JP2785432B2 - Method and apparatus for coagulating coagulable solution - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aggregating method and an aggregating apparatus for an aggregating solution in which a solute component is aggregated and precipitated by adjusting pH, and more particularly, to processing of a photoresist developing waste liquid. The present invention relates to a coagulation treatment method and a coagulation treatment device suitable for use in the present invention.

[Related Art] As an example of a conventional method for aggregating a cohesive solution, a resist process technology, which is one of semiconductor process technologies, can be mentioned. This technique forms a variety of patterns on the substrate by coating a photosensitive resin on a substrate such as a silicon wafer or bonding and adhering the film as a film, and exposing and developing the photosensitive resin using ultraviolet rays or the like. Things. As the above-mentioned photosensitive resin, a positive type photoresist composed of a sensitizer such as a quinonediazide type, a resin component such as an alkali-soluble phenol type or an acrylic type, and an organic solvent is generally used because of high resolution. Used in And the alkaline development waste liquid after developing this positive photoresist has a property that the resin component which is a solute component coagulates and precipitates when the pH is adjusted using an acidic solution, and is a typical example of the cohesive solution. . An apparatus as shown in FIG. 3 is generally used as an apparatus for coagulating this cohesive solution.

This coagulation treatment apparatus A is generally constituted by a treatment tank 1, a stirring means 2, a control liquid supply means 3, a cohesive solution supply means 4, and a PH measurement device 5.

The processing tank 1 is a tank for coagulating a resist developing waste liquid, which is an example of the cohesive solution S, and its main part is formed of a substantially cylindrical container. A drain pipe for discharging the treated coagulable solution T subjected to the coagulation treatment is provided at the lower end of the processing tank 1.
A drain pipe 12 for overflowing the treated cohesive solution T is connected near the upper end.

The stirring means 2 is used to quickly and uniformly react and coagulate the coagulable solution S and the pH-adjusting solution, thereby forming the coagulable solution S
Is for stirring. A stirring blade 13 constituting a main part of the stirring means 2 is provided in the processing tank 1 and is rotatable in a fixed direction about a substantially vertical axis.

The adjustment liquid supply means 3 is for supplying a PH adjustment liquid composed of an acidic aqueous solution containing an acid such as sulfuric acid or hydrochloric acid into the treatment tank 1. An adjusting liquid supply pipe 14, which is a main component of the adjusting tank, is provided from the adjusting liquid supply means 3 into the processing tank 1.

The cohesive solution supply means 4 is for supplying the cohesive solution S into the processing tank 1. From the cohesive solution supply means 4, a cohesive solution supply pipe 15, which is a main component of the treatment tank 1, is provided.

The PH measuring device 5 is for measuring the PH of the cohesive solution S. PH which is a main component of the PH measuring device 5
The detection electrode 14 is immersed in the cohesive solution S in the processing tank 1.

A method of coagulating the cohesive solution S using the coagulation apparatus A configured as described above will be described.

First, a predetermined amount of the cohesive solution S is supplied into the treatment tank 1 by the cohesive solution supply means 4. Next, the pH of the cohesive solution S is measured by the PH measurement device 5 while stirring the cohesive solution S using the stirring means 2. Next, the pH of the cohesive solution S is adjusted by supplying the PH adjustment liquid into the treatment tank 1 using the adjustment liquid supply means 3 while measuring the pH of the cohesive solution S. The pH of the cohesive solution S can be adjusted by alternately or simultaneously supplying the cohesive solution S and the pH adjusting solution into the treatment tank 1. When the PH adjusted (coagulated) coagulable solution T exceeds a predetermined amount, it overflows and is discharged from the drainage pipe 12 to the outside. The pH adjustment of the cohesive solution S is completed, and the cohesive solution T remaining in the processing tank 1 is finally discharged from the drain pipe 11 to the outside.

Thus, the cohesive solution S can be subjected to the coagulation treatment.

[Problems to be Solved by the Invention] By the way, in the above-mentioned coagulation treatment method, a PH adjustment liquid composed of an acidic aqueous solution is supplied to the coagulation solution S to adjust the PH of the coagulation solution S. When the pH of the neutral solution S decreases to near neutrality, the dissolved phenol-based or acrylic-based resin components easily aggregate and precipitate. Agglomeration,
Since these precipitated resin components have a slight tackiness, they aggregate on the wall surface 21 of the processing tank 1 as shown in FIG.
The precipitated resin component 22 will adhere. This adhesion phenomenon is particularly remarkable at the gas-liquid interface (the periphery of the liquid surface).
These resin components 22 form a large lump as the adhesion to the wall surface 21 progresses, and the grown resin components 22 fall off the wall surface 21 and float in the cohesive solution S as a lump. Therefore, these resin components 22 may cause problems such as closing the inside of the drainage pipes 11 and 12 during drainage, damaging the stirring blades 13, and reattaching to the PH detection electrode 16. large.

An object of the present invention is to provide a method and an apparatus for coagulating a cohesive solution that effectively solve the above problems.

[Means for Solving the Problems] In order to solve the above problems, the present invention employs the following aggregating method and apparatus for aggregating solution.

In the present invention, the method for coagulating a coagulable solution according to claim 1 is a method for coagulating a coagulable solution in which a solute component is coagulated and precipitated by adjusting pH, wherein the coagulating solution is stored. The pH adjusting solution is supplied into the coagulable solution while stirring the inside, and the coagulable solution is sprayed on the liquid interface portion of the inner wall surface of the processing tank and a portion slightly higher than the liquid interface portion. It is characterized by supplying a solution.

The method for coagulating a cohesive solution according to claim 2 is as follows:
The method for coagulating a coagulable solution according to claim 1 is characterized in that, as a pretreatment, a solid in the coagulable solution is pulverized and / or the solid is collected.

The coagulation solution coagulation apparatus according to claim 3 is
An apparatus for coagulating a cohesive solution in which a solute component is coagulated and precipitated by pH adjustment, comprising: a treatment tank for coagulating the coagulable solution; and a stirring means for stirring the coagulable solution stored in the treatment tank. Adjusting liquid supply means for supplying a PH adjusting liquid into the processing tank; and a coagulable solution sprinkler for sprinkling the coagulable solution on a liquid interface part of the inner surface of the processing tank and a part slightly above the liquid interface. Means.

[Action] According to the method for coagulating a coagulable solution according to claim 1 of the present invention, the coagulable solution is sprayed on the liquid interface of the inner wall surface of the processing tank and a portion slightly higher than the liquid interface. The solute component of the cohesive solution once coagulated and precipitated in the vicinity of the liquid interface on the inner wall surface of the processing tank dissolves again, preventing the solute component from aggregating and precipitating in the vicinity of the liquid interface section on the inner wall surface of the processing tank.

In addition, according to the method for coagulating a coagulable solution according to claim 2, by pulverizing a solid in the coagulable solution as a pretreatment of the coagulable solution, and / or collecting the solid, Solids in the cohesive solution are micronized or removed.

Further, according to the coagulation solution coagulation treatment apparatus according to claim 3, the coagulation solution sprinkling means for sprinkling the coagulation solution on the liquid interface portion of the inner wall surface of the processing tank and a portion slightly above the liquid interface portion is provided. By providing, once agglomerated in the vicinity of the liquid interface on the inner surface of the processing tank, dissolution of the solute component of the coagulable solution deposited,
Further, aggregation and precipitation of solute components in the vicinity of the liquid interface on the inner wall surface of the processing tank are efficiently prevented.

Hereinafter, an embodiment of the present invention will be described with reference to FIGS. 1 and 2.

First, an apparatus for coagulating a cohesive solution according to claim 3 will be described. In the figure, reference numeral B denotes an agglomeration processing apparatus according to the present invention.

The aggregating apparatus B is obtained by modifying some of the same components as the aggregating apparatus A described in the conventional example, and is the same as the components shown in FIG. 3 in FIGS. 1 and 2. The same reference numerals are given to the elements after the reference number B, and the description of the same elements will be omitted.

The coagulation treatment device B is generally constituted by a treatment tank B1, a stirring means 31, a control liquid supply means B3, a cohesive solution spraying means 32, and a PH measurement device B5.

Above the central part of the processing tank B1, a cohesive solution spraying means 32 is provided. The cohesive solution spraying means 32 is provided with a cohesive solution supply pipe 33 piped to the processing tank B1.

The cohesive solution supply pipe 33 is for transporting the cohesive solution BS into the processing tank B1, and the lower end portion 34 is movable vertically in the upper part of the center of the processing tank B1 and fixed at an arbitrary position. It is free. A sprinkling mechanism 35 is attached to the lower end 34.

The main part of the liquid spraying mechanism 35 is substantially constituted by a sprinkler as shown in FIG. 1 (a), and the liquid is aggregated on the liquid interface of the wall surface 36 in the processing tank 1 and a part slightly above the liquid interface. This is for dispersing the cohesive solution BS radially and dissolving again the resin component of the cohesive solution BS which aggregates and precipitates near the liquid interface on the wall surface 36. This sprinkling mechanism 35 has a thick disk shape, and has a large number of sprinkling holes 37, 37,. The sprinkling mechanism 35 is rotatable at a given number of rotations in a fixed direction about a vertical axis during the sprinkling of the cohesive solution BS.

The main part of the sprinkling mechanism 35 is not limited to the sprinkler described above, and various modifications are possible. For example, as shown in FIG. 1 (b), a pipe shower having a large number of holes 38, 38,.

The stirring means 31 is used to quickly and uniformly react and coagulate the coagulable solution BS and the PH adjustment solution.
Is for stirring. The stirring blade 39 constituting a main part of the stirring means 31 is provided coaxially with the spray mechanism 35 of the cohesive solution spray means 32, and rotates independently of the spray mechanism 35, and is vertically rotated. It is freely rotatable around the axis of the direction at an arbitrary rotation speed.

Next, a method for aggregating a cohesive solution BS based on the method for aggregating a cohesive solution according to claim 1 will be described.

First, the cohesive solution supply pipe 33 is fixed at an appropriate position above the center of the processing tank B1, and a predetermined amount of the cohesive solution BS is supplied into the processing tank B1.

When a solid substance is contained in the cohesive solution BS, it is necessary to perform a pretreatment in order to prevent clogging of a device that may occur during the coagulation treatment. As a pre-treatment, a method of pulverizing solids in the cohesive solution BS using an emulsifier or a pulverizer such as a homogenizer, collecting these solids by filtration or the like, and removing the solids from the cohesive solution BS. good. Depending on the amount and degree of solids, these solids may be collected only by filtration or the like. By performing these pretreatments on the cohesive solution BS, solids in the cohesive solution BS are formed into fine particles and removed.

Next, the pH of the cohesive solution BS is measured by the PH measurement device B5 while stirring the cohesive solution BS using the stirring means 31.
Next, while measuring the pH of the cohesive solution BS, the adjusting liquid supply means
Supply the PH adjustment liquid into the processing tank B1 using B3, and
Adjust the BS PH.

Next, the sprinkling mechanism 35 is rotated at an appropriate number of revolutions, and the cohesive solution BS is spouted radially from the holes 37, 37,. The number of rotations of the liquid spray mechanism 35 is adjusted so that the liquid strikes the liquid interface of the wall surface 36 in the processing tank B1 and a portion slightly above the liquid interface (preferably about 10 cm above the liquid interface). By dispersing the cohesive solution BS radially, the resin component of the cohesive solution BS which coagulates and precipitates in the vicinity of the liquid interface on the wall surface 36 is dissolved again. During this time, the pH of the cohesive solution BS is adjusted by alternately or simultaneously supplying the cohesive solution BS and the PH adjustment liquid into the treatment tank B1. When the PH adjusted (coagulated) coagulable solution BT exceeds a predetermined amount, it overflows and is discharged from the drain pipe B12 to the outside. The pH adjustment of the cohesive solution BS is completed, and the cohesive solution BT remaining in the treatment tank B1 is finally discharged outside from the drain pipe B11.

As described above, when the cohesive solution BS is radially sprinkled by the sprinkling mechanism 35, and the pH-adjusted cohesive solution BT
Is discharged to the outside by overflowing, the liquid is sprinkled at a position slightly above the drain pipe B12 as shown in FIG. 2 (a), or the drain pipe B12 is discharged as shown in FIG. 2 (b). If the weir plate 40 is provided at the front part, the outflow of the unreacted cohesive solution BS can be prevented.

In this way, the aggregation treatment of the aggregation solution BS can be performed.

As described above, according to the method for aggregating the cohesive solution BS according to the present invention, the treatment tank B1 storing the cohesive solution BS
The pH adjustment solution is supplied into the cohesive solution BS while stirring the inside, and the cohesive solution BS is dispersed by spraying the cohesive solution BS on the liquid interface of the wall surface 36 in the processing tank B1 and slightly above the liquid interface. Since the cohesive solution BS is supplied, the solute component of the cohesive solution BS once coagulated and precipitated in the vicinity of the liquid interface of the wall surface 36 in the processing tank B1 is dissolved again, and the liquid on the wall surface 36 in the processing tank B1 is dissolved. The solute component does not aggregate or precipitate near the interface. Therefore, a lump of solid matter does not float in the cohesive solution BS, causing clogging of the drainage pipes B11, B12, etc., damaging the stirring blade 37, and reattaching to the PH detection electrode B16. The problem of dripping is eliminated.

Further, as a pretreatment of the cohesive solution BS, the solids in the cohesive solution BS are pulverized by removing the solids in the cohesive solution BS and collecting these solids, or are removed. . Therefore, problems such as clogging of the cohesive solution spraying means 32 and damage to the stirring blade 39 and the PH detection electrode B16 are eliminated.

Further, according to the coagulation processing apparatus B, the wall surface 36 in the processing tank B1
Cohesive solution at the liquid interface and slightly above
Since the cohesive solution dispersing means 32 for dispersing the BS is provided, the resin component of the cohesive solution BS once coagulated and deposited in the vicinity of the liquid interface of the wall surface 36 in the processing tank B1, and Wall
Aggregation and precipitation of the resin component in the vicinity of the liquid interface 36 can be efficiently prevented, the failure rate of the aggregation processing apparatus B itself decreases, and maintenance and management become easy.

As described above, the method is improved in various points, and the method and apparatus for coagulating a cohesive solution can be further improved.

In addition, the cohesive solution of the present invention is not limited to the cohesive solution BS of the above-described embodiment, and various solutions can be selected. As an example, an aggregating solution that aggregates and precipitates as it approaches a strong acid or strong alkali may be used.

[Effects of the Invention] As described in detail above, according to the method for coagulating a coagulable solution according to claim 1 of the present invention, a coagulating solution in which a solute component is coagulated and precipitated by pH adjustment is coagulated. A method comprising: supplying a pH-adjusting liquid into the coagulating solution while stirring the inside of the processing tank storing the coagulating solution, and a liquid interface portion on the inner wall surface of the processing tank and a portion slightly above the liquid interface. The cohesive solution is supplied by dispersing the cohesive solution into the solution, so that the solute component of the cohesive solution once coagulated and precipitated in the vicinity of the liquid interface on the inner wall surface of the processing tank is dissolved again, and the treatment is performed. The solute component does not aggregate or precipitate near the liquid interface on the inner wall surface of the tank. Therefore, a lump of solid matter does not float in the cohesive solution, causing problems such as clogging of the drainage pipe, damage to the stirring blade, and reattachment to the PH detection electrode. Disappears.

Further, according to the method for coagulating a coagulable solution according to claim 2, in the method for coagulating a coagulable solution according to claim 1, a solid in the coagulable solution is pulverized as a pretreatment, and / or Alternatively, the solid matter is collected, so that the solid matter in the cohesive solution is micronized or removed. Therefore, problems such as clogging of the cohesive solution spraying means and damage to the stirring blade and the PH detection electrode are eliminated.

According to the aggregating solution aggregating apparatus according to claim 3, the aggregating solution in which the solute component is agglomerated and precipitated by pH adjustment is agglomerated, and a treatment tank for aggregating the agglomerated solution. Stirring means for stirring the cohesive solution stored in the processing tank, adjusting liquid supply means for supplying a PH adjusting liquid into the processing tank, and a liquid interface portion on the inner wall surface of the processing tank and slightly less than this. Since it is provided with a cohesive solution spraying means for sprinkling the cohesive solution in the upper part,
It is possible to efficiently dissolve the solute component of the cohesive solution once coagulated and precipitated in the vicinity of the liquid interface on the inner wall of the processing tank, and prevent the aggregation and precipitation of the solute component in the vicinity of the liquid interface on the inner wall of the processing tank. As a result, the failure rate of the coagulation processing apparatus itself is reduced, and maintenance and management are facilitated.

As described above, the present invention can be improved in various points, further improve the method of aggregating a flocculant solution, and further improve the aggregating apparatus.

[Brief description of the drawings]

1 and 2 are views showing an embodiment of the present invention. FIG. 1 (a) is a schematic explanatory view of a coagulation treatment apparatus, and FIG. Partial perspective view of the coagulation treatment apparatus in the case where the liquid is dispersed by a perforated fixed pipe regardless of the mechanism. FIG. 3 (c) shows the coagulation solution on the liquid interface on the inner wall surface of the processing tank and slightly above it. FIGS. 2 (a) and 2 (b) are illustrations showing a method of preventing an unreacted cohesive solution from flowing out, FIG. 3 is a schematic illustration of a conventional coagulation apparatus, FIGS. 4 (a) and 4 (b) are explanatory diagrams showing that a solute component adheres to and falls off near the liquid interface on the inner wall surface of the processing tank. BS: Cohesive solution, BT: PH adjusted cohesive solution, B
Coagulation treatment device, B1 treatment tank, B3 adjustment liquid supply means, B5 PH measurement device, 31 stirring means, 32 coagulation solution spraying means, 36 wall surface.

Claims (3)

(57) [Claims] 1. A method for coagulating a coagulant solution in which a solute component coagulates and precipitates by adjusting the pH, wherein the coagulable solution is added to the coagulable solution while stirring the inside of a treatment tank storing the coagulable solution. And supplying the cohesive solution by spraying the cohesive solution on the liquid interface part of the inner wall surface of the processing tank and a portion slightly above the liquid interface part. Processing method. 2. The method for coagulating a coagulable solution according to claim 1, wherein, as a pretreatment, a solid in the coagulable solution is pulverized and / or the solid is collected. Coagulation treatment method for cohesive solution. 3. An apparatus for coagulating a coagulant solution in which a solute component is coagulated and precipitated by pH adjustment, comprising: a treatment tank for coagulating the coagulant solution; and the coagulant solution stored in the treatment tank. , A control liquid supply means for supplying a PH control liquid into the processing tank, and a liquid interface part of the inner wall surface of the processing tank and a part slightly above the liquid interface to disperse the cohesive solution. An aggregating solution aggregating apparatus, comprising: an aggregating solution dispersing means.