JP2007241077A - Developer concentration adjustment method in color filter manufacture, and developing device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a developer concentration adjustment method for preventing adverse effects on the quality of a product due to the decrease in a developer constituent concentration and the contamination of a developer by the dissolution of a photosensitive resin composition, which are caused in the development process of the color filter manufacture of the developer circulation system, and to provide a developing device. <P>SOLUTION: The present invention is a developer concentration adjusting method to which the developer circulation system is applied, in which a developer is filtered in an ultrafiltration unit 9, after developing processing is performed in a developing tank 2 by using the developer containing a developer component such as an alkaline component, a filtrate is mixed with a high alkaline concentration liquid, after the developer component amount of the filtrate is measured quantitatively, the alkaline component concentration is adjusted, and the developer after the adjustment is used for development again. The developer concentration adjustment method determines the amount of the replenishment quantity of the high alkaline concentration liquid, in correspondence with the result of the measurement of the alkaline component concentration of the filtrate obtained by the ultrafiltration unit 9, and the correlation between the high alkaline concentration liquid replenishment quantity to the dissolved photosensitive resin composition concentration in the developer tank 4 and the concentration recovery amount. The invention includes the developing device that uses the method. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a developer concentration adjusting method and a developing apparatus in a development process in the photolithography field, particularly in a color filter production, in a development patterning process for a black matrix, a colored pixel, and the like.

  A color filter used in a liquid crystal display or the like is an optical element having a fine pattern such as black, red, green, and blue. The manufacturing process of the color filter includes a process of applying, exposing, and developing a photosensitive resist on a cleaned transparent substrate such as glass, and the same process is repeated for each color. The prior art and problems will be described below from the viewpoint of the developing process in the production of color filters.

  In the development process in color filter production, the photosensitive resin composition applied on the substrate is irradiated with light through a mask to form a desired pattern on the substrate, and then the uncured photosensitive resin composition is developed. It is a step of dissolving and removing using a liquid. In the photolithography process, this is an important process that affects the pattern shape to be formed.

  Many developers are composed of inorganic and organic alkali components. The alkali component in the developer functions to dissolve and remove the uncured photosensitive resin composition in the exposure process by reacting with a functional group having an acid value of a polymer contained in the photosensitive resin composition. .

  In addition, many developers have a surfactant added in addition to the alkali component. By adding the surfactant, the permeability of the developer component into the photosensitive resin composition is improved, and this has the effect of improving the development speed and improving the pattern shape.

  As a method of using the developer in the development step, there are a method of discarding the used developer as it is and a method of circulating the used developer repeatedly and repeatedly using it.

  In the method of using a developing solution in which the used developing solution is discarded as it is, the developing is performed using a developing solution (developing new solution) that is managed at a concentration suitable for development and has no liquid contamination. It can be said that the process control is easy because the developer concentration is appropriately managed, and there is no quality defect because there is no liquid contamination.

  However, since it is necessary to always supply a new developer, there is a disadvantage that the amount of the developer used is enormous and the running cost is high. In particular, in recent years when the size of the apparatus is increased as the substrate size is increased, reduction in running cost is required, and the disadvantage of this method is a serious problem.

  On the other hand, the method in which the used developer is circulated and used repeatedly has a lower running cost than the method in which the used developer is discarded as it is. Such a method is disclosed in Patent Document 1, for example.

  However, circulating the developer and repeatedly using it means that the photosensitive resin composition component dissolved in the developer gradually increases, and when the component in the developer exceeds the allowable amount. There is a problem that product defects occur.

  Further, there is a disadvantage that the liquid component is reduced by repeatedly using the developer by circulating it. Insufficient control of the developer concentration affects the development speed and makes process management difficult.

As long as the developer is circulated in order to reduce the running cost, it is impossible to avoid a decrease in the developer component. Since fluctuations in developer components have a greater effect on product quality than liquid contamination, developer concentration management is an issue in this method.
Japanese Patent No. 3355837

  The present invention has an adverse effect on product quality caused by developer concentration due to a decrease in developer component concentration or dissolution of a photosensitive resin composition, which is caused by a method in which a developer is circulated and used repeatedly in the development process of color filter production. It is an object of the present invention to provide a developer concentration adjusting method and a developing device for preventing the above-described problems and to enable developer concentration management in a developing process.

  The present invention relates to a developing process in color filter production. In a developing method in which a developer is circulated and repeatedly used, the developer after development is filtered into the developer by using an ultrafiltration filter. The dissolved photosensitive resin composition is removed, the amount of the alkali component and / or surfactant contained in the obtained filtrate is quantitatively measured, and the filtrate is subjected to high alkali concentration and / or high surfactant. Concentrated solution is replenished, these components are adjusted, and the adjusted developer is used again for development. The measurement result and the concentration and concentration of the high-concentration solution relative to the dissolved amount of the photosensitive resin composition in the developing tank Replenish high-concentration solution containing each component according to the correlation with the recovery amount, and revise the high-concentration solution replenishment amount as needed from the developer component measurement results, thereby developing the alkaline component of the developer used for development. The surface active agent concentration becomes properly manageable.

The invention described in claim 1
After developing with a developer containing an inorganic or organic alkali component, the developer is filtered using an ultrafiltration filter, and the amount of alkali component in the filtrate is quantitatively measured. A developer concentration adjustment method for a color filter manufacturing development process using a developer circulation method in which an alkali concentration solution is mixed, an alkali component concentration is adjusted, and the adjusted developer solution is subjected to development again.
According to the correlation between the alkali component concentration measurement result of the filtrate obtained by the ultrafiltration filter, the replenishment amount of the high alkali concentration solution with respect to the dissolved photosensitive resin composition concentration in the developing tank, and the concentration recovery amount Determining the amount of liquid replenishment,
Is a developer concentration adjusting method.

The invention described in claim 2
After developing with a developer containing a surfactant, the developer is filtered using an ultrafiltration filter. After quantitative measurement of the amount of surfactant in the filtrate, the filtrate has a high surface activity. A developer concentration adjustment method for a color filter manufacturing development process using a developer circulation system in which a developer concentration solution is mixed, a surfactant concentration is adjusted, and the adjusted developer solution is subjected to development again. ,
According to the correlation between the surfactant concentration measurement result of the filtrate obtained by the ultrafiltration filter, the high surfactant concentration liquid replenishment amount with respect to the concentration of the dissolved photosensitive resin composition in the developing tank, and the concentration recovery amount Determining the replenishment amount of high surfactant concentration solution,
Is a developer concentration adjusting method.

The invention described in claim 3
A developing device for producing a color filter using a developer circulation system, wherein the developer concentration is adjusted by the developer concentration adjusting method according to claim 1,
It has an ultrafiltration unit and a measuring device that quantitatively measures the amount of alkali components,
The replenishment amount of the high alkali concentration liquid is determined from the measured value of the alkali component by the measuring device, and the high alkali concentration liquid is periodically supplied to the filtrate.
The supply amount of the high alkali concentration solution is determined while revising the replenishment amount of the high alkali concentration solution for each measurement, and the high alkali concentration solution is periodically supplied to the filtrate.
This is a developing device.

The invention according to claim 4
A developing device for producing a color filter using a developer circulation system, wherein the developer concentration is adjusted by the developer concentration adjusting method according to claim 2,
Equipped with an ultrafiltration unit and a measuring device for quantitatively measuring the amount of surfactant,
The replenishment amount of the high surfactant concentration solution is determined from the measured amount of the surfactant by the measuring device, and the high surfactant concentration solution is periodically supplied to the filtrate.
The supply amount of the high surfactant concentration solution is determined while revising the replenishment amount of the high surfactant concentration solution for each measurement, and the high surfactant concentration solution is periodically supplied to the filtrate.
This is a developing device.

  According to the present invention, it is effective in dissolving and removing the photosensitive resin composition during development by quantitatively measuring the amount of alkali components and surfactant contained in the filtrate of the developer filtered by the ultrafiltration filter. In other words, since it is possible to measure the amount of the effective alkali component and the amount of the surfactant, it is possible to accurately adjust the concentration based on this information.

According to the invention of claim 1, the alkaline component concentration measurement result of the filtrate obtained by the ultrafiltration filter, the high alkaline concentration liquid replenishment amount with respect to the dissolved photosensitive resin composition concentration in the developing tank, the concentration recovery amount, By determining the high alkaline concentration liquid replenishment amount according to the correlation of
1) the amount of an alkali component that decreases by adsorption to the photosensitive resin composition during development;
2) The amount of alkali component that decreases by adsorbing to the dissolved photosensitive resin composition while maintaining the equilibrium state in the developing tank by mixing the developer whose concentration is adjusted;
Therefore, the alkali concentration is adjusted in consideration of the above. This makes it possible to maintain a desired concentration of the alkali component in the developing tank.

According to the invention of claim 2, the surfactant concentration measurement result of the filtrate obtained by the ultrafiltration filter, the high surfactant concentration solution replenishment amount with respect to the dissolved photosensitive resin composition concentration in the developing tank, the concentration By determining the high surfactant concentration liquid replenishment amount according to the correlation with the recovery amount,
1) the amount of a surfactant that decreases by adsorbing to the photosensitive resin composition during development;
2) The amount of surfactant that decreases by adsorbing to the dissolved photosensitive resin composition while maintaining an equilibrium state in the developing tank by mixing the concentration-adjusted developer;
Therefore, the surfactant concentration is adjusted in consideration of the above. This makes it possible to maintain the desired concentration of the surfactant in the developing tank.

  According to the third aspect of the present invention, the replenishment amount of the high alkali concentration liquid is determined by the method according to the first aspect for each measurement, and is revised to the replenishment amount for each measurement until the next measurement result is obtained. By supplying periodically, the alkali concentration of the developer component can be managed with high accuracy.

  According to the invention of claim 4, the replenishment amount of the high surfactant concentration solution is determined by the method of claim 2 for each measurement, and the replenishment amount is revised for each measurement to obtain the next measurement result. It is possible to manage the surfactant concentration of the developer component with high accuracy by periodically supplying it until it is obtained.

  From the above, according to the present invention, it is possible to accurately grasp the amount of developer component effective for development, the reduction of the effective component due to the information and development, and the effective component due to adsorption to the dissolved photosensitive resin composition in the development tank. Even in the developing method in which the developer is circulated and used repeatedly by adjusting the density in consideration of the decrease and by revising the replenishment amount of the high-concentration liquid necessary for the density adjustment every time the developer component amount is measured. It becomes possible to appropriately manage the concentration of each component of the developer used for development.

  In addition, since the developer component concentration can be appropriately managed, it is possible to provide a developing process in which product quality defects are unlikely to occur at a low running cost.

  The embodiment of the present invention will be further described below.

  FIG. 1 is a diagram for explaining an embodiment of a developing device according to the present invention. Development is performed in the developing tank 2 by discharging the developer from the developer discharge mechanism 1. That is, since the developer in the developer tank 4 is used, it is required to properly manage the concentration of the developer.

  The developing solution after the development processing is stored in the developing tank 4 through the developing solution return path 3, and then conveyed to the ultrafiltration tank 6 through the liquid feeding path 5. In order to prevent the photosensitive resin composition concentration in the developing tank 4 from continuing to increase due to repeated development, a certain amount of developer is drained using the path 7. The developer in the ultrafiltration tank 6 is sent to an ultrafiltration unit 9 having an ultrafiltration filter via a liquid supply path 8, and after ultrafiltration, a part of the developer is supplied to the liquid supply path. 10 is sent to the filtrate tank 11. The filtrate is sampled and the alkali component and / or the surfactant (developer component) is measured by the developer component concentration measuring device 12. At this time, the molecular weight cut-off of the ultrafiltration filter is based on the condition that the influence of operating conditions such as the circulation flow rate and the required filtrate amount should be considered, and that alkali components and surfactants effective for development should not be trapped. It is desirable to select as

  In addition, to measure the amount of alkali components and surfactant in the filtrate obtained, select from the measurement using a chromatograph, ultrasonic densitometer, etc. in consideration of conditions such as measurement accuracy and the number and composition of developer components. . Since concentration management requires quantitative measurement with relatively high accuracy, measurement by a titration method is more desirable.

  When the measured alkali component amount and surfactant amount are lower than the desired concentration, the developer component high concentration solution is replenished from the replenishment concentration adjusting high concentration solution tank 13 to the filtrate tank 11. Adjust the density. The developer whose density has been adjusted is returned to the developing tank 4 through the liquid supply path 14 and is again subjected to the developing process.

  Regarding the replenishment amount of the high-concentration liquid that is replenished to adjust the concentration, the replenishment amount of the high-concentration liquid that is necessary to adjust the filtrate to the concentration that you want to use during development based on the measurement results However, in the replenishment amount, it is necessary to correct the replenishment amount because the alkali component adsorbed and reduced by the dissolved photosensitive resin composition when the solution is fed to the developing tank 4 cannot be taken into consideration.

  In order to correct the replenishment amount, it is necessary to verify the concentration of the dissolved photosensitive resin composition in the developer and the concentration recovery amount with respect to the replenishment amount of the high-concentration solution before actual operation. This is because the concentration of the developer component does not recover proportionally with respect to the high concentration liquid replenishment amount. From the obtained verification results, the correction amount is determined with reference to the relationship of the developer concentration recovery amount to the dissolved photosensitive resin composition concentration in the developer. Naturally, the final replenishment amount is replenished by a larger amount than the replenishment amount calculated by simple density calculation.

  FIG. 2 is a diagram showing the concentration of the developer component in the developer tank when the high concentration solution replenishment amount is determined without using the method of the present invention. In FIG. 2, reference numeral 15 denotes a developer component concentration in the developing tank at a certain replenishment amount when the photosensitive resin composition is not dissolved in the developing tank. If the photosensitive resin composition is not dissolved in the developing tank, the replenishment amount of the high concentration solution may be determined simply by calculating the concentration of the developing solution component. Can be shown. On the other hand, reference numeral 16 denotes a developer component concentration in the developing tank when the developing tank dissolved photosensitive resin composition concentration is low. The high-concentration liquid replenishment amount was the same as in the case of reference numeral 15. In this case, since the dissolved photosensitive resin composition is present in the developing tank, even if the high concentration liquid is replenished in the same manner as described above, the desired developer component amount is not obtained. This is particularly remarkable when the concentration of the dissolved photosensitive resin composition is high. Therefore, it is shown that the concentration can be managed by correcting the replenishment amount of the high concentration solution according to the concentration of the dissolved photosensitive resin composition in the developer. For the correction, the verification result is fed back.

  The concentration of the dissolved photosensitive resin composition in the developing tank 4 is determined by the developing tank capacity, the amount of the photosensitive resin composition dissolved in the developing tank by one development, and the drain amount of the developer used. It is desirable to determine conditions such as the capacity of the developing tank so that the concentration of the dissolved photosensitive resin composition in the developing tank is a concentration that does not affect the occurrence of product quality defects in the developing process.

  When the replenishment amount of the high-concentration liquid to the filtrate is determined, the replenishment amount is periodically supplied to the filtrate tank 11 to appropriately control the concentration. When a new measurement result is obtained, the information is reflected in the high-concentration liquid replenishment amount, and the amount of regular replenishment is revised as needed. It is desirable to measure the developer component of the filtrate frequently in a short span in consideration of the developer component that changes every moment.

  The invention is further illustrated by the following examples.

  The developer used was an inorganic alkaline component and a surfactant dissolved therein. In order to prevent the photosensitive resin composition concentration in the tank from continuing to increase due to repeated development, the developer was drained at 7.5 L / min using path 7. The developer whose concentration was adjusted in the filtrate tank 11 was sent to the developer tank 4 through the path 14 and mixed with the developer in the developer tank 4. This developer was discharged by the developer discharge mechanism 1 and developed in the developing tank 2.

  As the ultrafiltration filter, a cross flow type filter made of a polyethersulfone material having a molecular weight cut off of 150,000 was selected and used. Part of the developer sent to the ultrafiltration unit 9 through the path 8 is sent to the filtrate tank 11 as filtrate, and the rest is circulated to the ultrafiltration tank 6.

  In the developer component concentration measurement, the filtrate sent to the filtrate tank 11 is quantitatively measured by the developer component concentration measuring device 12. Here, the concentration of the developer component was measured by a titration method. Neutralization titration was used for the alkali component, and complex titration using the complex as a titrant for the surfactant.

  The replenishment amount of the high-concentration solution is the final amount obtained by adding the correction amount to the replenishment amount calculated so as to adjust the concentration of the filtrate and the concentration of the high-concentration solution to the concentration to be used at the development. Determined as replenishment amount.

  The concentration of the photosensitive resin composition in the developing tank 4 was calculated assuming that the developing tank capacity was 600 L and the photosensitive resin composition dissolved in the developing tank 4 by one development was 12 g.

  The concentration measurement of the filtrate was carried out once / 10 min, and the replenishment amount of the high concentration solution was revised as needed based on the information.

  When the developer in the developing tank 4 thus obtained was ultrafiltered and the concentration of the filtrate was measured, the concentration desired to be used for development irrespective of the concentration of the dissolved photosensitive resin composition in the developing tank 4 Was measured.

  According to the present invention, in the development process of color filter production, the product quality accompanying the developer contamination caused by the decrease in the developer component concentration and the dissolution of the photosensitive resin composition, which is caused by the method of repeatedly using the developer by circulation. The developing solution concentration adjusting method and developing device for preventing the adverse effect of the developing solution can be provided, and the developing solution concentration control in the developing process can be made possible.

It is a figure for demonstrating one Embodiment of the image development apparatus in this invention. It is a figure which shows the developing solution component density | concentration in a developing tank at the time of determining the high concentration liquid replenishment amount without using the method of this invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Developer discharge part, 2 ... Developer tank, 3 ... Developer return path, 4 ... Development tank, 5 ... Liquid feed path to ultrafiltration tank, 6 ... Ultrafiltration tank , 7... Developer drain path, 8... Liquid feed path to ultrafiltration filter, 9... Ultrafiltration filter, 10... Liquid feed path to filtrate tank, 11. Developer component concentration measuring device, 13... High concentration liquid tank for concentration adjustment, 14... Liquid feeding path to developer tank, 15... Photosensitive resin composition is not dissolved in developer tank at a certain replenishment amount When the developer component concentration in the developing tank is 16, the developing tank dissolved photosensitive resin composition concentration at a certain replenishment amount is low, 17... When the concentration of the dissolved photosensitive resin composition is high Image tank developer component concentrations.

Claims (4)

After developing with a developer containing an inorganic or organic alkali component, the developer is filtered using an ultrafiltration filter, and the amount of alkali component in the filtrate is quantitatively measured. A developer concentration adjustment method for a color filter manufacturing development process using a developer circulation method in which an alkali concentration solution is mixed, an alkali component concentration is adjusted, and the adjusted developer solution is subjected to development again.
According to the correlation between the alkali component concentration measurement result of the filtrate obtained by the ultrafiltration filter, the replenishment amount of the high alkali concentration solution with respect to the dissolved photosensitive resin composition concentration in the developing tank, and the concentration recovery amount Determining the amount of liquid replenishment,
A developer concentration adjusting method characterized by the above. After developing with a developer containing a surfactant, the developer is filtered using an ultrafiltration filter. After quantitative measurement of the amount of surfactant in the filtrate, the filtrate has a high surface activity. A developer concentration adjustment method for a color filter manufacturing development process using a developer circulation system in which a developer concentration solution is mixed, a surfactant concentration is adjusted, and the adjusted developer solution is subjected to development again. ,
According to the correlation between the surfactant concentration measurement result of the filtrate obtained by the ultrafiltration filter, the high surfactant concentration liquid replenishment amount with respect to the concentration of the dissolved photosensitive resin composition in the developing tank, and the concentration recovery amount Determining the replenishment amount of high surfactant concentration solution,
A developer concentration adjusting method characterized by the above. A developing device for producing a color filter using a developer circulation system, wherein the developer concentration is adjusted by the developer concentration adjusting method according to claim 1,
It has an ultrafiltration unit and a measuring device that quantitatively measures the amount of alkali components,
The replenishment amount of the high alkali concentration liquid is determined from the measured value of the alkali component by the measuring device, and the high alkali concentration liquid is periodically supplied to the filtrate.
The supply amount of the high alkali concentration solution is determined while revising the replenishment amount of the high alkali concentration solution for each measurement, and the high alkali concentration solution is periodically supplied to the filtrate.
A developing device. A developing device for producing a color filter using a developer circulation system, wherein the developer concentration is adjusted by the developer concentration adjusting method according to claim 2,
Equipped with an ultrafiltration unit and a measuring device for quantitatively measuring the amount of surfactant,
The replenishment amount of the high surfactant concentration solution is determined from the measured amount of the surfactant by the measuring device, and the high surfactant concentration solution is periodically supplied to the filtrate.
The supply amount of the high surfactant concentration solution is determined while revising the replenishment amount of the high surfactant concentration solution for each measurement, and the high surfactant concentration solution is periodically supplied to the filtrate.
A developing device.

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