JP5477531B2 - Developing apparatus and developing method - Google Patents

Description

  The present invention relates to a developing device and a developing method, and more particularly, to a developing device and a developing method used in a developing process of black matrix, colored pixels and the like in color filter manufacturing using a developer circulation system.

  A color filter used in a color liquid crystal display device or the like includes a transparent glass substrate as a structural support, and the opposite side (back side) of the screen observer is divided into a large number of pixel areas. A pattern of a light shielding layer (black matrix: hereinafter abbreviated as BM) is provided at an inter-pixel position located at the boundary, and colored pixels are arranged in each of the pixel regions. The colored pixels color the transmitted light for each pixel, and generally, three colored pixels of red (R), green (G), and blue (B) corresponding to the three primary colors of light are arranged.

  As a typical manufacturing method of a color filter substrate, a photolithography technique using a color material (resist) in which a pigment is dispersed in a photosensitive resin is used. As a general manufacturing process, starting from the introduction of a glass substrate, the process proceeds to the formation of BM and the formation of R, G, and B colored pixels. In each color process, pre-cleaning of the glass substrate, photosensitive resin liquid Coating, solvent drying, pre-baking, pattern exposure, development, post-baking, and inspection are repeated. Hereinafter, a conventional developing process in color filter production will be described.

  The development process is aimed at dissolving and removing the uncured resist after exposure, and is an important process that influences the shape of the pattern to be formed in the photolithography process. Items managed in the development process include development time, temperature of the developer, and the like, and all depend on the developing power of the developer to be used, although it varies depending on the configuration and system of the developer tank.

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

  In a developing device used in a conventional developing process, there are two methods of using a developer: a method of discarding a used developer as it is, and a method of repeatedly using a used developer by circulation.

  In the method of using a developing solution that discards the used developing solution as it is, a developing solution (developing solution) free from liquid contamination is used, so that the process control is easy because the developing solution concentration is appropriately controlled. It can be said that it is a method in which quality defects are unlikely to occur due to the absence of 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.

  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. However, recirculating and repeatedly using the image liquid means that the photosensitive resin composition component dissolved in the developer gradually increases, and if the component in the developer exceeds the allowable amount. There is a problem that product defects occur. In addition, there is a drawback that the liquid component is reduced by repeatedly using the used developer in a circulating manner. Insufficient control of the developer concentration affects the development speed and makes process management difficult.

  Furthermore, in recent years, the photolithography production line has been increasing in size. This is particularly related to the increase in the size of glass substrates accompanying the widespread use of large-screen liquid crystal televisions. For example, there is a need for a color filter substrate using a large glass substrate whose mother glass is called the sixth generation (1500 × 1800 mm) or the eighth generation (2160 × 2400 mm). Increasing the size of a developing apparatus in which a large glass substrate having a thickness of 1 mm or less and a side of 1 to 2 m or more flows increases utility usage, makes process management difficult, and deteriorates the maintainability of the apparatus. In particular, as the substrate size is increased, the size and cost of the apparatus is increased, and the running cost is required to be reduced.

  Therefore, in Patent Document 1, the developer supplied for development is processed by an ultrafiltration (UF) filter to recycle the filtrate and circulate the concentrated solution. A developing device and a developing method that can keep running costs low without degrading quality, and prevent a decrease in the amount of filtrate due to clogging of the limit filtration filter when used for a long time, thereby facilitating maintenance. Is disclosed. In Patent Document 2, using the same apparatus as Patent Document 1, the alkali component concentration measurement result of the filtrate obtained by the ultrafiltration unit and the high alkalinity with respect to the concentration of the dissolved photosensitive resin composition in the developing tank are described. A developer concentration adjustment method for determining a high alkaline concentration solution replenishment amount according to the correlation between the concentration solution replenishment amount and the concentration recovery amount, and a developing device using the same are disclosed.

However, even in the developing devices of Patent Documents 1 and 2 described above, when the ultrafiltration device is used, the ultrafiltration filter absorbs the pigment component contained in the developer on the surface of the UF membrane or blocks the liquid-permeable holes. Cause a decrease in filtrate flow rate over time. As a countermeasure, self-cleaning called reverse cleaning operation is periodically performed for each ultrafiltration filter, but the reverse cleaning operation is one means for extending the life of the ultrafiltration filter. It is necessary to periodically replace the ultrafiltration filter, and perform the regeneration treatment by cleaning the removed ultrafiltration filter with an off-line device (external) of the developing device. In this case, since the apparatus is large-sized, replacement of the ultrafiltration filter and chemical cleaning require a lot of work time and work load.
WO2005 / 040930 JP 2007-241077 A

  The present invention has been made in view of the above problems, and is a circulation type developing device including an ultrafiltration unit used for manufacturing color filters, and is an efficient ultrafiltration filter during continuous operation and operation. Providing a developing device capable of cleaning and regenerating, reducing the replacement load of the ultrafiltration filter, stabilizing the flow rate of the filtrate, and realizing a long life of the entire ultrafiltration unit Is an issue.

The invention according to claim 1 of the present invention is at least a developing device used in a developing process of manufacturing a color filter using a developer circulation system,
(1) a developing tank for containing a developing solution;
A path for sending the developer in the developing tank to a developing tank in which a developing process is performed;
A path for returning the developer after being used in the developing process in the developing tank to the developing tank;
A path for sending the developer stored in the developer tank to the ultrafiltration circulation tank;
(2) a path for feeding liquid to a plurality of ultrafiltration filters in order to filter the developer in the ultrafiltration circulation tank;
A path for sending the filtrate to the filtrate reserve tank;
(3) means for measuring the concentration of the filtrate sent to the filtrate reserve tank;
A path for feeding a developer stock solution from the stock solution tank to the filtrate reserve tank to adjust the concentration of the filtrate;
(4) a path for supplying the developer stock solution from the stock solution tank to the preparation tank;
A path for feeding a developer (filtrate) whose concentration is adjusted from the filtrate reserve tank to a reserve tank to which a developer (new solution) is supplied through the preparation tank;
A path for feeding liquid from the reserve tank to the developing tank;
A developing device comprising means for measuring the developer concentration in the reserve tank to be constant,
In the developing device, the plurality of ultrafiltration filters are ultrafiltration filters having a molecular weight cut-off of 1000 or more .

The invention according to claim 2 of the present invention uses the developing device according to claim 1 and uses the developer (new solution + filtrate) sent from the reserve tank in the developing tank, The developing method is characterized in that the development processing of the body is performed .

  According to the developing device of the present invention, since the chemical solution supply piping path is provided in the filtration unit piping system so that the chemical solution for regeneration of the ultrafiltration filter can be supplied, the efficient limit during continuous operation and operation is provided. The filter can be cleaned and regenerated. Since the work of exchanging the ultrafiltration filter and the chemical cleaning process in the off-line apparatus, which are conventionally performed regularly, are almost unnecessary, the working time and work load can be reduced.

  In addition, since the conventional ultrafiltration filters are regularly replaced regardless of the decrease in the filtrate flow rate, there is a difference in the filtrate flow rate state between the ultrafiltration filters at the time of replacement. This was not appropriate from the viewpoint of extending the life of the entire filtration unit and stabilizing the filtrate flow rate. On the other hand, in the developing device of the present invention, it becomes possible to perform chemical cleaning / regeneration processing of each ultrafiltration filter at an optimum time based on the results of the filtrate flow rate value of each ultrafiltration filter. The filtrate flow rate is stable, and the lifetime of the entire ultrafiltration unit can be extended.

  Further, in the developing device of the present invention, the cleaning effect of the chemical solution itself is improved by providing air purge air, pure water, and hot water supply channels in the chemical solution supply piping path. In addition, the chemical solution can be supplied to both sides of the hollow fiber system and the liquid permeation hole, and controlled using a three-way valve to control any one of the ultrafiltration filters. Switching between filtering with a filtration filter and regeneration of an ultrafiltration filter can be easily performed, and the chemical solution can be prevented from being mixed into the original piping system during the supply of the chemical solution by controlling the three-way valve.

  Hereinafter, a developing device and a developing method of the present invention will be described based on an embodiment.

FIG. 1 is a schematic flow diagram illustrating the overall configuration of an embodiment of the developing device of the present invention. A new developing solution containing sodium carbonate (Na ₂ CO ₃ ) as a main developing solution is supplied to the developing tank 4 through the developing new solution supply line 3. Development is performed in a closed state in a clean room, and the developer is discharged from the developer discharge mechanism 1 through the liquid supply path 25 from the developer tank 4, and the target acrylic resin-based photosensitive resin is applied and developed in the developer tank 2. It carries out with respect to the to-be-developed glass substrate exposed to pattern. In FIG. 1, the developer discharge mechanism 1 is a showering step, but the method is not limited to this method. The developing solution after the development processing is stored in the developing tank 4 through the developing solution return path 24, and then is carried to the ultrafiltration circulation 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 drain path 7, and the decreased amount is reduced from the reserve tank 40 to the developing tank. The new solution is replenished to the developer 4 through the developing new solution supply line 3.

  The developer in the ultrafiltration circulation tank 6 is provided with five ultrafiltration filters in the present embodiment through the liquid feeding path 8, and the reverse cleaning tank 13 for backwashing each ultrafiltration filter, etc. Are sent to a filtration unit 9 including back-cleaning means for ultrafiltration. Thereafter, the filtrate that has passed through the ultrafiltration filter is sent to the filtrate reserve tank 12 through the liquid sending path 11, and the remaining concentrated liquid in which the components that do not pass through the ultrafiltration filter have increased is the ultrafiltration filter concentrated liquid circulation line. 21 is returned to the ultrafiltration circulation tank 6. In the developing device of the present invention, the regeneration chemical solution tank 10 is provided via the chemical solution supply path 50 so that the regeneration chemical solution can be supplied to the filtration unit 9, and any limit can be applied while the developing device is operating. Means are added to chemically clean the outer filter and restore its function.

  Here, an ultrafiltration filter having an optimum filtration accuracy is selected according to the degree of contamination of the developer and the type of the dissolved photosensitive resin composition. The fractionation molecular weight of the ultrafiltration filter needs to take into account the influence of operating conditions such as the circulation flow rate and the required filtrate amount, and it is necessary not to trap alkali components and surfactants effective for development. Is intended for an ultrafiltration filter having a molecular weight cut-off of 1000 to a particle size of 10 μm. In the case of an ultrafiltration filter having a filtration molecular weight of less than 1000, the permeation of dissolved ions is also blocked, so there is a risk that even the developer itself may be lost. Conversely, the ultrafiltration filter with a filtration accuracy exceeding 10 μm. In this case, contaminants cannot be trapped and the cleanliness of the filtrate is reduced.

The developer main component (Na ₂ CO ₃ ) concentration of the filtrate sent to the filtrate reserve tank 12 is measured, the developer stock solution is replenished so as to be a constant concentration, and the developer (filtrate) whose concentration has been adjusted is The developer is circulated by being sent to the reserve tank 40 in the clean room through the liquid feeding path 22. The reserve tank 40 is supplied with a developing solution (new solution) from the stock solution tank 42 through the preparation tank 41, and is measured and monitored so that the concentration of the developing solution becomes constant. Incidentally, in this embodiment, the sodium carbonate concentration is constant at 1.5 kg / m ³ .

  FIG. 2 is a partial schematic view showing a state in which the chemical supply path 50 for regenerating the ultrafiltration filter is provided in the piping system of the filtration unit 9 of the developing device of the present invention described in FIG. In addition to the chemical tank 10, the chemical supply path 50 is further provided with a hot water supply path 51, a pure water supply path 52 for cleaning, and an air supply path 53 for air purge in order to improve the cleaning and regeneration effect. Has been. The cleaning chemical solution can be supplied to the hollow fiber of the ultrafiltration filter or to both sides of the liquid permeation hole, so that the chemical solution does not enter the original filtration piping system while the chemical solution is being supplied. The cleaning chemical solution is discharged out of the system through the drainage system, and the ultrafiltration filter unit is washed with pure water, and air-purged and regenerated as necessary.

Next, a specific operation flow of the ultrafiltration filter regeneration in the developing device of the present invention will be described with reference to the flowchart of FIG. FIG. 3A is an example of the operation flow shown below, and shows the state of (STEP 1). In this case, each of the five ultrafiltration filters UF-1 to UF-5 has an operation flow shown below, and UF-2 to UF-5 are normal operation flows in which UF-2 is back-washed. is there. In UF-1, chemical solution cleaning is selected, the chemical solution is sent from the chemical solution tank A side, the chemical solution is sent from the circulation out side of UF-1, and is discharged from the circulation in side. While the cycle of UF-2 to UF-5 makes one round, the chemical solution washing and water washing of UF-1 are performed, and thereafter, the operation flow cycle (STEP 2) described later is performed.
-UF-1: chemical washing (circulation out-> circulation in) and water washing-UF-2: reverse washing-> filtrate supply-> filtrate supply-> filtrate supply-UF-3: filtrate supply-> reverse wash-> filtrate supply-> filtrate supply-UF -4: Filtrate supply-> filtrate supply->backwash-> filtrate supply / UF-5: filtrate supply-> filtrate supply-> filtrate supply-> backwash Figure 3 (b) shows an example of the operational flow shown below, with the state of (STEP2) It is shown. Each of the five ultrafiltration filters UF-1 to UF-5 has the operational flow shown below, and in this case as well, UF-2 to UF-5 are back-washed with UF-2. It is a normal operation flow. In UF-1, chemical cleaning is selected. In this cycle, the chemical is sent from the chemical tank B side, the chemical is sent from the filtration out side of UF-1 into the filter, and from the circulation out or circulation in side. Waste liquid. This cycle is performed for one or more cycles for a certain period of time, followed by sufficient water washing and replacement, and then the next stage is the UF-2 drug washing.
UF-1: chemical washing (circulation out → circulation in) and water washing → chemical washing (filtration out → circulation out or circulation in)
-UF-2: Reverse washing-> Filtration supply-> Filtration supply-> Filtration supply-> Reverse washing-UF-3: Filtrate supply-> Reverse washing-> Filtration supply-> Filtrate supply-> Filtrate supply-UF-4: Filtrate supply-> Filtrate supply-> Reverse Washing → Filtrate supply → Filtrate supply / UF-5: Filtrate supply → Filtrate supply → Filtrate supply → Backwash → Filtrate supply

FIG. 3 is a schematic flow diagram illustrating the overall configuration of an embodiment of the developing device of the present invention. FIG. 3 is a schematic view in which a filtration chemical unit of the developing device of the present invention is provided with a chemical solution supply path for regeneration. Explanatory drawing of the operation | movement flow of the ultrafiltration filter reproduction | regeneration in the image development apparatus of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Developer discharge mechanism 2 ... Developer tank 3 ... Developer new solution supply line 4 ... Developer tank 5 ... Liquid feed route 6 ... Ultrafiltration circulation tank 7 ... Drain path 8 ... Liquid feed path 9 ... Filtration unit 10 ... Chemical liquid tank 11 ... Liquid feed path 12 ... Filtrate reserve tank 13 ... Backwash tank 21 ... Ultrafiltration filter Concentrated liquid circulation line 22 ... Liquid feed path 24 ... Developer return path 25 ... Liquid feed path 40 ... Reserve tank 41 ... Preparation tank 42 ... Stock solution tank 50 ... Chemical solution Supply path 51 ... Warm water supply path 52 ... Pure water supply path 53 ... Air supply path

Claims (2)

At least a developing device used in a developing process of color filter manufacturing using a developer circulation system,
(1) a developing tank for containing a developing solution;
A path for sending the developer in the developing tank to a developing tank in which a developing process is performed;
A path for returning the developer after being used in the developing process in the developing tank to the developing tank;
A path for sending the developer stored in the developer tank to the ultrafiltration circulation tank;
(2) a path for feeding liquid to a plurality of ultrafiltration filters in order to filter the developer in the ultrafiltration circulation tank;
A path for sending the filtrate to the filtrate reserve tank;
(3) means for measuring the concentration of the filtrate sent to the filtrate reserve tank;
A path for feeding a developer stock solution from the stock solution tank to the filtrate reserve tank to adjust the concentration of the filtrate;
(4) a path for supplying the developer stock solution from the stock solution tank to the preparation tank;
A path for feeding a developer (filtrate) whose concentration is adjusted from the filtrate reserve tank to a reserve tank to which a developer (new solution) is supplied through the preparation tank;
A path for feeding liquid from the reserve tank to the developing tank;
A developing device comprising means for measuring the developer concentration in the reserve tank to be constant,
The developing device , wherein the plurality of ultrafiltration filters are ultrafiltration filters having a molecular weight cut-off of 1000 or more .   A developing method comprising: using the developing device according to claim 1, and performing development processing of a developing object using a developing solution (new solution + filtrate) sent from the reserve tank in the developing tank. .

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