JPH11244607A - Liquid chemical deaeration and deaerator - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid chemical deaeration method and a deaerator which is effective so that bubbles are not incorporated with liquid chemical finally fed and furthermore in which pressure drop in the system is low. SOLUTION: This deaerator is provided with a vessel 2 and a hollow fiber membrane element 1 installed therein. The vessel 2 is provided with a liquid chemical introducing port 21, a liquid chemical bring-out port 31, and discharge ports 23, 23. The hollow fiber membrane element 1 is fixed to a fixing member 5 with both ends of hollow fiber membranes 4, 4,... having air permeability, 50-500 μm fiber inner diameter, and 1-150 μm membrane thickness being kept open. Both ends of the hollow fiber membrane element 1 are connected to the chemical liquid introducing port 21 and the liquid chemical bring-out port 31, respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for degassing a chemical solution, and more particularly, to a dissolved gas in a chemical solution such as a developing solution and a resist solution, which causes a loss of precision in a semiconductor manufacturing process. The present invention relates to a degassing method and a degassing apparatus suitable for use in degassing a chemical solution.

[0002]

2. Description of the Related Art Conventionally, in a semiconductor manufacturing process, various inconveniences are likely to occur due to the presence of bubbles in a supplied chemical solution. For example, a resist made of a photosensitive polymer is applied on a thin film laminated on a semiconductor wafer such as silicon by spin coating or the like, and a mask with a pattern is directly adhered to the semiconductor wafer or at a predetermined interval. And expose it through this mask.
In the step of forming a pattern on a thin film by etching after development, when a semiconductor wafer is spin-coated in a state where bubbles are present in a resist solution or a developing solution, processing unevenness due to bubbles occurs. Pattern defects occur.

Therefore, various methods have been proposed for degassing bubbles in a chemical solution such as a resist solution and a developing solution. For example,
There are a method of providing an air vent for degassing air bubbles in a device using a chemical solution, a method of degassing a chemical solution such as a developer stored in a storage tank, and the like.

[0004]

By the way, in the above-mentioned method of providing an air vent for degassing air bubbles in the above-described apparatus,
Since the degassing effect is insufficient, bubbles in the chemical solution have not been sufficiently degassed. Further, in the method of degassing the chemical solution stored in the storage tank, when the chemical solution is transported from the storage tank to the discharge nozzle, a gas for transportation or the like is mixed, and the chemical solution at the time when the chemical solution is supplied from the discharge nozzle is mixed. There is a problem that generation of bubbles is inevitable.

When a chemical solution such as a developing solution or a resist solution is transported, it is general to transport it using a gas such as nitrogen. In the transport, mixing of gas and generation of bubbles are unavoidable. There is a problem.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has been devised efficiently and with a low pressure loss in a system so that air bubbles do not mix into a finally supplied chemical solution. It is an object to provide a method and a degassing device.

[0007]

In order to solve the above problems, the present invention provides the following chemical solution degassing method and degassing apparatus. That is, the method for degassing a drug solution according to claim 1 of the present invention is a method for degassing a drug solution using a hollow fiber membrane, which has gas permeability, an inner diameter of 50 to 500 μm, and a film thickness of 10 μm.
Dissolving gas in the chemical solution is removed by passing the chemical solution through a hollow fiber membrane having a thickness of about 150 μm and reducing the pressure on the outer surface side of the hollow fiber membrane.

According to a second aspect of the present invention, there is provided the chemical solution degassing method according to the first aspect, wherein a plurality of the hollow fiber membranes are connected to form a plurality of stages, and the hollow fiber membranes pass through the preceding hollow fiber membrane. The method is characterized in that after a chemical solution is once merged, it is passed through a hollow fiber membrane at a later stage.

A third aspect of the present invention is a method of degassing a chemical solution according to the first or second aspect, wherein the hollow fiber membrane has a porous layer disposed on both sides of a non-porous layer. It is characterized by using a composite hollow fiber membrane having a layer structure.

In a fourth aspect of the present invention, there is provided a chemical solution degassing apparatus, comprising: a container provided with a chemical solution inlet, a chemical solution outlet, and an exhaust port; and a gas permeable and inner diameter provided in the container. 500
μm, a hollow fiber membrane element having a thickness of 10 to 150 μm, wherein both ends of the hollow fiber membrane are fixed by a fixing member while maintaining an open state, and both ends of the hollow fiber membrane element are provided with a chemical solution inlet of the container and It is characterized in that it is connected to each chemical solution outlet.

A chemical solution degassing apparatus according to a fifth aspect is the chemical solution degassing apparatus according to the fourth aspect, wherein a plurality of the hollow fiber membrane elements are connected to form a hollow fiber membrane module, and the adjacent hollow fiber membrane is provided. It is characterized in that a chemical solution merging chamber is formed between the elements.

According to a sixth aspect of the present invention, in the chemical solution degassing apparatus according to the fourth or fifth aspect, the hollow fiber membrane has a porous layer disposed on both sides of a non-porous layer. It is characterized by being a composite hollow fiber membrane having a layer structure.

In the method for degassing a chemical solution according to claim 1 of the present invention, the system is degassed by a hollow fiber membrane having gas permeability, an inner diameter of 50 to 500 μm, and a film thickness of 10 to 150 μm. It is possible to perform degassing of a chemical solution in which the pressure loss in the inside is low and the hollow fiber membrane is less damaged even when the pressure fluctuates.

[0014] In the method for degassing a chemical solution according to the second aspect, the chemical solution that has passed through the hollow fiber membrane in the former stage is once merged and then passed through the hollow fiber membrane in the latter stage, thereby dissolving the dissolved gas in the chemical solution. After the concentration is once made uniform, the gas is again degassed by the hollow fiber membrane at the subsequent stage, and the dissolved gas is removed with high degassing efficiency.

According to a third aspect of the present invention, a three-layer composite hollow fiber membrane having a porous layer disposed on both sides of a non-porous layer is used as the hollow fiber membrane. It is possible to degas a chemical solution with little leakage and high degassing efficiency.

The composite hollow fiber membrane is preferably a composite hollow fiber membrane in which the thickness of the non-porous layer is 0.3 to 2 μm and the thickness of the porous layer is 5 to 100 μm. When this composite hollow fiber membrane is used, the mechanical strength is increased, and the amount of gas permeation during degassing is improved. further,
As the composite hollow fiber membrane, the pore size of the porous layer is 0.01 to
When a composite hollow fiber membrane having a thickness of 1 μm is used, the non-porous layer is less likely to be wet by the chemical solution, the deterioration of the non-porous layer due to the chemical solution is reduced, and the amount of gas permeation during degassing is improved.

According to a fourth aspect of the present invention, the chemical solution degassing apparatus has gas permeability, an inner diameter of 50 to 500 μm, and a film thickness of 10 to 10 μm.
By using a hollow fiber membrane element fixed by a fixing member while both ends of a 150 μm hollow fiber membrane are kept open, the pressure loss in the system is low, and even when a pressure fluctuation occurs, the hollow fiber membrane can be used. It is possible to easily degas a less damaged chemical solution. This makes it possible to stably degas the chemical solution with low pressure loss.

In the chemical liquid degassing apparatus according to the present invention, the concentration of the dissolved gas in the chemical liquid is once uniformed by forming the chemical liquid junction chamber between the adjacent hollow fiber membrane elements. Later, the liquid is sent to the next hollow fiber membrane element, and the degassing efficiency increases.

According to a sixth aspect of the present invention, the hollow fiber membrane is a composite hollow fiber membrane having a three-layer structure in which a porous layer is disposed on both sides of a non-porous layer. Dissolved gas can be degassed with little leakage and high degassing efficiency.

The composite hollow fiber membrane is preferably a composite hollow fiber membrane in which the thickness of the non-porous layer is 0.3 to 2 μm and the thickness of the porous layers is 5 to 100 μm. When this composite hollow fiber membrane is used, a deaerator having high mechanical strength and an improved gas permeation amount during deaeration can be obtained. When a composite hollow fiber membrane having a porous layer with a pore size of 0.01 to 1 μm is used as the composite hollow fiber membrane, the non-porous layer is less likely to be wet by the chemical solution, and the deterioration of the non-porous layer due to the chemical solution is reduced. It is possible to obtain a degassing device that is reduced and has an improved gas permeation amount when performing degassing.

The material of the porous layer is preferably polyethylene. Preferably, the material of the non-porous layer is a urethane-based polymer. Further, the material of both the porous layer and the non-porous layer may be polypropylene.

[0022]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of a method and a device for degassing a chemical solution according to the present invention will be described with reference to the drawings. [First Embodiment] FIG. 1 is a schematic longitudinal sectional view showing a chemical solution deaerator according to a first embodiment of the present invention.
Is a hollow fiber membrane element, and 2 is a can (container) in which the hollow fiber membrane element 1 is stored. Hollow fiber membrane element 1
As shown in FIG. 2, a cylindrical porous case 3 having a large number of holes or voids in a wall surface has an inner diameter of 50 to 50.
A large number of hollow fiber membranes 4 having a gas permeability of 0 μm and a film thickness of 10 to 150 μm are accommodated. These hollow fiber membranes 4, 4,. The membrane 4 is focused and fixed by the fixing member 5 such that the ends of the membrane 4 are opened. Further, O-rings 6 for connection are mounted at two places on the outer periphery of the end of the cylindrical porous case 3.

The can body 2 is composed of a cylindrical can body 11 and can body caps 12 and 13 disposed above and below the can body 11. The can body 11 and the can body caps 12 and 13 are connected to a gasket 14. More airtight. The can body cap 12 is provided with a chemical solution inlet 21 and an introduction connection port 22 communicating with the chemical solution inlet 21, an exhaust port 23 is provided on a side wall thereof, and a condensate is appropriately provided at a lower end thereof. A drain outlet 24 and a cock 25 for removal to the outside of the can 2 are provided. In addition, in the can body cap 13,
A liquid outlet 31 and a lead-out port 32 communicating with the liquid outlet 31 are provided, and an exhaust port 23 is provided on a side wall thereof.

The exhaust port 23 is connected to a vacuum pump or the like to depressurize the inside of the can 2 to a vacuum. Dissolved gas is removed. Note that this exhaust port 23 is
1 may be arranged.

One fixing member 5 of the hollow fiber membrane element 1
Is the chemical solution outlet 3 of the can body cap 13 provided at the upper part.
It is connected to a lead-out connection port 32 provided in communication with 1. Further, the other fixing member 5 is connected to an introduction connection port 22 provided in communication with the chemical solution introduction port 21 of the can body cap 12 provided at the lower part. In this way, the hollow fiber membrane element 1 in which the hollow fiber membrane element 1 is mounted in the can body 11 is a hollow fiber membrane module, and constitutes a main part of the deaerator.

It is preferable that the material of the cylindrical porous case 3 has appropriate mechanical strength and durability against a chemical solution. Examples of the material include hard polyvinyl chloride resin, polycarbonate resin, polysulfone resin, and polypropylene. Polyolefin resins, acrylic resins, ABS resins, modified PPO resins, and the like can be used.

The hollow fiber membrane 4 preferably has gas permeability, an inner diameter of 50 to 500 μm, and a thickness of 10 to 150 μm. By using the hollow fiber membrane 4 having the inner diameter and the film thickness in the above ranges, the pressure loss in the hollow fiber membrane element 1 is low, and even if the vibration of the hollow fiber membrane 4 occurs, the hollow fiber membrane 4 4 can be degassed without damaging the chemical solution. As such a hollow fiber membrane 4, a porous hollow fiber membrane or a hollow fiber membrane composed of a non-porous homogeneous layer can be used. Furthermore, when a composite hollow fiber membrane having a three-layer structure in which a porous layer is formed on both sides of a gas-permeable non-porous layer is used, there is no leakage of a chemical solution,
In addition, the chemical solution can be degassed with excellent dissolved gas removal efficiency.

Examples of the polymer material constituting the non-porous layer of such a composite hollow fiber membrane include a silicone rubber-based polymer having excellent gas permeability, polydimethylsiloxane, and a copolymer of silicon and polycarbonate. Silicon rubber-based polymer, poly (4-methylpentene-1), low-density polyethylene, polyolefin-based polymer such as polypropylene, fluorine-containing polymer such as perfluoroalkyl-based polymer, cellulose-based polymer such as ethylcellulose, polyphenylene oxide, poly-vinylvinylpyridine , Urethane-based polymers and copolymers of these polymer materials, blended polymers, and the like can be used.

Examples of the polymer material constituting the porous layer include polyolefin polymers such as polyethylene, polypropylene, poly (3-methylbutene-1) and poly (4-methylpentene-1), and fluorine such as polyvinylidene fluoride and polytetrafluoroethylene. A polymer such as a system polymer, polystyrene, polyetheretherketone, or polyetherketone can be used.

The combination of the polymer material constituting the non-porous layer and the polymer material constituting the porous layer is not particularly limited, and may be different types of polymers or same types of polymers. As the non-porous layer, a urethane-based polymer is preferable from the viewpoint of high gas permeability and film formation stability. As the porous layer, polyethylene is preferable because of its high flexibility as a hollow fiber membrane and high film formation stability.

More preferably, polypropylene is used, which has high durability against chemicals, has relatively high mechanical strength, and has better thermal properties than polyethylene and urethane resins. This is a preferred material for both non-porous and porous layers. When polypropylene is applied to the non-porous layer, it is excellent in that it is not easily deteriorated by the chemical solution.When it is applied to the porous layer, the mechanical strength is high as well as the chemical solution. Excellent workability.

The hollow fiber membrane 4 has a non-porous layer thickness of 0.3 to 2 μm and a porous layer thickness of 5 to 1 μm, respectively.
When a composite hollow fiber membrane within the range of 00 μm is used, breakage and the like are less likely to occur due to high mechanical strength, and
This is preferable because the amount of gas permeation is improved. More preferably, as the composite hollow fiber membrane, the pore size of the porous layer is 0.01 to
The use of a composite hollow fiber membrane having a thickness of 1 μm is preferable because the non-porous layer is hardly wetted, the deterioration of the non-porous layer due to the chemical solution is reduced, and the gas permeation increases.

The composite hollow fiber membrane having such a three-layer structure is prepared by, for example, melt-spinning a polymer forming a homogeneous layer and a polymer forming a porous layer using a multi-cylindrical compound spinning nozzle. Next, it can be produced by a method in which the homogeneous layer is stretched under the condition of making only the portion to be a porous layer porous without making it porous.

The fixing member 5 includes a large number of hollow fiber membranes 4, 4,.
, While maintaining the open state of both ends, and also functions as a member that partitions the chemical liquid flow path side and the exhaust gas flow path side in an airtight state. As the fixing member 5, a thermosetting resin or an ultraviolet curable resin obtained by curing a liquid resin such as an epoxy resin, an unsaturated polyester resin, or a polyurethane resin, or a resin obtained by melting and cooling and solidifying a polyolefin or the like is preferable. Used.

The shape of the hollow fiber membrane element 1 is not particularly limited as long as both ends of the bundle of the hollow fiber membranes 4, 4,... Are bundled and fixed by the fixing member 5 and the drain can be easily removed. Although it is not necessary, the one stored in the cylindrical porous case 3 prevents damage to the hollow fiber membranes 4, 4,... When the hollow fiber membrane element 1 is processed, and allows the hollow fiber membrane element 1 to have a high dimension. This is a preferable shape because it can be processed with high accuracy.

In this chemical solution degassing apparatus, the chemical solution s supplied from the chemical solution inlet 21 is sent to the hollow fiber membrane element 1 through the inlet 22 and the hollow portions of the hollow fiber membranes 4, 4,. While flowing, it undergoes deaeration through the surface of the hollow fiber membrane 4.
The chemical solution s subjected to the degassing process is taken out of the chemical solution outlet 31 via the outlet connection port 32. Further, since the drain port 24 is provided in the can body cap 12 provided at the lower portion, the drain liquid obtained by condensing water vapor or the like evaporated from the chemical solution s through the hollow fiber membrane 4 is discharged to the outside of the can body 2. Can be easily discharged to

Here, each embodiment of the chemical solution deaerator will be described. Example 1 A hollow fiber membrane element 1 as shown in FIG. 2 was prepared by using a composite hollow fiber membrane in which a porous layer of polyethylene was provided on both sides of a non-porous layer made of a urethane polymer as the hollow fiber membrane 4. Then, it was used for degassing a developer used in a semiconductor manufacturing process. The hollow fiber membrane 4 has an inner diameter of 200 μm.
m, a film thickness of 40 μm, a non-porous layer having a thickness of 0.8 μm, and a porous layer having a pore diameter of 0.1 μm.

An epoxy resin was bundled and fixed as a fixing member 5 with both ends of the hollow fiber membrane 4 kept open in a porous cylindrical case 3 made of a modified PPO resin. The effective hollow fiber length of this hollow fiber membrane element 1 was 20 cm, and the membrane area was 2.4 m ² . The hollow fiber membrane element 1 was mounted in the can 2 shown in FIG. 1, and the developer was degassed.
As a developing solution, a developer was used. The developer was passed through the hollow portion of the hollow fiber membrane 4 at 25 ° C. at a flow rate of 1 L / min, and the outside of the hollow fiber membrane 4 was depressurized to 3 kPa to degas the developer.

As a result, the concentration of the gas dissolved in the developer before degassing was 16.0 ppm for nitrogen and 8.2 for oxygen.
By performing deaeration using the hollow fiber membrane element 1, the gas concentration after the treatment was reduced to 8.5 ppm with nitrogen and 0.4 ppm with oxygen,
It became clear that the degassing efficiency was improved.

Example 2 A hollow fiber membrane element 1 was produced. Here, the effective hollow fiber length was set to 60 cm, and other specifications were the same as those of the hollow fiber membrane element 1 manufactured in Example 1. This hollow fiber membrane element 1
Was mounted in the can 2, and the developer was degassed in the same manner as in Example 1. In addition, the conditions of liquid passing and pressure reduction were the same as in Example 1.

As a result, the concentration of the gas dissolved in the developer before the degassing treatment was 16.2 ppm for nitrogen and 8.2 for oxygen.
ppm, the gas concentration after the treatment was reduced to 6.7 ppm for nitrogen and 0.27 ppm for oxygen by performing deaeration using the hollow fiber membrane element 1. It has become clear that it has improved.

As described above, according to the chemical solution degassing apparatus of the present embodiment, the cylindrical porous case 3 has an inner diameter of 50 to 500 μm, a film thickness of 10 to 150 μm, and has gas permeability. A large number of hollow fiber membranes 4 are housed, and these hollow fiber membranes 4, 4,... Are bundled and fixed by a fixing member 5 such that the ends of the hollow fiber membranes 4 are open at both ends of the cylindrical porous case 3. Since the hollow fiber membrane element 1 is used, the pressure loss in the system is low, and even when the pressure fluctuates, the chemical solution with little damage to the hollow fiber membrane 4 can be easily degassed. Therefore, a degassed drug solution can be stably obtained with a low pressure loss.

According to the chemical solution degassing method of the present embodiment, the chemical solution s sent from the chemical solution inlet 21 to the hollow fiber membrane element 1 flows through the hollow portions of the hollow fiber membranes 4, 4,. Deaeration through the surface of the hollow fiber membrane 4 by the
Since it is taken out from 1, the pressure loss in the system is low, and even when the pressure fluctuates, it is possible to perform degassing of the chemical solution with little damage to the hollow fiber membrane 4.

[Second Embodiment] FIG. 3 is a schematic longitudinal sectional view showing a chemical solution deaerator according to a second embodiment of the present invention. The major difference between the chemical solution degassing device of the present embodiment and the chemical solution degassing device of the above-described first embodiment (FIG. 1) is that, in the first embodiment, a single hollow fiber membrane element is provided in the can 2. In contrast, in the chemical solution degassing apparatus of the present embodiment, a plurality of hollow fiber membrane elements 1 (here, 3
Are connected in series to form a multistage hollow fiber membrane module 41, and this hollow fiber membrane module 41 is housed in a long cylindrical can body (vessel) 42. The other points are substantially the same as those of the first embodiment described above. Therefore, in FIG. 3, the same components as those shown in FIG. Is omitted.

In this hollow fiber membrane module 41, the fixing member 5 of the uppermost hollow fiber membrane element 1 is connected to the outlet port 32 provided in communication with the chemical outlet 31 of the can body cap 13 provided on the upper part. It is connected to the. Further, the fixing member 5 of the lowermost hollow fiber membrane element 1 is connected to an introduction connection port 22 provided in communication with a chemical solution introduction port 21 of a can body cap 12 provided at a lower portion.

The can 42 is a long cylindrical can 43
And can caps 12 and 13 disposed above and below the can cap 43 and the can caps 12 and 13, respectively.
Are hermetically connected by a gasket 14.

As shown in FIG. 4, the hollow fiber membrane module 41 includes a plurality of hollow fiber membrane elements 1, 1,... ), And a central portion of the connecting member 44 is opened to form a drug solution merging chamber 45. Connecting member 44
Is good as long as it has mechanical strength and durability to a chemical solution, for example, hard polyvinyl chloride resin, polycarbonate, polysulfone resin, polyolefin resin such as polypropylene, acrylic resin, ABS resin,
Modified PPO resin and the like, and those made of metal such as stainless steel are also preferably used.

In this chemical solution degassing device, the chemical solution s supplied from the chemical solution inlet 21 flows into the hollow fiber membrane module 41 in the can 42 and the hollow fiber membrane element 1 in the lowermost hollow fiber membrane element 1 While flowing through the hollow part, the hollow fiber membrane 4 is subjected to deaeration through the surface. Lowermost hollow fiber membrane element 1
The chemical solution passed through the hollow fiber membrane 4 is once merged in a chemical solution merging chamber 45 formed between the lowermost hollow fiber membrane element 1 and the middle hollow fiber membrane element 1 and dissolved in the chemical solution s. After the gas concentration is made uniform, the liquid is sent to the middle-stage hollow fiber membrane element 1.

In the hollow fiber element 1 in the middle stage,
Degassing treatment is performed through the surface of the hollow fiber membrane 4 in the same manner as the lowermost hollow fiber membrane element 1, and a chemical solution combining chamber 45 formed between the middle hollow fiber membrane element 1 and the uppermost hollow fiber membrane element 1. Once, the dissolved gas concentration in the chemical solution s is made uniform again, and then the uppermost hollow fiber membrane element 1
Liquid.

The uppermost hollow fiber membrane element 1 is similarly degassed through the surface of the hollow fiber membrane 4 and then taken out of the chemical solution outlet 31 via the outlet 32.
Thus, in this chemical solution deaerator, compared with the case where the hollow fiber membrane module having no chemical solution merging chamber 45 is used,
Since the degassing efficiency per membrane area is improved, the dissolved gas in the chemical can be degassed with a high chemical liquid treatment amount.

Here, each embodiment of the chemical solution deaerator will be described. Example 3 Three hollow fiber membrane elements 1 similar to the hollow fiber membrane element 1 produced in Example 1 were used, and these hollow fiber membrane elements 1, 1,. Connected in series by a connecting member 44 via the ring 6,
As shown in FIG. 3, the hollow fiber membrane module 41 was mounted in a can body 42, and a developer was degassed in the same manner as in Example 1 described above.

The conditions for the liquid passing and the pressure reduction were the same as those in Example 1 described above.
The same as above. As a result, the concentration of the gas dissolved in the developer before the degassing treatment was 16.2 ppm for nitrogen and 8.8 for oxygen.
Although the gas concentration was 2 ppm, the gas concentration after the treatment was reduced to 2.3 ppm for nitrogen and 0.087 ppm for oxygen by performing degassing using the hollow fiber membrane module 41. It became clear that the degassing efficiency was further improved as compared with the hollow fiber membrane module of the element 1 alone.

Example 4 Three hollow fiber membrane elements 1 were produced in the same manner as in Example 1 using a composite hollow fiber membrane in which both the non-porous layer and the porous layer were formed of polypropylene. did. The hollow fiber membrane 4 used here is
The inner diameter was 180 μm, the film thickness was 35 μm, the thickness of the non-porous layer was 0.6 μm, and the pore diameter of the porous layer was 0.1 μm.

The three hollow fiber membrane elements 1 are connected in series by the connecting member 44 in the same manner as in the third embodiment, and
The hollow fiber membrane module 41 was set in a stage, and this hollow fiber membrane module 41 was mounted in the can 42, and the developer was degassed in the same manner as in Example 1 described above. As a result, the concentration of the gas dissolved in the developer before the degassing treatment was 16.3 pp with nitrogen.
m and oxygen were 8.1 ppm, but by performing deaeration using the hollow fiber membrane module 41, the gas concentration after the treatment was 1.1 ppm with nitrogen and 0.050 p with oxygen.
pm, and it became clear that the degassing efficiency was further improved as compared with the hollow fiber membrane module using the hollow fiber membrane element 1 alone.

As described above, according to the chemical solution degassing apparatus of the present embodiment, the hollow fiber membrane module 41 in which the plurality of hollow fiber membrane elements 1 are connected in series to form a multistage
Since it is housed in the chamber 2, the pressure loss in the system is low, and even when the pressure fluctuates, the chemical solution with little damage to the hollow fiber membrane 4 can be easily degassed. Moreover, since the multistage hollow fiber membrane module 41 is used, a chemical solution with further improved degassing efficiency can be obtained.

Also, since the hollow fiber membrane elements 1, 1,... Constituting the hollow fiber membrane module 41 are connected by the connecting member 45, they can be easily attached and detached. Can be easily replaced. In addition, the length of the can 42 and the length of the hollow fiber membrane module 41 can be changed according to the required degassing specifications. Since the number of the members 45 can be easily changed by changing the number, the optimum design can be easily performed.

Further, according to the chemical solution degassing method of this embodiment, the chemical solution s is supplied from the chemical solution inlet 21 to the hollow fiber membrane modules 41 in a plurality of stages, and the hollow fiber membrane elements 1 in each stage are degassed. Since the liquid is taken out from the chemical liquid outlet 31, the pressure loss in the system is low, and even when the pressure fluctuates, the chemical liquid with little damage to the hollow fiber membrane 4 can be degassed. Moreover, since the chemical solution s is passed through the multistage hollow fiber membrane module 41, the degassing efficiency of the chemical solution can be further improved.

In the chemical liquid degassing apparatus according to the present embodiment, the hollow fiber membrane module 41 having a plurality of hollow fiber membrane elements 1 connected in series to form a multi-stage hollow fiber membrane module 41 is inserted into a long cylindrical can 42. But a plurality of hollow fiber membrane elements 1
Can be connected in parallel to form a hollow fiber membrane module, and this hollow fiber membrane module can be housed in a can body provided with a plurality of chemical solution introduction ports 21, introduction connection ports 22, and discharge connection ports 32.

[0059]

As described above, according to the method for degassing a drug solution according to claim 1 of the present invention, a hollow fiber having gas permeability, an inner diameter of 50 to 500 μm, and a film thickness of 10 to 150 μm. Since degassing is performed by the membrane, it is possible to degas a chemical solution with low pressure loss in the system and little damage to the hollow fiber membrane even when the pressure fluctuates.

According to the method for degassing a chemical solution according to claim 2,
After the chemicals that have passed through the hollow fiber membrane of the former stage are once merged,
Since the liquid is passed through the subsequent hollow fiber membrane, the concentration of the dissolved gas in the chemical solution is once made uniform, and then the degassing is performed again by the latter hollow fiber membrane, whereby the dissolved gas can be removed with high degassing efficiency.

According to the method for degassing a chemical solution according to claim 3,
As the hollow fiber membrane, a composite hollow fiber membrane having a three-layer structure in which a porous layer is disposed on both sides of a non-porous layer is used, so that the leakage of the chemical solution is small and the chemical solution with high degassing efficiency is degassed. be able to.

According to the chemical solution degassing apparatus of the fourth aspect,
It has gas permeability, inner diameter is 50-500 μm, and film thickness is 1
Since a hollow fiber membrane element fixed by a fixing member is used while both ends of the hollow fiber membrane of 0 to 150 μm are kept open, the pressure loss in the system is low, and even when the pressure fluctuates, the hollow fiber membrane element is hollow. Degassing of the drug solution with less damage to the thread membrane can be easily performed. Therefore, the chemical solution can be stably degassed with a low pressure loss, and a chemical solution with high degassing efficiency can be obtained.

According to the chemical solution degassing apparatus of the fifth aspect,
Since a chemical solution merging chamber is formed between the adjacent hollow fiber membrane elements, the dissolved gas concentration in the chemical solution is once made uniform in the chemical solution merging chamber, and then sent to the next hollow fiber membrane element, thereby dissolving the chemical solution. Gas degassing efficiency can be increased.

According to the chemical solution degassing apparatus of the sixth aspect,
Since the hollow fiber membrane is a composite hollow fiber membrane having a three-layer structure in which a porous layer is disposed on both sides of a non-porous layer, the leakage of the chemical solution is small, and the dissolved gas is degassed with high degassing efficiency. be able to.

[Brief description of the drawings]

FIG. 1 is a schematic vertical sectional view showing a chemical solution deaerator according to a first embodiment of the present invention.

FIG. 2 is a schematic longitudinal sectional view showing a hollow fiber membrane element of the chemical solution deaerator according to the first embodiment of the present invention.

FIG. 3 is a schematic vertical sectional view showing a chemical solution deaerator according to a second embodiment of the present invention.

FIG. 4 is a schematic longitudinal sectional view showing a hollow fiber membrane module of a chemical solution deaerator according to a second embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Hollow fiber membrane element 2 Can body (container) 3 Cylindrical porous case 4 Hollow fiber membrane 5 Fixing member 6 O-ring 11 Can body container 12, 13 Can body cap 14 Gasket 21 Chemical solution inlet 22 Inlet connection port 23 Exhaust port 24 Drain Discharge port 25 Cock 31 Chemical solution outlet 32 Outlet connection port 41 Hollow fiber membrane module 42 Can body (container) 43 Can body container 44 Connecting member 45 Chemical solution merging chamber

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI H01L 21/30 H01L 21/30

Claims (6)

[Claims] 1. A method for performing degassing of a chemical solution using a hollow fiber membrane, which has gas permeability, an inner diameter of 50 to 500 μm, and a thickness of 1
A method of degassing a chemical solution, comprising passing the chemical solution through a hollow fiber membrane having a diameter of 0 to 150 μm and reducing the pressure on the outer surface side of the hollow fiber membrane to remove dissolved gas in the chemical solution. 2. The method according to claim 1, wherein a plurality of the hollow fiber membranes are connected to form a plurality of stages, and the chemicals that have passed through the preceding hollow fiber membranes are merged once and then passed through the subsequent hollow fiber membranes. The method for degassing a drug solution according to claim 1. 3. The method according to claim 1, wherein the hollow fiber membrane is a composite hollow fiber membrane having a three-layer structure in which a porous layer is disposed on both sides of a non-porous layer. Damn way. 4. A container provided with a chemical solution inlet, a chemical solution outlet, and an exhaust port, provided in the container, having gas permeability, and having an inner diameter of 50 to 50.
A hollow fiber membrane element having both ends of a hollow fiber membrane having a thickness of 500 μm and a thickness of 10 to 150 μm fixed by a fixing member while maintaining an open state, wherein both ends of the hollow fiber membrane element are provided with a chemical solution inlet of the container and A chemical solution degassing device, which is connected to each of the chemical solution outlets. 5. A chemical solution removing device according to claim 4, wherein a plurality of said hollow fiber membrane elements are connected to form a hollow fiber membrane module, and a chemical solution merging chamber is formed between adjacent hollow fiber membrane elements. Qi device. 6. The method according to claim 4, wherein the hollow fiber membrane is a composite hollow fiber membrane having a three-layer structure in which a porous layer is disposed on both sides of a non-porous layer. Qi device.