of using the conventional developing device is 100 per color filter, the developing device of the present embodiment is greatly reduced. From this result, it can be seen that the device of this embodiment can provide a very large cost reduction effect.

It is a flowchart of the developing device according to an embodiment of the present invention. FIG. 4 is a cross-sectional view showing a developing unit of the developing device according to the embodiment of the present invention. It is a figure which shows the correlation of the developing solution contamination degree of a conventional system and the system of this invention, and time.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... development part, 2 ... development unit, 3 ... ultrafiltration circulation tank, 4 ... development processing solution drain pipe line, 5 ... ultrafiltration filter, 6 ... ultra Filtration device, 7 ... ultrafiltration circulating fluid feed pump, 8 ... ultrafiltration circulation fluid line, 9 ... ultrafiltration circulation fluid return line, 10 ... ultrafiltration filtrate tank 11 ... Ultrafiltrate supply line, 12 ... Backwash tank, 13 ... Backwash liquid feed pump, 14 ... Backwash liquid feed line, 15 ... Ultrafiltration Filtrate feed pump, 16 ... ultrafiltrate filtrate feed line, 17 ... three-way valve, 18 ... ultrafiltrate circulating fluid regular drain line, 19 ... developer new solution supply line, 21 ... Ultrasonic vibrator, 22 ... Upper ultrasonic unit, 23 ... Lower unit, 24 ... Developing chamber, 25 ... Developer introduction port, 2 ... developer discharge port 27 ... to be developed substrate.

Claims (10)

  A developing unit that includes means for applying ultrasonic vibration to the developer, the developing unit that performs development of the developing object with the developer that has been subjected to the ultrasonic vibration, and a filter that filters the developer after being used for the development. A developing device comprising: an ultrafiltration device comprising a filtration filter; and means for returning the filtrate that has passed through the ultrafiltration filter to the development unit as a developer.   The flow rate of the developer required for the development and the flow rate of the filtrate permeated through the ultrafiltration filter are [the flow rate of the filtrate per unit area of the ultrafiltration filter × the area of the ultrafiltration filter × A = the flow rate of the developer required for development]. The developing apparatus according to claim 1, wherein the relationship is satisfied and A is 0.1 to 30.   The developing device according to claim 1, wherein a time during which the developing solution to which the ultrasonic vibration is applied contacts the developing object is 5% to 70% of the entire developing time.   The developing device according to claim 1, wherein the ultrafiltration filter exhibits a liquid permeability of 5 to 30%.   The developing device according to claim 1, wherein a frequency of the ultrasonic vibration is 0.8 to 1.2 MHz.   A developing unit that includes means for applying ultrasonic vibration to the developer, the developing unit performing development processing using the developer that has been subjected to the ultrasonic vibration, and an ultrafiltration circulation tank that stores the developer after being used for development; An ultrafiltration device that includes an ultrafiltration filter and filters the developer after being used for development, and means for supplying the developer in the ultrafiltration circulation tank from the development unit to the ultrafiltration device And a filtrate circulation tank that contains the filtrate that has passed through the ultrafiltration filter in the ultrafiltration device, and means for returning the filtrate as a developer from the filtrate circulation tank to the developing unit. Developing device.   The ultrafiltration circulation tank has means for periodically discarding a certain amount of the developer during continuous operation of the developing device, and the filtrate circulation tank periodically takes in a constant amount of the new developer. The developing device according to claim 6, further comprising: means.   The developing device according to claim 6, wherein the ultrafiltration device has means for periodically back-cleaning the ultrafiltration filter.  A developing method for developing a developing object using the developing device according to claim 1 and using a filtrate that has passed through the ultrafiltration filter in the developing unit.   The developing method according to claim 9, wherein the object to be developed is a photosensitive resist film formed on a substrate and exposed.

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