JP4322716B2 - Liquid processing module and method for manufacturing liquid processing module - Google Patents

Description

  The present invention relates to a liquid treatment module used for body fluid treatment, water treatment, and the like, and a method for producing the liquid treatment module, and more particularly, to a hydrophilic treatment of a semipermeable membrane provided in a casing.

  Liquid treatment modules are used in a wide range of fields including medical and industrial fields. For example, in the medical field, it is used as a blood purifier for blood purification of patients with diseases of the kidney and liver, and in the industrial field, it is used as a water treatment device for concentration and purification of beverages such as juice. The semipermeable membrane used in the liquid treatment module is subjected to a surface treatment (meaning treatment from the surface, including treatment of the surface in addition to treatment of the surface itself; the same applies hereinafter). There is. One type of semipermeable membrane that has undergone surface treatment is a hydrophilic membrane. This hydrophilized film is what imparted hydrophilicity to a hydrophobic film substrate. Here, the hydrophobic membrane base material is used because the membrane base material is easy to spin, and some of them are high in strength and excellent in heat resistance and chemical resistance. However, if the membrane substrate remains hydrophobic, it is difficult to immediately exhibit the original permeability. Moreover, before using as a material of a blood purification apparatus, an activation process must be performed, which is complicated. Therefore, in order to immediately demonstrate the original permeability of the membrane substrate, and to improve the operability and biocompatibility in the treatment preparation stage, the membrane substrate is subjected to surface treatment to impart hydrophilicity. ing.

  There are various surface treatment methods for membrane substrates, but one type is proposed: a treatment solution containing a treatment agent is poured over one membrane surface of the membrane substrate, and then this treatment solution is washed and removed with a washing solution. (For example, refer to Patent Document 1). In this method, the treatment agent (for example, a hydrophilizing agent) and the adsorption force on the surface of the membrane substrate are used to adhere and hold the treatment agent on the surface of the membrane substrate, so that there is no need to use a special insolubilizing treatment. Thus, the facility can be simplified and the processing can be simplified. Moreover, since one surface in a film | membrane base material can be selectively processed, it can use suitably in a specific use. For example, if a blood purifier is constructed using a hydrophilic membrane with one surface of a hydrophobic membrane substrate, excess water in the blood can be discharged to the dialysate side immediately after the start of dialysis, and exothermic substances such as endotoxin Substances can be adsorbed on hydrophobic surfaces.

Japanese Patent Laid-Open No. 10-151196 (page 5-6, FIG. 1)

By the way, in order to draw out the liquid processing capability (permeability) of the membrane more quickly during the liquid processing, it is necessary to sufficiently adjust not only the surface of the membrane base material but also the liquid such as an aqueous solution. However, in the treatment method described in Patent Document 1, insolubilization treatment of the hydrophilizing agent is unnecessary and simple, but it is difficult to impart hydrophilicity to the inside of the treated membrane substrate. Therefore, it takes time for the liquid to adjust to the inside of the membrane substrate.
For example, a blood purifier in which the inner surface of the membrane base material is hydrophilic and the inside of the membrane is hydrophobic, in which the filling water is not sealed in advance in the blood purifier (so-called dry type) A membrane permeability maintaining agent such as glycerin is attached to the membrane substrate. However, at the time of activation preparation before use, this membrane permeability maintenance agent is thoroughly washed away with physiological saline and the like, and if the physiological saline or the like is not sufficiently adapted to the inside of the membrane substrate, a blood purifier is used for dialysis. It cannot be made possible, and it takes time to start the dialysis operation (that is, the liquid processing operation). Therefore, there is room for improvement in terms of improving the efficiency of the entire dialysis operation.

  In addition, in manufacturing a liquid processing module, there is also a demand for controlling the processing capability of the liquid processing module by simply changing the permeability to a specific substance while using the same membrane substrate.

  The present invention has been made in view of such circumstances, and a liquid processing module that easily attaches a hydrophilizing agent to the inside of a membrane substrate by a simple process and easily exhibits the permeability of the membrane substrate. And it aims at providing the manufacturing method of a liquid processing module. And it aims at providing the manufacturing method of the liquid processing module which can be manufactured by changing processing capacity easily, and a liquid processing module.

The present invention has been proposed in order to achieve the above-mentioned object, and according to the first aspect of the present invention, a casing is provided with a semipermeable membrane in which a hydrophilic agent is held on a hydrophobic membrane base material. A semipermeable membrane divides the inside of the casing into a first liquid passing space on one membrane surface side and a second liquid passing space on the other membrane surface side, and the casing communicates with the first liquid passing space. In a liquid processing module provided with a port and a second port communicating with the second liquid passing space,
The hydrophilizing agent includes at least a first hydrophilizing agent and a second hydrophilizing agent, the first hydrophilizing agent and the second hydrophilizing agent being the same component as each other, and the second hydrophilic agent. The average molecular weight of the agent is set smaller than the average molecular weight of the first hydrophilizing agent,
For the casing loaded with the membrane substrate therein, the treatment liquid containing the hydrophilizing agent is injected into the first liquid passing space through the first port,
A pressure difference is generated between the first liquid passage space and the second liquid passage space, and the solvent component of the processing liquid is moved from the first liquid passage space to the second liquid passage space by the pressure difference. In the liquid processing module, 1 hydrophilizing agent is held on the surface of the membrane base on the first liquid passing space side, and the second hydrophilizing agent is held inside the membrane base.

According to a second aspect of the present invention, the hydrophilizing agent is polyvinylpyrrolidone, the first hydrophilizing agent has an average molecular weight of 500 × 10 ³ or more, and the second hydrophilizing agent has an average molecular weight of less than 100 × 10 ^3. The liquid processing module according to claim 1 , wherein the hydrophobic membrane base material uses a polyester-based polymer alloy as a main membrane material.

The pump of Claim 3, mixing ratio of the first hydrophilic agent and a second hydrophilizing agent is 1: 9 to 9: claim 1 or claim 2, characterized in that one This is a liquid processing module.

According to a fourth aspect of the present invention, a casing is provided with a semipermeable membrane in which a hydrophilic agent is held on a hydrophobic membrane substrate, and the inside of the casing is provided with a first liquid passing space on one membrane surface side by the semipermeable membrane. And a second liquid passage space on the other membrane surface side, and the casing is provided with a first port communicating with the first liquid passage space and a second port communicating with the second liquid passage space. In the manufacturing method of the liquid processing module,
The hydrophilizing agent includes at least a first hydrophilizing agent and a second hydrophilizing agent, the first hydrophilizing agent and the second hydrophilizing agent being the same component as each other, and the second hydrophilic agent. The average molecular weight of the agent is set smaller than the average molecular weight of the first hydrophilizing agent,
A treatment liquid injection step of injecting a treatment liquid containing the hydrophilizing agent into the first liquid passing space through a first port with respect to the casing in which the membrane substrate is loaded,
A pressure difference is generated between the first liquid passage space and the second liquid passage space, and the solvent component of the processing liquid is moved from the first liquid passage space to the second liquid passage space by the pressure difference. A membrane-fluidizing step in which 1 hydrophilizing agent is held on the surface of the membrane base on the first liquid passing space side and the second hydrophilizing agent is held inside the membrane base;
This is a method for manufacturing a liquid processing module.

According to a fifth aspect of the present invention, a decompression step for decompressing at least the second liquid passage space is performed before the treatment liquid injection step,
The membrane liquid passing step is performed by a pressure difference between the second liquid passing space that has been reduced in pressure by the pressure reducing step and the first liquid passing space into which the processing liquid has been injected by the processing liquid injecting step. It is a manufacturing method of the liquid processing module of Claim 4 .

According to a sixth aspect of the present invention, the first port includes a first injection port and a first discharge port,
The second port is composed of a second injection port and a second discharge port,
After the membrane liquid passing step, a first purge step for discharging the processing liquid remaining in the first liquid passing space and a second purge step for discharging the processing liquid remaining in the second liquid passing space are performed,
In the first purge step, the first injection port and the first discharge port are opened, and a gas is introduced into the first liquid passing space in a state where the second injection port and the second discharge port are closed,
In the second purge step, the second injection port and the second discharge port are opened, and a gas is introduced into the second liquid passing space in a state where the first injection port and the first discharge port are closed. A method for manufacturing a liquid processing module according to claim 5 .

According to a seventh aspect of the present invention, the hydrophilizing agent is polyvinylpyrrolidone, the first hydrophilizing agent has an average molecular weight of 500 × 10 ³ or more, and the second hydrophilizing agent has an average molecular weight of less than 100 × 10 ^3. The method for producing a liquid processing module according to any one of claims 4 to 6 , wherein the hydrophobic membrane substrate is made of a polyester-based polymer alloy as a main membrane material.

The pump of Claim 8, the mixing ratio of the first hydrophilic agent and a second hydrophilizing agent is 1: 9 to 9: any of claims 4 to claim 7, characterized in that the 1 It is a manufacturing method of the liquid processing module as described above.

  By adopting the above configuration, the present invention has the following effects. That is, the hydrophilizing agent is configured to include at least a first hydrophilizing agent and a second hydrophilizing agent, and the first hydrophilizing agent and the second hydrophilizing agent are the same component as each other, and the second hydrophilizing agent. An average molecular weight of the hydrophilizing agent is set to be smaller than that of the first hydrophilizing agent, and the treatment liquid containing the hydrophilizing agent is passed through the first port through the first port with respect to the casing in which the membrane substrate is loaded. Injecting into the space, a pressure difference is generated between the first liquid passage space and the second liquid passage space, and the solvent component of the processing liquid is moved from the first liquid passage space to the second liquid passage space by the pressure difference. Since the first hydrophilizing agent is held on the surface of the membrane base on the first liquid passing space side and the second hydrophilizing agent is held inside the membrane base, not only the surface of the membrane base but also the inside. In addition, the hydrophilizing agent can be attached by a simple process, and the permeability of the membrane substrate can be rapidly exhibited. Therefore, the liquid processing preparation time can be shortened, and the efficiency of the liquid processing operation can be improved.

  Moreover, by adjusting the mixing ratio of the first hydrophilizing agent and the second hydrophilizing agent between 1: 9 and 9: 1, the permeability of the semipermeable membrane can be adjusted without changing the membrane substrate, The processing capability of the liquid processing module can be easily changed and manufactured.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In the following, a case where a hydrophilization treatment is performed on a membrane base material of a hydrophobic semipermeable membrane will be described by taking a dialyzer, which is a kind of liquid treatment module, as a specific example, a blood purifier. . First, the configuration of the blood purifier 1 will be described with reference to FIGS. 1 and 2. The illustrated blood purifier 1 has a configuration in which a hollow fiber bundle 3 is provided inside a casing 2.

  The casing 2 includes a cylindrical casing body 4 that can store the hollow fiber bundle 3, a discharge-side cap member 5 that is connected to one end of the casing body 4 in the longitudinal direction of the cylinder (upper side in FIG. 1), and the casing body 4. And an injection side cap member 6 connected to the other end in the cylinder longitudinal direction (lower side in FIG. 1). The casing body 4 is a cylindrical member provided with an enlarged diameter portion 7 at both ends in the longitudinal direction of the cylinder, and is made of, for example, polycarbonate. The enlarged diameter portion 7 located on one end side in the longitudinal direction of the cylinder has a dialysate injection port 8 (a part of the second port of the present invention, which is in communication with the internal space of the casing body 4). Is projected toward the side of the tube. On the other hand, the enlarged diameter portion 7 located on the other end side in the longitudinal direction of the cylinder has a dialysate discharge port 9 (a part of the second port of the present invention, which is in communication with the internal space of the casing body 4). (Corresponding to the port) is projected toward the side of the tube. The dialysate injection port 8 functions as a second injection port for injecting a second liquid (for example, dialysate), and the dialysate discharge port 9 serves as a second discharge port for discharging the second liquid. Function.

  Sealing portions 10 are provided at both ends of the casing body 4 in the longitudinal direction of the cylinder. This sealing part 10 is a part for adhering and fixing the end of the hollow fiber bundle 3 to the casing body 4, and is constituted by, for example, a sealing material 11. For example, a urethane adhesive is used as the sealing material 11. The sealing material 11 is filled between the hollow fiber bundle 3 and the casing body 4 and between the hollow fiber membranes 12 constituting the hollow fiber bundle 3. As a result, both the end faces of the casing body 4 are in a state in which a plurality of hollow fiber membranes 12 whose end portions are open are densely packed, and the sealing material 11 is in a sealed state in which the gaps between the hollow fiber membranes 12 are closed. ing.

  And as shown in FIG. 1, this sealing part 10 is provided in the edge part side of a cylinder longitudinal direction rather than the opening position of the dialysate injection | pouring port 8 and the dialysate discharge | emission port 9. As shown in FIG. For this reason, the hollow fiber membrane 12 and the sealing portion 10 divide the internal space of the casing body 4 into an inner space and an outer space of the hollow fiber membrane 12. Further, the outer space of the hollow fiber membrane 12 communicates with the outside of the casing 4 through the dialysate injection port 8 and the dialysate discharge port 9. The inner space of the hollow fiber membrane 12 functions as a first fluid passage space for passing a first liquid (for example, blood), and the outer space of the hollow fiber membrane 12 is a first passage for passing a second liquid. Functions as a two-fluid space.

  The discharge-side cap member 5 is a substantially funnel-shaped cap member having a blood discharge port 13 and is screwed to the other end side in the cylinder longitudinal direction. The discharge-side cap member 5 is provided with an O-ring 14 that can be in close contact with the outer peripheral portion of the outer surface of the sealing portion. The O-ring 14 is in close contact with the outer surface of the sealing portion, thereby sealing the boundary between the casing body 4 and the discharge-side cap member 5 in a liquid-tight manner. The injection-side cap member 6 has a structure similar to that of the discharge-side cap member 5 and is a substantially funnel-shaped cap member provided with a blood injection port 15. And this injection | pouring side cap member 6 is screwed by the cylinder longitudinal direction one end side of the casing main body 4, O-ring 16 closely_contact | adheres to a sealing part outer surface in the screwed state, and the casing main body 4 and the injection | pouring side cap member 6 The boundary between and is sealed fluid-tight.

  Here, the blood discharge port 13 functions as a first discharge port (a part of the first port of the present invention) for discharging the first liquid, and the blood injection port 15 is for injecting the first liquid. It functions as a first injection port (a part of the first port of the present invention). In the screwed state of the cap members 5 and 6, the internal space of the discharge side cap member 5 and the internal space of the injection side cap member 6 are blood flow paths through which blood passes along with the inner space of each hollow fiber membrane 12. Configure. In this embodiment, this blood flow path functions as a first liquid passing space for allowing the first liquid to pass therethrough.

  The hollow fiber membrane 12 is a kind of hydrophilic membrane in the present invention. As shown in FIGS. 2B and 4, the hollow fiber membrane 12 is a semipermeable membrane in which a hydrophilic agent 18 is held on a hollow fiber membrane substrate 17. It is a membrane. And this hollow fiber membrane 12 is a very thin thing with a film thickness of about 5-50 micrometers and an internal diameter of about 100-500 micrometers.

  The membrane base material 17 is a semipermeable membrane made of a hydrophobic polymer made mainly of a polyester resin and a polysulfone resin. Here, the said polyester-type resin is polyarylate resin which has a repeating unit represented by following formula (1), for example.

  The polysulfone resin is, for example, a polysulfone resin having at least one of a repeating unit represented by the following formula (2) and a repeating unit represented by the following formula (3).

  The film forming stock solution for spinning the hydrophobic membrane substrate 17 defines a mixing weight ratio (A / B) of the polyester resin (A) and the polysulfone resin (B) in the range of 0.1 to 10. At the same time, it is prepared by dissolving in an organic solvent such that the total amount (A + B) of both resins is in the ratio of 10 wt% to 25 wt%. When the membrane-forming stock solution thus prepared is discharged into the coagulating solution together with the core solution using a double tube spinneret, a hollow fiber-shaped membrane substrate 17 using a polyester polymer alloy as a membrane material is obtained. And this film | membrane base material 17 is bundled as a unit about 3000-15000 pieces.

  The hollow fiber-like membrane substrate 17 has a dense layer formed on the inner surface thereof, and a porous layer is formed so as to cover the outside of the dense layer. The dense layer is a part that defines the permselectivity and the permeation rate of the substance in the membrane substrate 17. For example, the dense layer has pores having an average pore diameter of less than 500 angstroms, specifically, a pore radius of 30 to 200 angstroms. A hole is formed. Further, the porous layer functions as a support layer that supports the dense layer and maintains the strength of the film, and pores that are considerably coarser than the dense layer are formed.

  And this film | membrane base material 17 has the molecular weight fractionation characteristic shown in FIG. As shown in this figure, for example, for a substance having a molecular weight of 35,000, the sieve coefficient (SC) is about 0.5, that is, about 50% of the total amount permeates the membrane substrate 17 (specifically, Pass through the pores formed in the dense layer), and for a substance having a molecular weight of 70,000, the sieve coefficient is about 0.05, that is, about 5% of the total amount permeates the membrane substrate 17, It can be seen that the remaining 95% cannot be transmitted. Further, for substances having a molecular weight of 100,000 or more, almost the entire amount (100%) cannot penetrate the membrane substrate 17.

  Further, as the hydrophilizing agent 18 held by the membrane substrate 17, a hydrophilic polymer having hydrophilicity is used. And as this hydrophilizing agent 18, the substance which does not detach | leave easily from the film | membrane base material 17 at the time of use is selected. Therefore, as this hydrophilizing agent 18, various substances can be selected as long as the above conditions are satisfied. As a result of research by the present inventors, it has been found that polyvinylpyrrolidone (PVP) is most suitable as the hydrophilizing agent 18 (hydrophilic polymer) that satisfies the above-mentioned conditions. This is largely due to the good biocompatibility of polyvinylpyrrolidone.

However, this polyvinyl pyrrolidone also has a plurality of types depending on the molecular weight. And with polyvinylpyrrolidone having an average molecular weight of 500 × 10 ³ or more, for example, K-90 having an average molecular weight of 1,200,000 (1200 × 10 ³ ), the permeation of the membrane substrate 17 can be prevented and once adhered and retained. It is difficult to detach from the membrane surface easily. Therefore, polyvinyl pyrrolidone having an average molecular weight of 500 × 10 ³ or more can be suitably used for selectively imparting hydrophilicity to one surface of the film substrate 17. In contrast, in the case of K-30 having an average molecular weight of less than 100 × 10 ³ , for example, K-30 having an average molecular weight of 40,000 (40 × 10 ³ ), a large amount of polyvinylpyrrolidone permeates into the membrane substrate 17. For this reason, if polyvinyl pyrrolidone having an average molecular weight of less than 100 × 10 ³ is used, it can be suitably used when it is infiltrated in the thickness direction of the film substrate 17 to impart hydrophilicity.

In the hollow fiber membrane 12 of this embodiment, as shown in FIG. 4, the average molecular weight of about 1200 × 10 ³ is mainly used as the first hydrophilizing agent 18 a on one surface of the membrane substrate 17, specifically, the inner surface. Polyvinylpyrrolidone (K-90) is attached. In the thickness direction of the membrane substrate 17, polyvinylpyrrolidone (K-30) having an average molecular weight of about 40 × 10 ³ is mainly attached as the second hydrophilizing agent 18b. In this way, the hollow fiber membrane 12 is given hydrophilicity not only on the inner surface of the membrane substrate 17 but also inside the membrane substrate. The polyvinyl pyrrolidone as the hydrophilizing agent is not limited to K-90 or K-30 described above, and any material can be used as long as it can be adhered and held on the surface of the membrane substrate 17 or inside the membrane. It is preferable that a molecular weight of 500 × 10 ³ or more and an average molecular weight of less than 100 × 10 ³ are adhered and held inside the film.

In the present embodiment, two types of polyvinyl pyrrolidone, K-90 and K-30, distinguished by average molecular weight, are applied. However, the present invention is not limited to this, and the types of polyvinyl pyrrolidone to be mixed are classified according to average molecular weight. Can be any number. And even if it is polyvinyl pyrrolidone specified by one kind of average molecular weight, what is necessary is just to have two or more peaks in the molecular weight distribution. Further, for example, it is preferable that one of the peaks is 500 × 10 ³ or more and any of the other peaks is less than 100 × 10 ³ .

  Any hydrophilizing agent capable of adhering to the inner surface and pores of the membrane substrate 17 is not limited to the above-described average molecular weight, and can be suitably used. Note that not all hydrophilizing agents having molecular weights smaller than the pores of the membrane substrate 17 permeate the membrane substrate 17. This is because the pores have a wide and narrow distribution, and the hydrophilizing agent having a small molecular weight is difficult to pass through and is easily retained in the narrow portion of the pores. This is because the pores are further narrowed and a hydrophilizing agent having a smaller molecular weight is easily retained. If a large amount of a hydrophilization treatment liquid described later moves from the inside to the outside of the membrane substrate, even a small hydrophilizing agent is easily held in the pores and is easily attached and held on the membrane substrate. The method for attaching the hydrophilizing agent 18 to the membrane substrate 17 will be described in detail later.

  In this blood purifier 1, during the dialysis treatment, the inflow side blood tube is connected to the blood injection port 15 of the injection side cap member 6, and the discharge side blood tube is connected to the blood discharge port 13 of the discharge side cap member 5. Are connected (both not shown). Here, the inflow side blood tube is a flexible tube made of synthetic resin through which the blood derived from the patient's body passes, and the discharge side blood tube passes the blood (processed blood) to be returned to the patient's body. It is a flexible tube made of synthetic resin. In addition, a supply-side dialysate tube is connected to the dialysate injection port 8 of the casing body 4, and a discharge-side dialysate tube is connected to the dialysate discharge port 9 (both not shown). Here, the supply-side dialysate tube is a flexible tube made of synthetic resin through which a new dialysate supplied from the dialysate reservoir passes, and the discharge-side dialysate tube is a synthetic resin through which the dialysate after processing passes. A flexible tube made of In this case, the blood is a kind of the first liquid in the liquid processing module, and the dialysate is a kind of the second liquid in the liquid processing module.

  Next, the manufacturing method of the hydrophilization film | membrane which makes the membrane base material 17 hold | maintain the hydrophilizing agent 18 is demonstrated in detail. Here, FIG. 5 is a schematic view for explaining a processing apparatus (that is, a kind of manufacturing apparatus for a liquid processing module) used in this manufacturing method. The hydrophilic membrane is manufactured after the bundled membrane base material 17 (referred to as a membrane base material bundle for convenience) is loaded in the casing 2. In other words, the blood purification device 1 assembled in the state of the membrane substrate bundle is subjected to a hydrophilic treatment.

  The illustrated processing device 19 is a device that performs processing by the so-called negative pressure method, and decompresses the inside of the casing 2 of the blood purifier 1, that is, the inner space and the outer space of the hollow fiber membrane 12 in advance before injecting the processing liquid, Then, a pressure difference is provided between the inner surface and the outer surface by injecting the treatment liquid into the inner surface of the membrane substrate 17, and ultrafiltration is performed by this pressure difference. The processing device 19 includes a waste liquid storage unit 20, a gas supply source 21, a processing liquid storage unit 22, a purifier mounting unit 23, a decompression pump 43, a gas supply pipe 44, a discharge pipe 45, a processing liquid. A supply pipe 46, an intake pipe 47, and a control unit (not shown) are provided.

  The waste liquid storage unit 20 is a part (chamber) that can store the discharged hydrophilic treatment liquid. The gas supply source 21 is a portion that supplies a compressed gas such as compressed air, and is constituted by a compressor, for example. The treatment liquid storage unit 22 is a part that stores a hydrophilic treatment liquid (a kind of the treatment liquid of the present invention). The purifier mounting part 23 is a part where the blood purifier 1 to be processed is set, and in this embodiment, the blood is discharged in a state where the blood discharge port 13 and the blood injection port 15 are directed in the vertical direction (vertical direction). The purifier 1 is set. The control unit includes a CPU, a ROM, a RAM, and the like, and controls operations of an on-off valve and the like described later.

  The decompression pump 43 decompresses the inside of the casing body 4 set in the purifier mounting portion 23 and is always operated while the processing device 19 is in operation.

  The gas supply pipe 44 is a pipe that communicates between the gas supply source 21 and the purifier mounting section 23, and the first gas supply branch pipe 44 a and the second gas supply branch are connected to the purifier mounting section 23 side (downstream side). The pipe 44b is branched. The first gas supply branch pipe 44a has a downstream end at one of the blood discharge port 13 and the blood injection port 15 of the blood purifier 1 set in the purifier mounting portion 23 (in FIG. 5, the blood discharge port 13). ). Therefore, the first gas supply branch pipe 44 a allows the space inside the hollow fiber membrane 12 and the gas supply source 21 to communicate with each other in the blood purifier 1. The first gas supply branch pipe 44a merges with the processing liquid supply pipe 46 on the way, and details thereof will be described later.

  In addition, the second gas supply branch pipe 44b has one of the dialysate injection port 8 and the dialysate discharge port 9 of the blood purifier 1 set in the purifier mounting portion 23 at the downstream end (in FIG. 5, Connected to dialysate injection port 8). Therefore, the outer space of the hollow fiber membrane 12 and the gas supply source 21 in the blood purifier 1 are communicated with each other by the second gas supply branch pipe 44b. The second gas supply branch pipe 44b merges with the intake pipe 47 in the middle, and details will be described later.

  A first on-off valve 51 is provided on the gas supply source 21 side (upstream side) from the branch point H of the gas supply pipe 44. A second opening / closing valve 52 is provided in the middle of the first gas supply branch pipe 44a, and a third opening / closing valve 53 is provided in the middle of the second gas supply branch pipe 44b.

  The discharge pipe 45 is a pipe that communicates between the purifier mounting part 23 and the waste liquid storage part 20, and the purifier mounting part 23 side (upstream side) is connected to the first discharge branch pipe 45a and the second discharge branch pipe 45b. It is composed of branches. The first discharge branch pipe 45a has an upstream end connected to the other of the blood discharge port 13 and the blood injection port 15 (blood injection port 15 in FIG. 5). Therefore, in the blood purifier 1, the inner space of the hollow fiber membrane 12 and the waste liquid storage unit 20 are communicated with each other through the first discharge branch pipe 45 a. In addition, the 5th on-off valve 55 is provided in the middle of the 1st discharge branch pipe 45a. Further, the first discharge branch pipe 45a merges with the processing liquid supply pipe 46 on the way, and details thereof will be described later.

  The second discharge branch 45b connects the upstream end to the other of the dialysate injection port 8 and the dialysate discharge port 9 (dialysate discharge port 9 in FIG. 5). Therefore, in the blood purifier 1, the outer space of the hollow fiber membrane 12 and the waste liquid storage unit 20 are communicated with each other by the second discharge branch pipe 45 b.

  The processing liquid supply pipe 46 communicates between the processing liquid storage part 22 and the purifier mounting part 23, and the purifier mounting part 23 side (downstream side) is connected to the first processing liquid supply branch pipe 46 a and the second. It branches off to the processing liquid supply branch pipe 46b. The first treatment liquid supply branch pipe 46 a has a downstream end connected to one of the blood discharge port 13 and the blood injection port 15 (blood discharge port 13 in FIG. 5). Therefore, the inner space of the hollow fiber membrane 12 and the processing liquid reservoir 22 are communicated with each other by the first processing liquid supply branch pipe 46a.

  The second treatment liquid supply branch pipe 46b has a downstream end connected to the other of the blood discharge port 13 and the blood injection port 15 (blood injection port 15 in FIG. 5). Accordingly, the inner space of the hollow fiber membrane 12 and the treatment liquid storage unit 22 in the blood purifier 1 are communicated with each other by the second treatment liquid supply branch pipe 46b.

  In the present embodiment, the first treatment liquid supply branch pipe 46a and the first gas supply branch pipe 44a are merged in the middle of the purifier mounting part 23 side. For this reason, a pipe (first common pipe) 60 from the junction C between the first treatment liquid supply branch pipe 46a and the first gas supply branch pipe 44a to the end on the purifier mounting part 23 side is a treatment liquid supply pipe. It functions as a part of 46 and also functions as a part of the gas supply pipe 44. The end of the first common pipe 60 on the purifier mounting 23 side is configured as a first connection portion 29 connected to one of the blood injection port 15 and the blood discharge port 13.

  Further, the second treatment liquid supply branch pipe 46b and the first discharge branch pipe 45a are joined in the middle of the purifier mounting part 23 side. Therefore, the pipe (second common pipe) 61 from the junction D of the second processing liquid supply branch pipe 46b and the first discharge branch pipe 45a to the end on the purifier mounting part 23 side is the processing liquid supply pipe 46. As well as a part of the discharge pipe 45. The end of the second common tube 61 on the purifier mounting part 23 side is configured as a second connection part 30 connected to the other of the blood injection port 15 and the blood discharge port 13.

  A liquid feed pump 35 is provided between the treatment liquid reservoir 22 and the branch point in the treatment liquid supply pipe 46. In addition, a seventh on-off valve 62 is provided in the middle of the second processing liquid supply branch pipe 46b in the middle of the first processing liquid supply branch pipe 46a and on the upstream side (branch point side) of the first common pipe 60. The eighth on-off valve 63 is upstream of the second common pipe 61 (branch point side), the ninth on-off valve 64 is in the middle of the first common pipe 60, and the eighth on-off valve is in the middle of the second common pipe 61. Ten open / close valves 65 are provided.

  A first manual valve 66 is provided in the middle of the first processing liquid supply branch pipe 46a and upstream of the seventh on-off valve 62, and in the middle of the second processing liquid supply branch pipe 46b. A second manual valve 67 is provided upstream of the eighth on-off valve 63. The first manual valve 66 and the second manual valve 67 are normally opened by adjusting the opening degree in advance so that the flow rate of the processing liquid flowing in from the blood injection port 15 and the blood discharge port 13 is balanced.

  The intake pipe 47 is a pipe that communicates between the decompression pump 43 and the purifier mounting portion 23, and is in the middle of the second gas supply branch pipe 44 b and closer to the purifier mounting portion 23 side than the third on-off valve 53. It is connected to the junction point E. The intake pipe 47 is connected to the upstream part of the second gas supply branch pipe 44b from the connection point E, the branch part H of the gas supply pipe 44, the first gas supply branch pipe 44a and the first common pipe 60. Thus, it communicates with one of blood discharge port 13 and blood injection port 15 (blood discharge port 13 in FIG. 5). Furthermore, the second gas supply branch pipe 44b is connected to one of the dialysate injection port 8 and the dialysate discharge port 9 (dialysate injection port 8 in FIG. 5) via the downstream portion from the connection point E. Connected. Therefore, the intake pipe 47 communicates the inside of the blood purifier 1 (that is, the inner space and the outer space of the hollow fiber membrane 12) with the decompression pump 43.

  An eleventh on-off valve 71 is provided in the middle of the intake pipe 47. Further, a twelfth on-off valve 72 is provided in the middle of the portion of the second gas supply branch pipe 44b from the connection point E to the purification liquid mounting portion 23 side (downstream side).

  Furthermore, the processing device 19 connects the second gas supply branch pipe 44b and the second discharge branch pipe 45b by a connection pipe 73. More specifically, the connection pipe 73 has one end at the junction F between the connection point E and the twelfth on-off valve 72 in the second gas supply branch pipe 44b and the other end at the second discharge branch pipe 45b. Are connected to the junction G in the middle. A thirteenth on-off valve 74 is provided in the middle of the connecting pipe 73. Since the thirteenth on-off valve 74 is normally closed in the hydrophilization process described later, the connecting pipe 73 and the thirteenth on-off valve 74 need not be provided.

  A thirteenth on-off valve 74 is installed in the middle of the connecting pipe 73, and a purifier is installed in the middle of the second discharge branch pipe 45b, rather than at the junction G of the connection pipe 73 and the second discharge branch pipe 45b. Fourteenth on-off valves 75 are provided on the part 23 side.

  The first on-off valve 51 to the fourteenth on-off valve 75 are electrically controlled by the control unit, and are independently converted into a closed state and an open state.

  And although compressed air is supplied from the gas supply source 21, it is not limited to this. For example, compressed nitrogen may be supplied as the compressed gas. Moreover, said purifier mounting | wearing part 23 functions as a casing mounting | wearing part in which the casing 2 which loaded the membrane base material bundle | flux inside is set.

  Further, the treatment liquid reservoir 22 stores a polyvinylpyrrolidone aqueous solution as a hydrophilic treatment liquid. This treatment liquid is a mixture of K-90 as the first hydrophilizing agent 18a having a large average molecular weight and K-30 as the second hydrophilizing agent 18b having an average molecular weight smaller than that of the first hydrophilizing agent 18a. This mixed polyvinyl pyrrolidone is contained at a concentration of 0.3 to 3.0 wt%, for example. When the hydrophilization treatment liquid is set to the above concentration, if it is less than 0.3 wt%, a large amount of treatment liquid is used to hold a predetermined amount of the hydrophilizing agent on the membrane substrate 17 in the hydrophilization treatment described later. This is because a long processing time is required. On the other hand, when the concentration is 3.0 wt% or more, the treatment liquid is difficult to penetrate into the membrane substrate 17. The mixing ratio of K-90 and K-30 is 1: 9 to 9: 1, preferably 3: 7 to 7: 3. This is because if too much K-90 is mixed, there is a risk that the penetration of the hydrophilizing agent will be reduced, leading to insufficient activation, and if too much K-30 is mixed, on the membrane surface. This is because it is difficult to obtain the required fractionation characteristics. That is, in order to simultaneously impart hydrophilicity to both the surface and the inside (thickness direction) of the membrane substrate 17, according to the pore distribution of the membrane substrate 17 and the desired performance of the blood purifier 1, There is an appropriate mixing ratio.

  Further, the treatment liquid storage unit 22 includes a temperature adjustment means (not shown) such as a heater, and the temperature adjustment means adjusts the treatment liquid temperature between about 20 to 80 ° C., preferably around 50 ° C. Yes. This is because the viscosity of the processing liquid is controlled by adjusting the temperature so that the processing liquid can easily penetrate into the membrane substrate 17.

  Next, the negative pressure method hydrophilic treatment by the processing device 19 will be described. First, in the setting step, the blood purifier 1 to be hydrophilized is set on the purifier mounting portion 23, and for example, the casing main body 4 is grasped by a robot arm (not shown) and the robot arm is moved. Thus, the blood discharge port 13 is positioned on the first connection portion 29 side and the blood injection port 15 is positioned on the second connection portion 30 side. When the blood purifier 1 is set, the control unit recognizes it and connects the first connection portion 29 to the blood discharge port 13 and the second connection portion 30 to the blood injection port 15 to make it liquid-tight. .

  If the blood purifier 1 is set in the purifier mounting portion 23, the process proceeds to the pressure reducing process. In the decompression step, the control unit operates the eleventh on-off valve 71, the second on-off valve 52, the third on-off valve 53, the ninth on-off valve 64, the twelfth, with the decompression pump 43 activated, as shown in FIG. The on-off valve 72 and the tenth on-off valve 65 are controlled to be opened, and the other on-off valves are controlled to be closed. Thereby, as shown by the thick line in the figure, the gas (air) in the blood purifier 1 is sucked from the ports 8 and 13. Specifically, the air in the inner space of the hollow fiber membrane 12 is sucked from the blood discharge port 13 through the first common pipe 60, the first gas supply branch pipe 44 a and the intake pipe 47. Then, the air in the outer space of the hollow fiber membrane 12 is sucked from the dialysate injection port 8 through the second gas supply branch pipe 44 b and the intake pipe 47. Thereby, the outer space and inner space of the hollow fiber membrane 12 are depressurized. The inside of blood purifier 1 is preferably decompressed to -80 kPa or less. This is because when the degree of vacuum (degree of vacuum) is high, the hydrophilic treatment is uniformly performed over the entire hollow fiber membrane 12, and the progress of the hydrophilic treatment is accelerated, and the working efficiency is improved. It is.

  In the decompression step, air in the inner space of the hollow fiber membrane 12 may be sucked from both the blood discharge port 13 and the blood injection port 15. Further, the air in the outer space of the hollow fiber membrane 12 may be sucked from both the dialysate injection port 8 and the dialysate discharge port 9.

  If the inside of the blood purifier 1 is sufficiently depressurized, the processing liquid injection process is started. In the treatment liquid injection step, the hydrophilic treatment liquid is injected into the blood purifier 1. Therefore, the control unit operates the liquid feed pump 35, and as shown in FIG. 7, the first on-off valve 51, the second on-off valve 52, the third on-off valve 53, the eleventh on-off valve 71, the twelfth on-off valve. 72, the 14th on-off valve 75, and the 5th on-off valve 55 are controlled to be in a closed state, and the seventh on-off valve 62, the ninth on-off valve 64, the eighth on-off valve 63, and the 10th on-off valve 65 are controlled to be in an open state. . Then, the hydrophilization treatment liquid stored in the treatment liquid storage unit 22 is pressurized by the liquid feed pump 35, and the pressure difference between the hydrophilization treatment liquid and the inside of the blood purifier 1 increases. Thereby, as shown by the thick line in the figure, the hydrophilized treatment liquid stored in the treatment liquid reservoir 22 is treated with the treatment liquid supply pipe 46 (the first treatment liquid supply branch pipe 46a and the second treatment liquid supply branch pipe 46b). It is injected from both the upper and lower sides into the blood purifier 1 (blood flow path as the first liquid passing space) through the passage. The injected hydrophilic treatment liquid fills the inner space of the hollow fiber membrane 12 after filling the internal space of the discharge side cap member 5 and the injection side cap member 6. At this time, the eleventh on-off valve 71 and the twelfth on-off valve 72 may be opened while the decompression pump 43 is operated, and the outer space of the hollow fiber membrane 12 may continue to be decompressed.

  Then, when the hydrophilic treatment liquid is passed through the inner space of the hollow fiber membrane 12, the process proceeds to the membrane passing process. That is, a pressure difference is generated between the inner space of the hollow fiber membrane 12 (or the hydrophilization treatment liquid filled in the inner space) and the outer space in a reduced pressure state. Due to this pressure difference, the solvent component of the hydrophilization liquid passes through the membrane substrate 17 and moves to the outside of the membrane substrate 17. In this way, filtration of the hydrophilic treatment liquid is started. And among the hydrophilizing agents in the hydrophilization treatment liquid, those having a molecular weight larger than the pores of the membrane substrate 17 (for example, K-90) do not enter the pores, but enter the inner surface of the membrane substrate 17. Easy to adhere. On the other hand, a hydrophilizing agent having a molecular weight smaller than that of the pores of the membrane substrate 17 (for example, K-30) enters the pores together with the solvent component of the hydrophilization treatment liquid and exits into the outer space of the membrane substrate 17 as it is. However, many adhere to and hold in narrow pores.

  If the specified amount of the hydrophilization treatment liquid present on the blood flow path side of the blood purifier 1 is filtered, the control unit closes each on-off valve to stop the flow of the hydrophilization treatment liquid, and performs the first purge step. Transition. In this first purge step, air is passed through the blood flow path of the blood purifier 1 (the inner space of the hollow fiber membrane 12), thereby removing excess hydrophilization treatment liquid in the blood flow path and unstable. The hydrophilic polymer in a state of holding (a state in which the holding power is weak and can be easily detached) is also removed. Specifically, in the first purge step, as shown in FIG. 8, the control unit performs the first on-off valve 51, the second on-off valve 52, the ninth on-off valve 64, the tenth on-off valve 65, and the fifth on-off valve. The valve 55 is controlled to be in an open state, and other open / close valves are controlled to be in a closed state. Thereafter, gas, for example, compressed air is supplied from the gas supply source 21. Then, as shown by a thick line in the figure, the compressed air flows into the inner space of the hollow fiber membrane 12 through the first gas supply branch pipe 44a and the first common pipe 60, and is discharged from the first discharge branch pipe 45a. It flows out to 20. Therefore, the surplus hydrophilization treatment liquid is pushed out of the blood purifier 1 by the compressed air, and is discharged to the waste liquid storage unit 20 through the first discharge branch pipe 45a.

  When the first purge process is completed, the process proceeds to the second purge process. In the second purge step, air that has passed from the inner space of the hollow fiber membrane 12 is removed by passing air through the outer space of the hollow fiber membrane 12. Specifically, in the second purge step, as shown in FIG. 9, the control unit opens the first on-off valve 51, the third on-off valve 53, the twelfth on-off valve 72, and the fourteenth on-off valve 75. In addition to controlling, other open / close valves are controlled to be closed. Thereafter, compressed air is supplied from the gas supply source 21. Then, as shown by a thick line in the figure, the compressed air flows into the outer space of the hollow fiber membrane 12 through the second gas supply branch pipe 44b and flows out from the second discharge branch pipe 45b to the waste liquid storage section 20. Therefore, the solvent component of the hydrophilic treatment liquid is pushed out from the outer space of the hollow fiber membrane 12 by the compressed air, and is discharged to the waste liquid storage unit 20 through the second discharge branch pipe 45b.

  By the end of the second purge step, the hydrophilic treatment by this negative pressure method is completed. Then, the blood purifier 1 that has been processed is removed from the purifier mounting portion 23 by moving the robot arm or the like. Thereafter, the next blood purifier 1 is set on the purifier mounting portion 23 and the same processing as described above is repeated.

  As described above, the blood purifier 1 that has been subjected to the hydrophilization treatment by the processing device 19 can adhere and retain the hydrophilizing agent not only on the inner surface of the membrane base material 17 but also on the inside of the film thickness. Therefore, the permeability of the membrane base material can be exhibited quickly, and the activation treatment time for preparation before dialysis can be shortened. From this, the efficiency of the whole dialysis work can be improved.

  Further, in the hydrophilization treatment by the processing device 19 described above, the hydrophilizing agent 18 is retained in the process of filtering the treatment liquid, so that the hydrophilizing agent 18 in the hydrophilizing treatment liquid can be efficiently retained. Furthermore, the hydrophilizing agent can be retained on the inner surface and inside of the membrane substrate by a simple process without insolubilization.

  Moreover, in the processing apparatus 19, since the hydrophilic treatment liquid is injected after the air in the blood purifier 1 has been removed in advance, bubbles do not remain on the surface of the membrane substrate 17 when the treatment liquid is injected. Therefore, the contact between the treatment liquid and the membrane surface is not hindered by the bubbles, and the hydrophilic treatment is uniformly performed over the entire hollow fiber membrane 12. From this, the hydrophilic treatment of the membrane substrate 17 can be performed efficiently. Further, the hydrophilic treatment can be performed without applying excessive mechanical stress to the film substrate 17. In the decompression step, the outer space and the inner space of the hollow fiber membrane 12 are decompressed, but the present invention is not limited to this. For example, only the outer space may be depressurized. In this case as well, a pressure difference can be set between the outer space and the inner space of the hollow fiber membrane 12 in the membrane passing step, and the solvent of the hydrophilization treatment liquid The component can be moved from the inner space to the outer space.

  In the above-described embodiment, the second purge process is performed after the first purge process, but the present invention is not limited to this. For example, after the second purge step, the first purge step is performed, and first, the material that has moved to the outside of the hollow fiber membrane 12 is discharged out of the blood purifier 1, and then the hydrophilization liquid remaining in the blood channel is discharged. You may make it do. The order of performing these purge steps is preferably changed according to the strength of the hollow fiber membrane 12. That is, when the hollow fiber membrane 12 is easily stretched by the internal pressure and the pore size is easily changed, the first purge step (intramembrane purge step) is performed before the second purge step (outside membrane purge step). ) Is preferred. In this order, when air pressure is applied to the inside of the hollow fiber membrane 12, it is possible to prevent the hollow fiber membrane 12 from being elongated by the treatment liquid in the outer space and changing the size of the pores. If the strength of the hollow fiber membrane 12 is high, either purge process may be performed first.

  The blood purifier 1 as an example of the dialyzer described above includes a dialysate injection port 8 and a dialysate discharge port 9 in the casing body 4, and a blood discharge port 13 and a blood injection port 15 in the cap members 5 and 6. However, the present invention is not limited to this. For example, the dialyzer set in the processing apparatus may have a cap member provided with a blood port and a dialysis port.

  Moreover, in the said embodiment, although the space which faces the outer surface of the film | membrane base material 17 was made into the pressure-reduced state, the hydrophilic treatment liquid was moved, However, the space which faces the inner surface of the film | membrane base material 17 is made into a pressurized state. The hydrophilic treatment liquid may be moved. And in the said embodiment, the solvent component of the hydrophilization process liquid was moved from the inner space of the hollow fiber membrane 12 to the outer space, and the 1st hydrophilizing agent 18a was mainly adhere | attached and hold | maintained on the inner surface of the membrane base material 17. However, the present invention is not limited to this. That is, by injecting the hydrophilic treatment liquid into the outer space of the hollow fiber membrane and moving the solvent component of the hydrophilic treatment liquid from the outer space to the inner space of the hollow fiber membrane, 1 The hydrophilizing agent 18a may be adhered and held. In short, it is sufficient that a pressure difference is given between one and the other of the film surface and the pressure of the space into which the hydrophilization liquid is injected is high.

  Further, the hollow fiber membrane 12 is subjected to an operation of moving the solvent component of the hydrophilization treatment liquid from the inner space to the outer space and an operation of moving the solvent component of the hydrophilization treatment liquid from the inner space to the outer space. Alternatively, the first hydrophilizing agent 18a may be mainly attached and held on both the inner and outer surfaces of the membrane substrate 17, and the second hydrophilizing agent 18b may be mainly attached and held inside the membrane substrate 17.

  By the way, in the conventional blood purifier, the hollow fiber bundle previously treated with a membrane permeability maintaining agent such as glycerin is used to seal the end of the casing body with a sealing material (for example, urethane-based adhesive) with the end portion protruding from the casing body. Then, the end of each hollow fiber membrane is opened by cutting and removing the end of the hollow fiber bundle together with the sealing material. The cut surface is preferably formed in a smooth state. This is for avoiding that the components in the liquid to be processed, for example, blood cell components in blood, are damaged on the cut surface in the liquid processing operation.

  However, in the conventional hollow fiber membrane, since the membrane permeability maintaining agent penetrates into the pores, the sealing material cannot enter the pores. Therefore, the hardness of the hollow fiber membrane is different from that of the sealing material layer after curing (after bonding and fixing). Therefore, in order to make the finish of the casing end suitable for the liquid treatment (smooth state), it is necessary to set the cutting processing speed strictly, which is troublesome. For example, if the processing speed is set to be biased to the cutting conditions of the sealing material, the cut surface of the sealing material becomes a smooth finished surface, but the cut surface at the end of the hollow fiber membrane is rough and burrs are likely to occur.

  However, in the above-described embodiment, after the hollow fiber bundle made of the hydrophobic membrane base material is bonded to the casing body, the hydrophilic treatment can be performed on the inner surface and the inside of the film thickness of the membrane base material. Since the permeability of the base material is easily exhibited quickly, it is not necessary to previously treat the hollow fiber membrane with a membrane permeability maintenance agent. Therefore, when the end of the hollow fiber bundle is bonded to the end of the casing body, the sealing material easily penetrates into the outer surface and the pores at the end of the hollow fiber bundle. And the hardness of the hollow fiber membrane of a casing main body edge part can be closely approached to the hardness of a sealing material layer. For this reason, even if cutting is performed in accordance with conditions suitable for the sealing material, burrs or the like hardly occur at the cut end of the hollow fiber membrane, and the end of the casing body can be finished in a smooth state. Therefore, it is possible to relax the setting conditions for the cutting process, and it is possible to improve the work efficiency of manufacturing the liquid processing module. In addition, adverse effects on blood components can be suppressed.

  In the above embodiment, the blood purifier 1 loaded with the hollow fiber bundle 3 is illustrated, but the present invention can also be applied to a stacked blood purifier in which flat membranes are stacked in layers.

  Furthermore, the above-described method for producing a hydrophilic membrane can be applied not only to the exemplified liquid treatment module for dialysis but also to other liquid treatment modules. For example, in the liquid processing module having no second injection port, the predetermined component extracted from the first liquid in the first liquid passing space through the semipermeable membrane of the hollow fiber is converted into the second liquid passing space. It may be applied to what is taken out through the second discharge port. Specifically, a blood inlet port as a first injection port and a first outlet port and a blood outlet port are provided in communication with the first fluid passage space, and the plasma outlet port as a second port is provided in the second fluid passage space. The present invention may be applied to a plasma separation filter provided in a state where it is communicated with.

  In addition, the liquid processing module includes only the first injection port and the second discharge port, and the liquid flowing in from the first injection port is filtered through the semipermeable membrane to flow out from the second discharge port, so that the foreign matter in the liquid Even for a type that filters out water (for example, a sterilization filter), a pressure difference is applied between the first liquid passing space and the second liquid passing space, and the hydrophilizing agent in the processing liquid is applied to the membrane substrate. By holding it, a semipermeable membrane can be processed.

  By the way, in the said embodiment, although the hydrophilization process was performed with respect to the membrane base material with which the casing main body was loaded, this invention is not limited to this, With respect to the membrane base material single body before loading to a casing main body Processing may be performed. That is, in the method for producing a semipermeable membrane in which a hydrophilic agent is held on a hydrophobic membrane substrate, the hydrophilic agent includes at least a first hydrophilic agent and a second hydrophilic agent, and the first A treatment in which the hydrophilizing agent and the second hydrophilizing agent are the same component as each other, and the average molecular weight of the second hydrophilizing agent is set smaller than the average molecular weight of the first hydrophilizing agent, The liquid component is immersed in one surface of the membrane substrate, and a pressure difference is applied between the one surface side of the membrane substrate and the other surface side, so that the solvent component of the treatment liquid is transferred to one surface of the membrane substrate. To the other surface, the first hydrophilizing agent may be held on one surface of the membrane substrate, and the second hydrophilizing agent may be held inside the membrane substrate.

Specifically, for example, after spinning the membrane substrate, a treatment liquid containing at least a first hydrophilizing agent and a second hydrophilizing agent is passed through the inner space of the hollow fiber membrane, and the outer space of the hollow fiber membrane. The first hydrophilizing agent may be retained on the inner surface of the membrane substrate and the second hydrophilizing agent may be retained on the membrane substrate by depressurizing and / or pressurizing the treatment liquid.
Thus, if the said hydrophilic treatment is performed with respect to the membrane base material alone, the hydrophilizing agent can be easily attached and held on the inner surface and the inside of the film thickness without preparing a casing. Therefore, it is possible to efficiently produce a membrane base material that can quickly exhibit permeability.

  Next, the present invention will be described more specifically with reference to examples and comparative examples. The membrane substrates of the blood purifiers used in the examples and comparative examples are all hydrophobic membrane substrates made of polyester polymer alloy as a membrane material, and have the molecular weight fractionation characteristics shown in FIG. is there. Moreover, about the film | membrane base material in a comparative example, what surface-treated with glycerol (water-soluble film | membrane permeability maintenance agent) previously is used.

  (Example 1) By using the polyvinyl pyrrolidone aqueous solution (hydrophilic treatment liquid) in which the mixing ratio of K-90 and K-30 was set to 5: 5 and the treatment liquid concentration was set to 0.6 wt%, the treatment apparatus 19 was used. The membrane substrate of the blood purifier was hydrophilized.

  (Example 2) A membrane substrate of a blood purifier was treated by the treatment device 19 using a polyvinylpyrrolidone aqueous solution in which the mixing ratio of K-90 and K-30 was set to 7: 3 and the treatment solution concentration was set to 1.0 wt%. The material was hydrophilized.

  (Comparative Example 1) Using a polyvinylpyrrolidone aqueous solution containing only K-90 and having a treatment solution concentration of 0.5 wt%, the membrane substrate of the blood purifier was subjected to a hydrophilic treatment by the treatment device 19. .

  (Comparative example 2) The membrane base material of the blood purifier was hydrophilized by the above processing apparatus using a polyvinylpyrrolidone aqueous solution containing only K-30 and having a treatment solution concentration of 0.5 wt%.

(Evaluation)
In order to examine whether or not the fractionation performance has changed with respect to the blood purifier subjected to the hydrophilization treatment based on the above Examples and Comparative Examples, the amount of leakage of albumin (molecular weight: 66,000) (hollow fiber membrane) The amount of permeation through the The results are shown in Table 1.

  From the above results, it can be seen that in the blood purifier (Comparative Example 2) in which only K-30 is adhered to the hydrophobic membrane substrate, the amount of albumin leak is the largest among the Examples and Comparative Examples. And with the increase in the proportion of K-90 (Example 1 → Example 2), the leak amount of albumin also gradually decreased. Furthermore, albumin did not leak in the blood purifier (Comparative Example 1) hydrophilized with a hydrophilizing solution containing only K-90. From this, it can be seen that the amount of albumin leak can be changed by adjusting the amount of K-90 contained in the hydrophilization solution. That is, with respect to the hydrophilization treatment liquid supplied to the processing apparatus 19 without changing the state of the membrane substrate itself, specifically, the state of pores (pore diameter, length, etc.) formed in the membrane substrate. By adjusting the content of the high molecular weight hydrophilizing agent (K-90), the fractionation performance for a specific substance (albumin in this case) can be controlled, and the amount of the specific substance permeating through the hollow fiber membrane can be easily adjusted. be able to.

It is sectional drawing of the hollow fiber type blood purifier which cut and showed the middle of the longitudinal direction partially. (A) And (b) is a figure explaining the cut surface of the hollow fiber bundle in the edge part of a casing. It is a figure explaining the molecular weight fractionation characteristic of the membrane base material formed into a film. It is sectional drawing of a hollow fiber membrane. It is a schematic diagram explaining a processing apparatus. It is a schematic diagram explaining the pressure reduction process of a processing apparatus. It is a schematic diagram explaining the process liquid injection | pouring process and membrane-flowing process of a processing apparatus. It is a schematic diagram explaining the 1st purge process of a processing apparatus. It is a schematic diagram explaining the 2nd purge process of a processing apparatus.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Blood purifier 2 Casing 3 Hollow fiber bundle 4 Casing main body 5 Discharge side cap member 6 Injection side cap member 7 Diameter expansion part 8 Dialysate injection port 9 Dialysate discharge port 10 Sealing part 11 Sealing material 12 Hollow fiber membrane 13 Blood Ejection port 14 O-ring 15 Blood injection port 16 O-ring 17 Membrane substrate 18 Hydrophilizing agent 18a First hydrophilizing agent 18b Second hydrophilizing agent 19 Treatment device 20 Waste liquid reservoir 21 Gas supply source 22 Treatment liquid reservoir 23 Purification Equipment mounting part 43 Pressure reducing pump 44 Gas supply pipe 44a First gas supply branch pipe 44b Second gas supply branch pipe 45 Discharge pipe 45a First discharge branch pipe 45b Second discharge branch pipe 46 Treatment liquid supply pipe 46a First treatment liquid supply Pipe 46b Second treatment liquid supply pipe 47 Intake pipe 51 First on-off valve 52 Second on-off valve 53 Third on-off valve 55 Fifth on-off valve 60 First common pipe 61 Second Common pipe 62 7th on-off valve 63 8th on-off valve 64 9th on-off valve 65 10th on-off valve 71 11th on-off valve 72 12th on-off valve 73 Connection pipe 74 13th on-off valve 75 14th on-off valve

Claims (8)

A semipermeable membrane in which a hydrophilic agent is held on a hydrophobic membrane substrate is provided in the casing, and the semipermeable membrane allows the inside of the casing to pass through the first liquid passing space on one membrane surface side and the second on the other membrane surface side. In the liquid processing module, which is partitioned into a liquid passing space, and the casing is provided with a first port communicating with the first liquid passing space and a second port communicating with the second liquid passing space,
The hydrophilizing agent includes at least a first hydrophilizing agent and a second hydrophilizing agent, the first hydrophilizing agent and the second hydrophilizing agent being the same component as each other, and the second hydrophilic agent. The average molecular weight of the agent is set smaller than the average molecular weight of the first hydrophilizing agent,
For the casing loaded with the membrane substrate therein, the treatment liquid containing the hydrophilizing agent is injected into the first liquid passing space through the first port,
A pressure difference is generated between the first liquid passage space and the second liquid passage space, and the solvent component of the processing liquid is moved from the first liquid passage space to the second liquid passage space by the pressure difference. 1. A liquid treatment module, wherein a hydrophilizing agent is held on the surface of the membrane substrate on the first liquid passing space side, and a second hydrophilizing agent is held inside the membrane substrate. The hydrophilic agent is polyvinylpyrrolidone, and the average molecular weight of the first hydrophilic agent is 500 × 10 ³ The average molecular weight of the second hydrophilizing agent is 100 × 10 ³ The liquid processing module according to claim 1, wherein the hydrophobic membrane base material uses a polyester polymer alloy as a main membrane material.   The liquid processing module according to claim 1, wherein a mixing ratio of the first hydrophilizing agent and the second hydrophilizing agent is 1: 9 to 9: 1.   A semipermeable membrane in which a hydrophilic agent is held on a hydrophobic membrane substrate is provided in the casing, and the semipermeable membrane allows the inside of the casing to pass through the first liquid passing space on one membrane surface side and the second on the other membrane surface side. In the method for manufacturing a liquid processing module, the liquid processing module is provided with a first port communicating with the first liquid passing space and a second port communicating with the second liquid passing space.
  The hydrophilizing agent includes at least a first hydrophilizing agent and a second hydrophilizing agent, the first hydrophilizing agent and the second hydrophilizing agent being the same component as each other, and the second hydrophilic agent. The average molecular weight of the agent is set smaller than the average molecular weight of the first hydrophilizing agent,
  A treatment liquid injection step of injecting a treatment liquid containing the hydrophilizing agent into the first liquid passing space through a first port with respect to the casing in which the membrane substrate is loaded,
  A pressure difference is generated between the first liquid passage space and the second liquid passage space, and the solvent component of the processing liquid is moved from the first liquid passage space to the second liquid passage space by the pressure difference. A membrane-fluidizing step in which 1 hydrophilizing agent is held on the surface of the membrane base on the first liquid passing space side and the second hydrophilizing agent is held inside the membrane base;
A method for manufacturing a liquid processing module, which is manufactured through a process.   Performing a decompression step of decompressing at least the second fluid passage space before the treatment liquid injection step;
  The membrane liquid passing step is performed by a pressure difference between the second liquid passing space that has been reduced in pressure by the pressure reducing step and the first liquid passing space into which the processing liquid has been injected by the processing liquid injecting step. The manufacturing method of the liquid processing module of Claim 4.   The first port comprises a first injection port and a first discharge port,
  The second port is composed of a second injection port and a second discharge port,
  After the membrane liquid passing step, a first purge step for discharging the processing liquid remaining in the first liquid passing space and a second purge step for discharging the processing liquid remaining in the second liquid passing space are performed,
  In the first purge step, the first injection port and the first discharge port are opened, and the gas is introduced into the first liquid passing space in a state where the second injection port and the second discharge port are closed,
  In the second purge step, the second injection port and the second discharge port are opened, and a gas is introduced into the second liquid passing space in a state where the first injection port and the first discharge port are closed. The method for producing a liquid processing module according to claim 5.   The hydrophilic agent is polyvinylpyrrolidone, and the average molecular weight of the first hydrophilic agent is 500 × 10 ³ The average molecular weight of the second hydrophilizing agent is 100 × 10 ³ The method for producing a liquid processing module according to any one of claims 4 to 6, wherein the hydrophobic membrane base material uses a polyester polymer alloy as a main membrane material.   8. The liquid processing module according to claim 4, wherein a mixing ratio of the first hydrophilizing agent and the second hydrophilizing agent is 1: 9 to 9: 1. Method.

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