KR20030035814A - A developer regeneration apparatus - Google Patents

Abstract

PURPOSE: To provide a developer regeneration unit which can constantly maintain development performance and can significantly shorten an operating shutdown time and reduce overall production cost by automatically controlling the resist and alkali concentrations of alkali developer for photosensitive organic resin to a prescribed level, respectively. CONSTITUTION: This unit is characterized in that it is equipped with a first resist concentration measuring means 5 for measuring the resist concentration of waste developer, the first discharge means 7 and 61 for discharging waste developer of the portion based on the measured results of the first measuring means 5, the first replenishing means 9 and 71 for replenishing new developer of the portion based on the quantity of liquid wast to be disposed of by the first discharge means 7 and 61, a first measuring means 22 for measuring the alkali concentration of developer obtained as a result of replenishment by the first replenishing means 9 and 71 and the second replenishing means 16 and 72 for replenishing raw developer of the quantity based on the measured results by the first alkali concentration measuring means 22.

Description

Developer regeneration apparatus

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus for regenerating an alkaline developer for photosensitive organic resin after use in a liquid crystal substrate manufacturing process, a printed substrate manufacturing process, a semiconductor substrate manufacturing process, or the like.

In a liquid crystal substrate manufacturing process, a printed substrate manufacturing process, a semiconductor substrate manufacturing process, or the like, an aqueous alkali solution such as tetramethylammonium hydroxide (TMAH) aqueous solution (2.380 wt% as an example) and gallium hydroxide aqueous solution is used as a spray solution or dip. (dip) method is used. In the conventional method, the developer starts by filling a predetermined amount of a new liquid alkaline developer with a predetermined concentration, using the number of substrate treatments based on experience and the like as an index, and the alkali concentration and the resist concentration of the alkali developer are determined to have a predetermined concentration. When it is done, the total amount is exchanged with the new liquid prepared in advance.

However, in the conventional method, since the alkaline developer is continuously used until a predetermined deterioration state, the resist concentration and the alkali concentration of the alkaline developer change over time, and the shape of the developed resist pattern is determined. There was a problem in that the dimensions of the line width and the film thickness cannot be constantly controlled. Therefore, there is a problem that the quality of the product becomes unstable or the yield falls.

In addition, there is a problem in that all of the liquids need to be replaced, resulting in longer operation downtime during the liquid exchange, which leads to a significant decrease in the operation rate and higher labor costs associated with the liquid exchange operation.

Therefore, the present invention has been devised to solve the above problems, and the resist concentration and alkali concentration of the alkali developer for photosensitive organic resin repeatedly used in a liquid crystal substrate manufacturing process, a printed substrate manufacturing process, a semiconductor substrate manufacturing process, etc. It is an object of the present invention to provide a developer regenerating apparatus capable of maintaining a constant developing performance and at the same time significantly reducing the downtime and reducing the overall manufacturing cost.

1 is a schematic flowchart of a developer regeneration plant according to an embodiment of the present invention.

2 is a schematic flowchart of a developing solution regeneration plant according to another embodiment (second embodiment) of the present invention.

3 is a schematic flowchart of a developing solution regeneration plant according to another embodiment (third embodiment) of the present invention.

4 is a schematic flowchart of a developing solution regeneration plant according to another embodiment (fourth embodiment) of the present invention.

<Description of the symbols for the main parts of the drawings>

5: first absorbance photometer (first resist concentration measuring means)

7: second waste liquid control valve (part of the first waste means)

9: first fresh liquid supply amount control valve (part of the first supply means)

16: first feedstock supply control valve (part of the second supply means and third supply means)

22: second alkali concentration meter (first alkali concentration measuring means)

61: first waste pipe (part of the first disposal means)

71: first supply pipe (part of the first supply means)

72: second supply pipe (part of second supply means and third supply means)

100: developer recycling plant

200: developer recycling plant

203: first pump (part of the first supply means)

205: first nano filter (first membrane separation means)

206: second pump (part of the first supply means)

207: first absorbance photometer (second resist concentration measuring means)

208: first valve (part of the first reflux means)

209: second valve (part of the second disposal means)

211: second nano filter (second membrane separation means)

213: second absorbance photometer (second resist concentration measuring means)

214: third valve (part of the third reflux means)

215: fourth valve (part of the second disposal means)

220: first alkali concentration meter (part of second alkali concentration measuring means)

251: first liquid feed pipe (part of the first supply means)

252: first reflux pipe (part of the first reflux means)

253: first waste pipe (part of the second disposal means)

256: second reflux pipe (part of the third reflux means)

300: developer recycling plant

351: second reflux pipe (second reflux means)

400: developer recycling plant

In order to achieve this object, the developer regeneration apparatus according to claim 1 includes a first resist concentration measuring means for measuring a resist concentration of an alkaline developing waste solution for photosensitive organic resin and a measurement of the first resist concentration measuring means. First disposing means for disposing the developer waste in a proportion based on the result; and first supplying alkali developing developer or pure water based on the amount of the developer waste discarded by the first disposing means. Alkali-based developer stock solution based on the replenishment means, the first alkali concentration measuring means for measuring the alkali concentration of the developer obtained as a result of replenishment by the first replenishing means, and the measurement result by the first alkali concentration measuring means. And a second supply means for distributing the water.

The developer regeneration device according to claim 2 includes a cross-flow first membrane separation means for membrane separation of alkaline developing waste liquid for photosensitive organic resin, and the developer waste solution as the first membrane separation means. A first supply means for supplying the gas, a second cross separation type membrane separation means for further separating the first permeate obtained as a result of the membrane separation by the first membrane separation means, and the second membrane separation means. Second supply means for supplying a first permeate, first reflux means for refluxing the first non-permeate obtained as a result of membrane separation by the first membrane separation means into a developing waste solution supplied by the first supply means, Second resist concentration measuring means for measuring the resist concentration of the first non-permeate liquid before reflux by the first reflux means or the developing waste solution after reflux, and the side of the resist concentration by the second resist concentration measuring means Result and a second discarding means for discarding the first cucurbit gwaaek or developing waste solution after the reflux based on.

The developer regeneration apparatus according to claim 3 is the developer regeneration apparatus according to claim 2, wherein the second non-permeable liquid obtained as a result of membrane separation by the second membrane separation means is provided by the first supply means. And a second reflux means for refluxing the developing waste liquid supplied by the method.

The developer regeneration apparatus according to claim 4 is the developer regeneration apparatus according to claim 2, wherein the second non-permeate liquid obtained as a result of membrane separation by the second membrane separation means is supplied to the second supply means. Second resist concentration for measuring the resist concentration of the third reflux means for reflux in the first permeate supplied by the second permeate, the second non-permeate before reflux by the third reflux means, or the first permeate after reflux And a second disposal means for discarding the second non-permeate liquid or the first permeate liquid after reflux based on the measurement means and the measurement result of the second resist concentration measurement means.

The developer regeneration device according to claim 5 is the developer regeneration device according to any one of claims 2 to 4, wherein the developer regeneration device is obtained as a result of membrane separation by a second membrane separation means. 2nd alkali concentration measuring means for measuring the alkali concentration of the permeate and a third replenishment means for replenishing the alkali developing developer or the alkaline developing stock solution in an amount based on the measurement result of the second alkali concentration measuring means. Equipped with.

The developer regeneration device according to claim 6 is the developer regeneration device according to claim 5, wherein the solution supplied by the third replenishment means is an alkaline developer stock solution.

Further, according to the present invention, when the resist concentration of the developing waste liquid (alkali developing waste liquid for photosensitive organic resin) is measured by the first resist concentration measuring means, the first waste means is based on the measurement result of the resist concentration. The amount of developing waste liquid is discarded, and by the first replenishing means, the amount of developing new liquid or pure water based on the discarded amount is supplied. Therefore, the developing waste solution "which is a liquid after development" is regenerated in a state containing a resist component of a desired concentration (including the meaning of a suitable concentration. The following is the same), further maintaining high applicability. .

According to the present invention, after the replenishment of the developing solution or pure water, the alkali concentration of the developer obtained as a result of replenishment by the first replenishing means is measured by the first alkali concentration measuring means. 2 The replenishing means replenishes the alkaline developing stock solution in an amount based on the measurement result of the alkali concentration. Therefore, the alkali concentration of the developing waste liquid is sequentially regenerated to the desired concentration (including the meaning of the appropriate concentration. Hereinafter, the same).

In addition, according to the present invention, the crosslinking first membrane separation means separates the developing waste into a first permeate in which the resist component is removed and a first non-permeate in which the resist component is concentrated. By the second membrane separation means, the first permeate is further separated into a second permeate from which the resist component has been removed and a second non-permeate liquid in which the resist component is concentrated. Therefore, the resist component contained in the developing waste solution is thoroughly removed.

Further, according to the present invention, the developing waste solution supplied with the first non-permeable liquid by the first supply means is refluxed by the first reflux means, and the first non-permeate liquid or the developing waste solution after reflux by the second resist concentration measuring means. The resist concentration is measured, and the first non-permeate liquid or the developing waste solution after reflux is discarded by the second waste means based on the measurement result. Therefore, the developing waste solution in which the resist component is concentrated is discarded.

Further, according to the present invention, the second non-permeate liquid obtained as a result of membrane separation by the second membrane separation means is refluxed by the second reflux means into the developing waste solution supplied by the first supply means. Here, the second non-permeable liquid has already been membrane separated by the first membrane separation means, and the supply destination of the developing waste liquid by the first supply means is the first membrane separation means. That is, the developer in which the resist component has been once removed is once again separated by the first membrane separation means together with the developer waste. As a result, operating costs are reduced and resources are effectively utilized.

Further, according to the present invention, the second non-permeate obtained as a result of membrane separation by the second membrane separation means is refluxed by the third reflux means to the first permeate supplied by the second supply means. Then, the concentration of the second non-permeate liquid before reflux or the first permeate liquid after reflux is measured by the second resist concentration measuring means, and the second non-permeate liquid or the first non-permeate liquid based on the measurement result by the second disposal means. Permeate is discarded. That is, the developer in which the resist component is once removed is circulated to the second membrane separation means. As a result, operating costs are reduced and resources are effectively utilized.

According to the present invention, when the alkali concentration of the second permeate obtained as a result of membrane separation by the second membrane separation means is measured by the second alkali concentration measuring means, the second alkali is supplied by the third replenishment means. An alkali developing developer or an alkaline developing stock solution is supplied in an amount based on the measurement result of the concentration measuring means. Therefore, the alkali concentration of the developing waste solution provided for development can be sequentially reproduced to a desired concentration.

According to the present invention, the alkaline developing stock solution is supplied by the third supply means. Here, the first membrane separation means or the second membrane separation means is cross flow, and the ratio of the permeate and the concentrate is considerably higher in the permeate. Therefore, although the alkali concentration of the developing solution provided for image development falls, since the alkali concentration is adjusted to a desired density | concentration, the quantity of the developing solution itself is prevented from changing. When the amount of the solution is changed, complicated processing (work) for monitoring the amount of the developer to be in an appropriate range is forced. For example, when the amount of the developer is increased, the amount of the developer that is not deteriorated until disposal is increased. While the disposal is forced, when the amount of the developing solution is insufficient, the supply of the developing stock solution, the developing new solution and the pure water is forced so that the alkali concentration and the resist concentration of the developing solution become the desired concentrations.

[First Embodiment]

Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings. The developer regeneration plant of the present invention is used in the liquid crystal substrate manufacturing process, the printed substrate manufacturing process, or the semiconductor substrate manufacturing process, to perform the regeneration treatment of the developing waste solution provided for development. 1 is a schematic flowchart of a developer regeneration plant 100 according to an embodiment of the present invention. In addition, in each accompanying drawing, each plant simplified is shown in order to make understanding of an invention easy.

As shown in FIG. 1, the developer regeneration plant 100 includes a first storage tank 1, a first tank liquid supply valve 2, a first pump 3, and a first return liquid control valve ( 4), the first absorbance photometer (5), the first liquid supply amount control valve (6), the first waste liquid amount control valve (7), the first reuse liquid amount control valve (8), and the first new liquid supply amount Control valve 9, second storage tank 10, first alkali concentration meter 11, first thermometer 12, first load cell 13, and second tank liquid feed The valve 14, the third pump 15, the first feedstock supply control valve 16, the first combination tank 17, the second load cell 18, the third pump 19, The first heat exchanger 20, the first small tank 21, the second alkali concentration meter 22, the second thermometer 23, the first combination tank liquid supply valve 24, Fourth pump 25, fourth storage tank 26, fourth tank liquid supply valve 27, fifth pump 28, fine particle removal filter 29, nitrogen exhaust pipe 30 Is installed.

The 1st storage tank 1 is a tank used for the developing process (photolithography process), ie, storing the developing solution (development waste) after being provided for developing. The first storage tank 1 is formed with an inflow zone 1a through which the developing waste flows in and an outflow zone 1b through which the developing waste flows out, and a resin screen between the inflow zone 1a and the outflow zone 1b. The defoaming filter 1c which consists of these is provided. In the inflow zone 1a, a developing waste liquid (hereinafter referred to as "regeneration waste liquid" for convenience) is introduced into the inflow zone 1a. In the outflow zone 1b, a developing waste liquid which flows into the inflow region 1a and in which bubbles in the unregenerated developer waste liquid is removed by the defoaming filter 1c (hereinafter referred to as "unrecovered developer waste liquid" for convenience). ) Is supposed to be stored. In this way, since the bubbles in the unregenerated developer are removed by the defoaming filter 1c, it is possible to eliminate the disturbance of the subsequent developer regeneration process.

The first tank liquid supply valve 2 opens and closes the flow path of the first liquid supply pipe 51 connected to the lower end of the first storage tank 1, thereby allowing the first regeneration to be fed in the first liquid supply pipe 51. It is a valve for adjusting the flow rate of the processed waste liquid (of course, "0" l (liter) when the first tank liquid feed valve 2 is closed. The same applies to the valve described below.) The first pump 3 is a pump for feeding the developing waste solution after the first regeneration treatment to the next process side (downstream side) through the first liquid feeding pipe 51.

The 1st return liquid amount control valve 4 is a valve for adjusting the flow volume of the developing waste liquid conveyed in the 2nd liquid feeding pipe 52 by opening and closing the flow path of the 2nd liquid feeding pipe 52. The second liquid feed pipe 52 is one flow path branching from the first liquid feed pipe 51, and one end of the second liquid feed pipe 52 is connected to the first liquid feed pipe 51. The other end of the two liquid feed pipes 52 is connected to the first storage tank 1. That is, the amount of the developing waste liquid returned (returned) to the first storage tank 1 side is adjusted by the first return liquid amount adjusting valve 4.

The first absorbance photometer 5 is a measuring device for measuring the resist concentration of the developer waste solution after the first regeneration treatment, which is delivered through the second liquid feed pipe 52, and is disposed in parallel with the second liquid feed pipe 52. It is. The proportion of the developer to be reused or discarded is controlled based on the measurement result of the first light absorption photometer 5, that is, based on the resist concentration of the developer waste after the first regeneration treatment.

The first liquid supply amount regulating valve 6 is for adjusting the flow rate of the developing waste solution after the first regeneration treatment which is fed through the third liquid feed pipe 53. The third liquid feed pipe 53 is a flow path branching from the first liquid feed pipe 51, one end thereof is connected to the first liquid feed pipe 51, and the other end thereof is connected to the second storage tank 10. Connected.

The first waste liquid amount control valve 7 is for adjusting the amount of the developing waste liquid after the first regeneration treatment flowing through the first waste liquid pipe 61 by opening and closing the flow path of the first waste liquid pipe 61. . Here, the first waste liquid pipe 61 is a flow path branching from the first liquid feed pipe 51, one end of which is connected to the first liquid feed pipe 51, and the other end thereof is a predetermined waste liquid tank or waste liquid treatment apparatus. And the like. On the other hand, the first reuse liquid amount control valve 8 opens and closes the flow path of the third liquid feed pipe 53 to adjust the liquid amount of the developer waste liquid after the first regeneration treatment flowing in the third liquid feed pipe 53. will be.

The first waste liquid amount control valve 7 and the first reuse liquid amount control valve 8 are interlocked with each other, and the opening amount of the first waste liquid amount control valve 7 and the first reuse liquid amount control valve 8 are interlocked with each other. And the opening time is controlled based on the measurement result of the first absorbance photometer 5. Moreover, the liquid amount which combined the quantity of the development waste liquid which passed the 1st waste-liquid control valve 7 through the 1st waste liquid quantity control valve 7, and the quantity of the developer waste liquid which passes through the 1st reuse liquid volume control valve 8 is a 1st liquid supply amount. The amount of the developing waste liquid passing through the regulating valve 6 is set to match. Therefore, the proportion of the developer to be reused or disposed in accordance with the resist concentration in the developer waste solution after the first regeneration treatment is controlled.

The first fresh liquid supply amount regulating valve 9 is for controlling the amount of the alkaline developing developer flowing through the first supply pipe 71 by opening and closing the flow path of the first supply pipe 71. Here, the alkali developing developer is a developer obtained by thinning an alkaline developer (tetramethylammonium hydrooxide) (TMAH) to 2.38 wt%. The alkali developer is usually 20 to 25 wt% of an alkaline developer that is produced in advance in a factory or the like and transported (transported) to the installation site of the developer regeneration plant 100 in order to reduce transportation costs.

The downstream end of the first supply pipe 71 is the downstream side of the first reuse liquid amount control valve 8 and is connected to the third liquid feed pipe 53. That is, by the 1st new liquid supply amount control valve 9, the quantity of the developing new liquid supplied further with respect to the developing waste liquid which flows in the 3rd liquid feed pipe 53 is controllable. The second storage tank 10 refers to a solution after additionally supplying a developing solution to the developing waste solution (hereinafter, a solution after additionally supplying a developing solution to the developing waste solution is referred to as a "developed second regeneration treatment"). ) Is a tank (gas) for temporary storage.

The first alkali concentration meter 11 is a measuring device for measuring the alkali concentration of the "developing solution after the second regeneration process" stored in the second storage tank 10. The measuring principle of the first alkali concentration meter 11 allows an electric current to flow between the primary coil and the secondary coil so that the developing waste solution becomes a catalyst, and measures the alternating current generated in the secondary coil. The alkaline concentration is measured by deriving the phase difference between the current flowing in the secondary coil and the current flowing in the secondary coil.

The first thermometer 12 is a measuring device for measuring the temperature of the developer waste solution after the second regeneration treatment stored in the second storage tank 10, and based on the measurement result of the thermometer, the first alkali concentration meter The temperature value of the developer waste solution after the second regeneration treatment derived from the measured value in (11) is corrected. Therefore, the precision of measuring the alkali concentration of the developing waste solution after the 2nd regeneration process can be improved. This is because the measured value of the first alkali concentration meter 11 fluctuates little by little in response to the temperature change of the developing waste solution after the second regeneration treatment.

The first load cell 13 outputs a current value corresponding to the magnitude of the load, and the protrusion 10a and the bottom portion 10b (base) installed in the state protruding from the outer wall of the second storage tank 10. It is sandwiched between. Therefore, the weight of the whole 2nd storage tank 10 can be measured by the electric current value output by the 1st load cell 13, Furthermore, by this weight as much as the weight of the 2nd storage tank 10 itself. Subtracting the value of, it is possible to derive the amount of the developing waste liquid stored in the second storage tank (10). And based on the measurement result of this 1st load cell 13, the opening amount and opening time of the 1st fresh-liquid supply amount control valve 9 can be controlled.

The second tank liquid supply valve 14 opens and closes the flow path of the fourth liquid supply pipe 54 connected to the lower side (lower end) of the second storage tank 10, thereby transferring the liquid supplied into the fourth liquid supply pipe 54. It is a valve to control the flow rate of developing waste after the second regeneration treatment. The third pump 15 is a pump for feeding the developing waste solution after the second regeneration treatment to the next process side (downstream side) through the fourth liquid feed pipe 54.

The first raw liquid supply amount control valve 16 opens and closes the flow path of the second supply pipe 72 to adjust the flow rate of the alkaline developing stock solution (20-25% TMAH aqueous solution) flowing through the second supply pipe 72. For the valve. The downstream end of the second supply pipe 72 is connected to the first combination tank 17.

The first combination tank 17 collects both liquids of the second developer recycling finished liquid fed through the fourth liquid feed pipe 54 and the alkaline developing stock solution fed through the first feed liquid supply control valve 16. It is a tank to store, and this 1st combination tank 17 is provided with the stirring blade 17a and the drive motor 17b. These stirring blades 17a and the driving motor 17b are for stirring and mixing the solution stored in the first combination tank 17. Therefore, it is possible to equally mix both the developer waste solution fed through the fourth liquid feed pipe 54 and the developer solution of the developer stock solution supplied through the second supply pipe 72. The developing solution mixed in this way is referred to as "developing waste solution after the third regeneration treatment".

Like the first load cell 13, the second load cell 18 outputs a current value corresponding to the magnitude of the load, and is provided with a protrusion 18a protruding from the outer wall of the first combination tank 17. And the bottom portion 18b (base). Therefore, the amount of developing waste stored in the first combination tank 17 can be derived in the same manner as in the case of the first load cell 13, so that the opening amount and opening of the first stock solution supply control valve 16 are opened. The control of time can also be made based on the output current value of this second load cell 18.

The third pump 19 is a pump for feeding the developing waste solution after the third regeneration treatment to the first heat exchanger 20 through the first circulation pipe 81. Here, the first circulation pipe 81 is a flow path for circulating the third waste recycling processing waste stored in the first combination tank 17, and the third waste recycling processing waste flowing through the flow passage is completed. By measuring the alkali concentration of, the alkali concentration of the developer waste solution after the third regeneration treatment can be accurately measured.

The first heat exchanger 20 is a device for cooling the developer flowing in the first circulation pipe 81. The third waste regenerated developing waste stored in the first combination tank 17 is agitated, so that the liquid temperature rises. An error occurs in the measurement result of the second alkali concentration meter 22 with the increase in the liquid temperature. It can prevent.

The 1st small tank 21 is a tank for storing the developer liquid circulated (circulated) through the 1st circulation pipe 81, and is provided in the downstream of the 1st heat exchanger 20. As shown in FIG. The second alkali concentration meter 22 is a measuring device for measuring the alkali concentration of the developing waste solution after the third regeneration treatment stored in the first small tank 21. Since the measuring principle of this 2nd alkali concentration meter 22 is the same as that of the 1st alkali concentration meter 11, the description is abbreviate | omitted.

The second thermometer 23 is for measuring the liquid temperature of the developing waste solution after the third regeneration treatment stored in the first small tank 21, and based on the measurement result of the second thermometer 23, the second thermometer 23 is used to measure the liquid temperature. By correcting the measurement result of the alkali concentration meter 22, the measurement accuracy of the second alkali concentration meter 22 can be improved.

The first combination tank liquid supply valve 24 opens and closes the flow path of the fifth liquid supply pipe 55 connected to the lower end of the first combination tank 17, thereby transferring the third liquid fed into the fifth liquid supply pipe 55. It is a valve for adjusting the flow rate of the regeneration treatment finished developer waste solution, and the fourth pump 25 is a pump for feeding the third regeneration treatment completed developer waste solution to the downstream side through the fifth feed pipe (55).

The 4th storage tank 26 is a tank for storing the 3rd regeneration processing completed waste liquid conveyed to the downstream side through the 5th liquid feed pipe 55, and is required by the 4th storage tank 26 at the image development process. The developing waste solution after the third regeneration treatment is stored. The fourth tank liquid supply valve 27 opens and closes the flow path of the sixth liquid delivery pipe 56 connected to the lower end of the fourth storage tank 26, thereby transferring the third liquid delivered into the sixth liquid delivery pipe 56. It is a valve for adjusting the flow rate of the developer waste after the regeneration treatment, the fifth pump 28 is the sixth liquid feed pipe 56 to the third regeneration treatment finished developer waste stored in the fourth storage tank (26) It is a pump for feeding the liquid to the next process side, that is, the developing process side.

The fine particle removal filter 29 is for further removing the fine particles in the developing waste solution after the third regeneration treatment, which is sent to the developing process, and the developing waste solution from which the fine particles have been removed is used as the developing solution after the regeneration treatment to the developing process side. It is sent.

The nitrogen supply pipe 30 is configured to supply nitrogen to the storage tanks of all of the first storage tank 1, the second storage tank 10, the first combination tank 17, and the fourth storage tank 26. It constitutes a flow path. Therefore, it is possible to prevent the developing waste liquid stored in each storage tank 1, 10, 17, 26 from reacting with air and changing the alkali concentration.

Hereinafter, the modified example of the said Example (1st Example) is demonstrated. FIG. 2 is a schematic flowchart of the developer recycling plant 200 of the second embodiment, FIG. 3 is a schematic flowchart of the developer recycling plant 300 of the third embodiment, and FIG. 4 is a schematic flowchart of the developer recycling plant 400 of the fourth embodiment. It is a schematic flowchart. Here, all of the developer recovery plants 200, 300, and 400 from the second embodiment to the fourth embodiment have a higher resist component removal capability than the developer recovery plant 100 of the first embodiment.

Second Embodiment

As shown in FIG. 2, the developer regeneration plant 200 of the second embodiment includes a first storage tank 201, a first storage tank liquid supply valve 202, a first pump 203, and a first filter. 204, first nanofilter 205, second pump 206, first absorbance photometer 207, first valve 208, second valve 209, and first heat exchange. Group 210, second nanofilter 211, first combination tank 212, second absorbance photometer 213, third valve 214, fourth valve 215, The first load cell 216, the third pump 217, the second heat exchanger 218, the first small tank 219, the first alkali concentration meter 220, the first thermometer 221, , The first combination tank liquid supply valve 222, the fourth pump 223, the second storage tank 224, the second storage tank liquid supply valve 225, the fifth pump 226, and the fine particles. The removal filter 227 is provided. In addition, the same code | symbol is attached | subjected to the same part as 1st Example, the description is abbreviate | omitted, and only another part is demonstrated.

The first storage pump 201, the first storage tank liquid supply valve 202, and the first pump 203 are respectively the first storage pump 1 and the first tank liquid supply valve 2 in the first embodiment. And since it has the structure substantially the same as the 1st pump 3, the description is abbreviate | omitted.

The first filter 204 removes the fine particles in the developer waste solution after the first regeneration treatment, which is delivered through the first liquid supply pipe 251, and the fine particles in the permeable membranes of the first and second nanofilters. Can be prevented from clogging and the removal process of the resist component can be performed smoothly.

A first nanofilter 205 is provided downstream of the first filter 204, and the first nanofilter 205 is an NF film capable of removing particles or polymers having a size of about several nanometers (nanometers). 205a, and has a cross flow type. Therefore, the developer waste solution that has passed through the NF film 205a is a developer waste solution in which the resist component has been substantially removed, and a large amount of the resist component is contained in the developer waste solution that has not passed through the NF film 205a.

The developing waste liquid that has not passed through the first nanofilter 205 is configured to join the developing waste liquid in the first liquid feeding pipe 251 through the first reflux pipe 252 and again through the second pump 206. The liquid is sent to the nano filter 205.

The first absorbance photometer 207 is a measuring device for measuring the resist concentration of the developing waste liquid returned through the first reflux tube 252 and is provided in parallel with the first reflux tube 252. The opening / closing amount of the first valve 208 and the second valve 209 is controlled based on the measurement result of the first light absorption photometer 207. Here, the first valve 208 is installed in the first reflux pipe 252, to control the amount of the developing waste liquid flowing in the first reflux pipe 252, the second valve 209 is a first waste pipe ( 253) to adjust the amount of developing waste liquid flowing in the first waste liquid pipe 253. Therefore, as a result of measuring the resist concentration by the first light absorption photometer 207, the developer waste solution can be reused until the resist concentration of the developer waste deteriorates to such an extent that it cannot withstand reuse. Furthermore, the amount of the developing waste liquid to be discarded can be reduced, the operating cost can be reduced, and the resources can be effectively utilized.

The first heat exchanger 210 is for cooling the developing waste liquid flowing in the first reflux tube 252. The first heat exchanger 210 causes an error in the measured value of the first absorbance photometer 207. It can be prevented from occurring.

The second nanofilter 211 has a structure substantially the same as that of the first nanofilter 205, and the developer waste solution containing a large amount of a resist component by membrane separation of the developer waste solution conveyed through the second liquid feed pipe 254. And the developer waste solution from which the resist component has been removed. The developing waste solution that has passed through the second nanofilter 211 is fed to the first combination tank 212 through the third liquid feed pipe 255, and the developing waste solution that has not passed through the second nanofilter 211 is subjected to the second reflux. It is joined to the second liquid pipe 254 through the pipe 256 again.

The second absorbance photometer 213 is a measuring device for measuring the resist concentration in the developing waste liquid fed to the first combination tank 212 through the third liquid feed pipe 255, and the measured value of the second absorbance photometer 213. Based on this, the opening / closing amount of the third valve 214 and the fourth valve 215 is controlled. Here, the third valve 214 is provided in the second reflux pipe 256, and the fourth valve 215 is provided in the second waste pipe 257. That is, the third valve 214 adjusts the flow rate of the second reflux pipe 256 and the fourth valve 215 adjusts the flow rate of the second exhaust pipe 257.

First combination tank 212, first load cell 216, third pump 217, second heat exchanger 218, first small tank 219, first alkali concentration meter 220, first thermometer 221, the first combination tank liquid supply valve 222, the fourth pump 223, the second storage tank 224, the second storage tank liquid supply valve 225, the fifth pump 226, and the fine particle removal The filter 227 is the first combination tank 17, the second load cell 18, the third pump 19, the first heat exchanger 20, and the first small tank 21 in the first embodiment. , The second alkali concentration meter 22, the second thermometer 23, the first combination tank feed valve 24, the fourth pump 25, the fourth storage tank 26, the fourth feed valve 27, and the first 5 pump 28 and fine particle removal filter 29 correspond to each other, and since the structure is substantially the same, the description is abbreviate | omitted.

Third Embodiment

Hereinafter, the developing solution regeneration plant 300 of the third embodiment will be described. In describing the third embodiment, the same parts as in the first embodiment and the second embodiment are denoted by the same reference numerals, and description thereof is omitted.

As shown in FIG. 3, the developer regeneration plant 300 of the third embodiment includes a first storage tank 201, a first storage tank liquid supply valve 202, a first pump 203, and a first pump. Filter 204, first nanofilter 205, second pump 206, first absorbance photometer 207, first valve 208, second valve 209, first The heat exchanger 210, the second nanofilter 211, the first combination tank 212, the second absorbance photometer 213, the first load cell 216, the third pump 217, , A second heat exchanger 218, a first small tank 219, a first alkali concentration meter 220, a first thermometer 221, a first combination tank liquid supply valve 222, and a fourth pump 223, a second storage tank 224, a second storage tank liquid supply valve 225, a fifth pump 226, and a fine particle removal filter 227.

The developer regeneration plant 300 of the third embodiment changes the reflux portion of the developer waste solution that has not passed through the second nanofilter 211 with respect to the developer regeneration plant 200 of the second embodiment. Specifically, the developing solution regeneration plant 300 of the third embodiment passes through the first storage tank 201 (via the second reflux pipe 351) to return the developing waste solution which has not passed through the second nanofilter 211. It is done. With this configuration, since the developing waste liquid passing through the second nano filter 211 is a developer waste liquid once separated by the first nano filter 205, the developer waste liquid is returned to the first storage tank 201 to effectively utilize the resources. It can be utilized. In addition, the reflux destination of the developing waste liquid that has not passed through the second nanofilter 211 is not limited to the first storage tank 201, but may be, for example, the first reflux tube 252.

[Example 4]

Hereinafter, the developer recycling plant 400 of the fourth embodiment will be described. In describing the fourth embodiment, the same parts as those in the first to third embodiments are denoted by the same reference numerals, and description thereof is omitted.

As shown in FIG. 4, the developer recycling plant 400 of the fourth embodiment includes a first storage tank 201, a first storage tank liquid supply valve 202, a first pump 203, and a first filter. 204, first nanofilter 205, second pump 206, first absorbance photometer 207, first valve 208, second valve 209, and first heat exchange. Group 210, the second nano filter 211, the third storage tank 401, the third storage tank liquid supply valve 402, the sixth pump 403, and the third reflux control valve ( 404, the third liquid supply control valve 405, the first combination tank 212, the second absorbance photometer 213, the first load cell 216, the third pump 217, The second heat exchanger 218, the first small tank 219, the first alkali concentration meter 220, the first thermometer 221, the first combination tank liquid supply valve 222, and the fourth pump ( 223, a second storage tank 224, a second storage tank liquid supply valve 225, a fifth pump 226, and a fine particle removal filter 227.

The third storage tank 401 is a tank for temporarily storing a developing waste solution that has passed through the NF film 205a of the first nano filter 205, and the third storage tank liquid supply valve 402 is a third storage tank 401. ), The amount of liquid to be delivered to the next process side is controlled, and the sixth pump 403 is to transfer the developing waste stored in the third storage tank 401 to the next process side.

The third reflux control valve 404 is for refluxing the developing waste liquid fed to the next process side by the sixth pump 403 back to the third storage tank 401 side, and the third liquid feed volume control valve 405 is It is a valve for controlling the flow rate of the developing waste liquid fed to the second nano-filter 211 side.

That is, the developer regeneration plant 400 of the fourth embodiment uses the third storage tank 401 between the first nanofilter 205 and the second nanofilter 211 of the developer regeneration plant 300 of the third embodiment. At the same time, the sixth pump 403 is installed. Therefore, although the pressure of the developing waste solution which permeate | transmitted the 1st nano filter 205 falls, it can press again by the 6th pump 403, and the area of the 2nd nano filter 211 becomes the case of a 3rd Example. It can be made significantly smaller than that. Therefore, manufacturing cost and operation cost can be reduced. Further, the third storage tank 401 may not necessarily be provided between the first nanofilter 205 and the second nanofilter 211.

As mentioned above, although this invention was demonstrated based on the Example, this invention is not limited to the said Example, It can be easily estimated that various improvement deformation is possible in the range which does not deviate from the main point of this invention. .

According to the developer regeneration apparatus according to claim 1, the developer waste liquid of the amount based on the measurement result (resist concentration of the developer waste solution) of the first resist concentration measuring means is discarded by the first disposal means. By the replenishing means, the developing new solution or pure water based on the discarded amount is replenished. After the replenishment of the developing new solution or the pure water, the alkali concentration of the developer obtained as a result of replenishment by the first replenishing means is measured by the first alkali concentration measuring means, and the first alkali concentration is measured by the second replenishing means. The amount of alkaline developing stock solution is replenished based on the measurement result by the means. Therefore, there is an effect that the resist concentration and the alkali concentration of the developing waste solution, which is the liquid after being provided for development, can be sequentially reproduced at a desired concentration (including the meaning of the appropriate concentration. The same applies hereinafter). Furthermore, it is possible to prevent the quality of the product from becoming unstable or to lower the yield, and also to maintain high applicability. Moreover, since the frequency | count which replaces all the liquids can be reduced significantly, there is also an effect which can prevent that operation rate falls and the labor cost accompanying liquid exchange operation becomes high.

According to the developer regenerating apparatus according to claim 2, the first permeate and the resist component in which the developer waste solution, which is a liquid after development, is removed by the cross flow first membrane separation means. The membrane is separated into the concentrated first non-permeate liquid, and similarly, the second permeate liquid in which the first permeate is further removed from the resist component and the second non-permeate in which the resist component is concentrated by a cross flow type second membrane separation means. Membrane is separated into the liquid. Therefore, the resist component contained in the developing waste solution can be removed thoroughly, and furthermore, there is an effect that a circuit faithful to the resist pattern can be formed on the substrate. Specifically, the resin solidified by exposure can be prevented from being dissolved. For example, when manufacturing a semiconductor device (LSI, memory, etc.), it becomes a fine circuit structure in many cases. However, even in this case, disconnection or crosstalk of the circuit can be prevented.

On the other hand, the first non-permeate obtained as a result of membrane separation by the first membrane separation means by the first reflux means is refluxed to the developing waste solution supplied by the first supply means, and by the second resist concentration measuring means, 1 The resist concentration of the non-permeate solution or the developing waste solution after reflux is measured, and the first non-permeate solution or the developing waste solution after reflux is discarded based on the measurement result. Therefore, the developer can be discarded in the state where the resist concentration is increased, and the amount of the developer to be discarded can be reduced. Moreover, the resist component is blocked by the membrane separation means, and there is also an effect that the membrane separation amount can be prevented from decreasing.

According to the developer regeneration device according to claim 3, in addition to the effect achieved by the developer regeneration device according to claim 2, the second non-permeable liquid is supplied by the second reflux means. Since it is refluxed to the developing waste solution supplied by the means, the developer which once removed the resist component is membrane-separated by the first membrane separation means together with the developing waste solution, thereby reducing the operating cost and further effectively utilizing the resources. There is.

According to the developer regeneration device according to claim 4, in addition to the effect achieved by the developer regeneration device according to claim 2, the second non-permeable liquid is first permeated by the third reflux means. Since the liquid is refluxed into a liquid and the liquid is discarded based on the concentration of the second non-permeate liquid before the reflux or the first permeate liquid after the reflux by the waste disposal means, the developer having once removed the resist component together with the developer waste solution is again subjected to the first film. The membrane is separated by the separating means to reduce the operating cost, and furthermore, the resource can be effectively utilized.

According to the developer regenerating apparatus according to claim 5, in addition to the effect of the developer regenerating apparatus according to any one of claims 2 to 4, furthermore, by the third replenishment means, Since the alkali developing developer or the alkaline developing stock solution in an amount based on the measurement result of the second alkali concentration measuring means is replenished, there is an effect that the alkali concentration of the developing waste solution provided after the development can be sequentially reproduced to a desired concentration. Furthermore, there is an effect that can prevent the product from becoming unstable or the yield is lowered. In addition, since the number of times of exchanging all the liquids can be greatly reduced, there is also an effect that the operation rate can be reduced and the labor cost caused by the liquid exchanging operation can be prevented from increasing.

According to the developer regeneration device according to claim 6, in addition to the effect achieved by the developer regeneration device according to claim 5, the solution supplied by the third replenishment means is an alkaline developer stock solution. Since the alkali concentration is regenerated to the desired concentration, there is an effect that the amount of the developer can be prevented from changing.

Claims (6)

First resist concentration measuring means for measuring the resist concentration of the alkaline developing waste liquid for photosensitive organic resin, First waste means for discarding the developer waste liquid in a proportion based on the measurement result of the first resist concentration measuring means; First replenishment means for replenishing alkali developing developer or pure water based on the amount of the developing waste solution discarded by the first disposal means; First alkali concentration measuring means for measuring an alkali concentration of a developer obtained as a result of replenishment by the first replenishing means; And a second replenishment means for replenishing an alkaline developer stock solution in an amount based on the measurement result by said first alkali concentration measurement means. A first cross separation type membrane separation means for membrane separation of alkaline developing waste liquid for photosensitive organic resin, First supply means for supplying the developing waste solution to the first membrane separation means; Cross-flow second membrane separation means for further membrane separation of the first permeate obtained as a result of membrane separation by said first membrane separation means; Second supply means for supplying the first permeate to the second membrane separation means; First reflux means for refluxing the first non-permeate liquid obtained as a result of membrane separation by the first membrane separation means into a developing waste solution supplied by the first supply means; Second resist concentration measuring means for measuring a resist concentration of the first non-permeate liquid before reflux by the first reflux means or the developing waste solution after reflux; And a second disposal means for discarding the first non-permeate solution or the developing waste solution after reflux, based on the measurement result of the resist concentration by the second resist concentration measurement means. The developer according to claim 2, further comprising a second reflux means for refluxing the second non-permeate liquid obtained as a result of membrane separation by the second membrane separation means into the developing waste solution supplied by the first supply means. Playback device. 3. The third reflux means according to claim 2, wherein the second non-permeate liquid obtained as a result of membrane separation by the second membrane separation means is refluxed to the first permeate supplied by the second supply means; Second resist concentration measuring means for measuring the resist concentration of the second non-permeate liquid before reflux by the third reflux means or the first permeate liquid after reflux; And second disposing means for disposing the second non-permeate liquid or the first permeate liquid after reflux, based on the measurement result of the second resist concentration measuring means. The second alkali concentration measuring means according to any one of claims 2 to 4, wherein the alkali concentration measurement means for measuring the alkali concentration of the second permeate obtained as a result of membrane separation by the second membrane separation means, And a third replenishment means for replenishing the alkali developing developer or the alkaline developing stock solution in an amount based on the measurement result of the second alkali concentration measuring means. A developing solution regeneration device according to claim 5, wherein the liquid supplied by the third replenishing means is an alkaline developing stock solution.