JPH01259870A - Hollow fiber membrane type liquid treatment device - Google Patents

Abstract

PURPOSE:To prevent the generation of a thrombus, the generation of clogging and residual blood and an increase in the pressure loss of a dialyzer caused by the deterioration of the flow of blood at the part of a partition wall, by bringing the part, which is in contact with the partition wall, of a hollow fiber membrane to a part hard to swell at the time of the contact with moisture. CONSTITUTION:A hydrophobic resin 4 is present on the inner and end surfaces of the hollow part of a dialyzing hollow fiber membrane 3 at the part in contact with a partition wall as well as present at a part in a hollow yarn at that part, and the inner surface at that part and the end surface of the hollow fiber membrane form hydrophobic surfaces and the hollow fiber membrane at the part in contact with the partition wall 5 becomes hard to absorb moisture. The inner surface of the hollow fiber membrane in contact with the part of the partition wall 5 is brought to the same state. Even when the hollow fiber membrane 3 at that part is in contact with a moisture-containing liquid, said hollow fiber membrane is brought to a state absorbing substantially no moisture and the expansion of the thickness of the hollow fiber membrane 3 is suppressed. As the substance contained in the hollow fiber membrane 3 at the part in contact with the partition wall or applied to the inner and end surfaces of the hollow part of the membrane, for example, silicon can be used.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a hollow fiber membrane type liquid treatment device,
For example, the present invention relates to hollow fiber model artificial dialyzers, plasma separators, etc., which are used for patients with renal failure, etc., to remove harmful substances and water from blood, and to adjust electrolytes.

[Prior Art] Conventionally, a hollow fiber membrane type artificial dialysis machine, for example, has been used as a hollow fiber membrane type liquid treatment device, and its boat structure consists of a cylinder having an inlet and an outlet for dialysate. A hollow fiber membrane bundle consisting of a large number of hollow fiber membranes for dialysis is inserted into a cylindrical housing, and both ends of the hollow fiber membrane bundle are made liquid-tight by partition walls formed with a potting agent at both ends of the cylindrical housing. A cap-shaped ladder is attached to the outside of this partition wall to form a blood inlet and a blood outlet. As the hollow fiber membrane for dialysis, a hydrophilic membrane such as regenerated cellulose such as cellulose acetate or cuprammonium cellulose is used, and as a botting agent, polyurethane or the like is used. Also, a plasma separation device having a similar configuration is used.

[Problems to be Solved by the Invention] FIGS. 6 and 7 show enlarged cross-sectional views of the partition wall of a conventional hollow fiber membrane dialyzer. FIG. 6 shows the dry state of the hollow fiber membrane 22 for dialysis, that is, the state before use of the dialyzer.

In this state, the hollow fiber membrane 22 for dialysis does not have any part where the inner diameter changes extremely, including the part that is in contact with (buried in) the partition wall 20, and the shape of the hollow fiber membrane when manufactured is The overall inner diameter is almost uniform.

Before the blood is circulated in the dialyzer, the part where the blood flows into the dialyzer (the inside of the hollow fiber membrane) is brimmed with physiological saline or the like to replace the air inside with liquid. . Further, the dialysate side (outside the hollow fiber membrane) is filled with dialysate.

In this state, the hollow fiber membrane 22 for dialysis becomes wet.

FIG. 7 shows an enlarged sectional view of the partition wall when the hollow fiber membrane 22 is in a wet state. Since the hollow fiber membrane 22 for dialysis is hydrophilic,
When it comes into contact with a liquid containing water, it absorbs water and swells, increasing its thickness.

In the portions not in contact with the partition wall 20, changes in wall thickness manifest as changes in the outer diameter, and the inner diameter hardly changes. On the other hand, in the part that is in contact with (buried in) the partition wall 20, the partition wall 2
Since the outside is fixed by 0, the outside diameter cannot be changed, and an increase in wall thickness appears as a decrease in the inside diameter. Therefore, the inner diameter of the hollow fiber membrane 22 becomes narrow at the portion where it is in contact with the partition wall 20, resulting in poor blood flow in the partition wall 20 portion, which may cause thrombus formation, clogging, and residual blood. , and may also lead to increased pressure loss in the dialyzer. This problem also occurred in plasma separators.

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to solve the above-mentioned problems, so that even when a hollow fiber membrane in a liquid treatment device, such as a hollow fiber membrane for dialysis, comes into contact with a liquid containing water, it does not come into contact with the partition wall portion. The inner diameter of the hollow fiber membrane does not change, and there is no risk of poor blood flow at the septum, causing thrombus formation, clogging, residual blood, or increased pressure loss in the dialyzer. An object of the present invention is to provide a hollow fiber type liquid processing device such as a thread membrane type artificial dialyzer.

Means for Solving Problem L] The object of the present invention described above is achieved by a housing, a hollow fiber membrane bundle consisting of a large number of hollow fiber membranes for liquid treatment inserted into the housing, and the hollow fibers. Connect both ends of the membrane bundle to No. 1 above.
a partition wall liquid-tightly fixed to the face end of the housing; and a first partition wall provided near both ends of the housing and communicating with a space formed by the outer surface of the hollow fiber membrane, the inner surface of the housing, and the partition wall. A hollow fiber model liquid processor having a liquid inlet and an outlet, and a second liquid inlet and an outlet respectively attached to both ends of the housing, the hollow fiber membrane being in contact with the partition wall. This is a hollow fiber membrane type liquid treatment device that has a part that does not swell easily when it comes into contact with moisture.

The hollow fiber membrane is, for example, a hollow fiber membrane for dialysis. Further, a portion of the hollow fiber membrane that comes into contact with the partition wall is
For example, it is treated with a substance having a reactive group that reacts with a polar group possessed by the hollow fiber membrane or a polar group possessed by a substance contained in the hollow fiber membrane. Further, the polar group possessed by the hollow fiber membrane or the polar group possessed by the substance contained in the hollow fiber or membrane is, for example, any one of a hydroxyl group, an amino group, and a carboxylic group.

Further, the reactive group is preferably any one of an isocyanate group, an epoxy group, a thiocyanate group, an acid chloride group, and an aldehyde group.

Further, a device for achieving the above object includes a housing, a hollow fiber membrane bundle consisting of a large number of hollow fiber membranes for liquid treatment inserted into the housing, and both ends of the hollow fiber membrane bundle being connected to both ends of the housing. a partition wall liquid-tightly fixed to the housing, and a first liquid inlet and a first liquid flow inlet provided near both ends of the housing and communicating with a space formed by the outer surface of the hollow fiber membrane, the inner surface of the housing, and the partition wall. A hollow fiber membrane type liquid processor having an outlet and second liquid inlets and outlets respectively attached to both ends of the housing, wherein the hollow fiber membrane in the portion that contacts the partition wall is in contact with the partition wall. This is a hollow fiber membrane type liquid treatment device that has a part that is substantially less likely to absorb moisture than other parts that do not come into contact with it.

Further, a device that achieves the above object includes a housing, a hollow fiber membrane bundle consisting of a large number of hollow fiber membranes for dialysis inserted into the housing, and both ends of the hollow fiber membrane bundle being connected to both ends of the housing. a partition wall to be fixed in a fluid-tight manner; and a dialysate inlet and a dialysis outlet provided near both ends of the housing and communicating with a space formed by the outer surface of the hollow fiber membrane, the inner surface of the housing, and the partition wall. , a hollow fiber membrane type artificial dialyzer having a blood inlet and a blood outlet respectively attached to both ends of the housing,
In a hollow fiber membrane type artificial dialysis machine, the portion of the hollow fiber membrane for dialysis that contacts the partition wall is a portion that is substantially less likely to absorb water than other portions that do not contact the partition wall.

Moreover, the hollow fiber membrane for dialysis is, for example, a hydrophilic hollow fiber membrane for dialysis. Furthermore, the hollow fiber membrane for dialysis in the portion that comes into contact with the partition wall has, for example, a hydrophobic surface on the inner surface of the hollow portion of the portion and the end face located on the partition wall surface.

Therefore, the hollow fiber membrane type liquid treatment device of the present invention will be explained using an embodiment shown in the drawings.

FIG. 1 is a partial sectional view of an embodiment of the liquid treatment device of the present invention applied to a hollow fiber membrane type artificial dialysis machine, and FIG. It is an enlarged sectional view of the partition part of a container.

This hollow fiber membrane type artificial dialyzer 1 includes a housing 2, a hollow fiber membrane bundle consisting of a large number of dialysis hollow fiber membranes 3 inserted into a housing 2, and both ends of the hollow fiber membrane bundle being connected to the housing 2.
partition walls 5 and 6 fixed liquid-tightly to both ends of the housing 2;
A dialysate inlet 11 and a dialysate outlet 12 are provided near both ends of the membrane and communicate with the space formed by the outer surface of the hollow fiber membrane 3, the inner surface of the housing 2, and the partition walls 5 and 6.
It has a blood inflow lower and a blood outflow port 8 attached to both ends of the housing 2, respectively.Furthermore, the hollow fiber membrane 3 for dialysis in the portion that comes into contact with the partition walls 5, 6 is connected to the partition walls 5, 6. Compared to other parts that do not come into contact with the water, it is a part that is substantially less likely to absorb moisture.

The hollow fiber membrane 3 for dialysis used in the hollow fiber membrane type artificial dialyzer 1 of the present invention is made of regenerated cellulose such as cellulose acetate, cuprammonium cellulose, cellulose derivatives, ethylene-
It is a hollow fiber membrane for dialysis having hydrophilic properties formed of vinyl alcohol copolymer, acrylonitrile copolymer, etc., and has a wall thickness of 5 to 35μ, preferably 10 to 20μ, and an outer diameter of 50 to 500μ, preferably. is 100-300
μm, and has a hollow portion extending through the entire length.

As a hollow fiber membrane type artificial dialyzer 1, FIG. 1 shows an assembled state of a hollow fiber membrane type artificial dialyzer which is one embodiment thereof.

This hollow fiber membrane type artificial dialyzer 1 includes a cylindrical housing 2 and 6,000 to 50,000 dialysis hollow fiber membranes 3 spread throughout the housing 2. The hollow fiber membrane 3 for dialysis is fluid-tightly fixed to the end of the housing 2 by means of partition walls 5.degree.6, with the openings at both ends thereof not being closed. Through these partition walls 5 and 6, the inside of the housing 2 is divided into a dialysate chamber formed by the outer wall of the hollow fiber membrane 3 for dialysis, the inner wall of the nousing 2, and the partition wall 5.6, and the inside of the hollow fiber membrane 3. It is divided into blood chambers that are formed.

The cylindrical housing 2 is made of polycarbonate, acrylonitrile-styrene copolymer, etc., and is cylindrical, preferably cylindrical.
A dialysate inlet 11 is provided near one end of the dialysate, and a dialysate outlet 12 is provided near the other end.

The partition wall 5.6 is formed of a botting agent such as polyurethane or silicone rubber.

Further, on the outside of the partition wall 5, a cap-shaped flow path forming member 9 having a blood inflow lower part and an annular convex part is fixed by a screw ring 13, and on the outside of the partition wall 6, a blood outflow port 8 and an annular convex part are fixed. Cap-shaped channel forming member 1G having a portion
is fixed by a screw ring 14. The convex part of the flow path forming member 9.10 has four annular parts, and as shown in FIG. 2, the concave part is provided with an O-ring 16 made of silicone rubber or the like. and
This O-ring is in contact with the partition wall, and the flow path forming member 9
, 10 are liquid-tightly fixed to the partition walls 5, 6.

Further, in the above explanation, the threaded ring is used, but the flow path forming member is not limited to this, and the flow path forming member may be directly fused to the housing using high frequency waves, ultrasonic waves, etc., or adhesives etc. may be used. It may also be glued.

Furthermore, as shown in FIG. 2, the hydrophobic resin 4 is present on the inner surface and end surface of the hollow part of the hollow fiber membrane 3 for dialysis in the part that contacts the partition wall 5, and also in a part of the inside of the hollow fiber in that part. The inner surface of that portion and the end surface of the hollow fiber membrane form a hydrophobic surface, so that the portion of the hollow fiber membrane that contacts the partition wall 5 is difficult to absorb moisture. In addition, the partition wall 6
The same applies to the inner surface of the hollow fiber membrane that contacts the part. In this way, by making the hydrophobic resin exist in the hollow fiber membrane 3 in the portion that contacts the partition wall, even if the hollow fiber membrane 3 in that portion comes into contact with a water-containing liquid, it is possible to prevent the hollow fiber membrane 3 from absorbing water substantially. This suppresses expansion of the wall thickness of the hollow fiber membrane 3.

The hydrophobic resin may be present, for example, by coating, and the hydrophobic resin may be present only on the hollow fiber surface of the coated portion, or may further flow into the entire or part of the hollow fiber. You can leave it there. The hydrophobic resin 4 is preferably also coated on the entire partition wall surface. This is because when the partition wall surface is sliced at the botting agent portion to form the partition wall surface, the surface may be rough, and the roughness of the partition wall surface can be smoothed. The thickness of the coating of the hydrophobic resin 4 is 0.01 to 100 μm, preferably 0.1 to 10 μm. Moreover, it is preferable that a part of the hydrophobic resin flows into the inside of the hollow fiber membrane.

Furthermore, the hydrophobic resin 4 is preferably solidified, and more preferably, a portion of the hydrophobic resin has flowed into the hollow fiber membrane and is further solidified. In this way, it is possible to reliably suppress the expansion of the membrane thickness of the hollow fiber membrane, and also to prevent the hydrophobic resin from flowing into the blood during blood circulation and from easily peeling off the hydrophobic resin. It is.

In addition, as a method other than coating the portion of the hollow fiber membrane 3 for dialysis that contacts the partition wall 5 with the hydrophobic resin 4,
The hollow fiber membrane 3 in this area contains a hydrophobic substance such as a hydrophobic resin so that even if the hollow fiber membrane in that area comes into contact with a liquid containing water, it does not substantially absorb water. Good too.

The material contained in the hollow fiber membrane 3 in the portion that contacts the partition wall or coated on the inner surface and end surface of the hollow portion is highly biocompatible, that is, has antithrombotic properties.
Preferably, the material is hydrophobic, such as silicone, urethane resin such as polyurethane, or fluororesin. Examples of the silicone include dimethyl silicone oil, methylphenyl silicone oil, methylchlorophenyl silicone oil, branched dimethyl silicone oil, two-component RTV silicone rubber (for example, a polymer of vinyl methyl siloxane and methyl hydrogen siloxane), 1 Liquid type RTV silicone rubbers or mixtures of these silicone rubbers and the above-mentioned silicone oils can be suitably used. Particularly preferred is a reactive modified silicone oil.

As the fluororesin, polytetrafluoroethylene, polytrifluoroethylene, perfluoroacrylate, etc. can be suitably used.

Incidentally, it is necessary that the above-mentioned substance be contained or coated only on the portion of the hollow fiber membrane that substantially contacts the partition wall. In other words, only the part that is in contact with the partition wall,
In addition, it is sufficient that the substance slightly exceeds the partition wall, but if the above substance is contained or coated far beyond the partition wall, the hollow fiber membrane in that area becomes hydrophobic.
This is not preferable because it forms a part that does not function as a dialysis membrane.

Further, the hollow fiber membrane type liquid treatment device of the present invention includes a housing, a hollow fiber membrane bundle consisting of a large number of hollow fiber membranes for liquid treatment inserted into the housing, and both ends of the hollow fiber membrane bundle inserted into the housing. partition walls liquid-tightly fixed to both ends of the housing; and a first liquid provided near both ends of the housing and communicating with a space formed by the outer surface of the hollow fiber membrane, the inner surface of the housing, and the partition walls. A hollow fiber membrane type liquid processor having an inlet and an outlet, and a second liquid inlet and an outlet respectively attached to both ends of the housing, the hollow fiber membrane being in contact with the partition wall. This is a part that does not easily swell when it comes into contact with moisture.

In particular, in order to make the portion of the hollow fiber membrane that contacts the partition wall 5 difficult to swell when it comes into contact with moisture, the portion of the hollow fiber membrane 3 that contacts the partition walls 5 and 6 is The treatment may be performed using a substance having a reactive group that reacts with a group or a polar group of a substance contained in the hollow fiber membrane 3.

FIG. 3 shows an enlarged sectional view of the partition wall portion of the hollow fiber membrane type liquid treatment device 1 in a state treated with the above substance.

Possible polar groups of the hollow fiber membrane 3 or of the substance contained in the hollow fiber membrane 3 include hydroxyl group, amino group, carboxyl group, etc. Hollow fiber membranes for liquid treatment include cellulose acetate, Regenerated cellulose such as cuprammonium cellulose, cellulose derivatives, ethylene-
Hollow fiber membranes for dialysis and hollow fiber membranes for plasma separation, such as vinyl alcohol copolymers and acrylonitrile copolymers, are suitable. Alternatively, water, glycerin, etc. can be considered as substances contained in the hollow fiber membrane.

Further, as the reactive group possessed by the substance used in the treatment of the hollow fiber membrane, an isocyanate group, an epoxy group, a thiocyanate group, an acid chloride group, an aldehyde group, etc. can be considered, and an epoxy group, an isocyanate group, etc. are preferable. Particularly preferred are substances having highly active isocyanate groups, such as diphenylmethane diisocyanate,
2,4-tolylene diisocyanate and carbodiimide-modified diphenylmethane diisocyanate are preferred. Further, as the substance having an epoxy group, epichlorohydrin, 1,4-butanediol, diglycidyl ether, etc. can be used.

Then, by treating the portion of the hollow fiber membrane that comes into contact with the partition wall with a substance having a reactive group as described above,
The reactive group of the above substance and the polar group of the hollow fiber membrane or the polar group of the substance contained in the hollow fiber membrane react to form a three-dimensional matrix, so the structure of the hollow fiber membrane in the treated area is immobilized, and the hollow fiber membrane 3 of that part is
Even if the hollow fiber membrane 3 comes into contact with a water-containing liquid, the hollow fiber membrane 3 is prevented from absorbing water substantially, and the expansion of the wall thickness of the hollow fiber membrane 3 is suppressed.

Further, it is preferable to flow the substance having the above-mentioned reactive group into the inside of the hollow fiber membrane and cause the reaction to reach the inside of the hollow fiber membrane. The molecular weight is 30.000 or less, more preferably 1.000 or less.

Furthermore, it is preferable that the above-mentioned substance is used after being dissolved in a solvent to reduce the viscosity.
The flow into the inside of the hollow fiber membrane is ensured, making the treatment easier and more reliable. The solvent varies depending on the substance having a reactive group used, but any solvent that has low reactivity with the above substance and dissolves the above substance may be used, such as acetone, chloroform, methyl ethyl ketone, benzene, ethyl acetate, dioxane, etc. , dimethyl sulfoxide, dimethyl formamide, etc. can be suitably used. By using a solvent whose viscosity has been made low by the above-mentioned solvent, the swelling effect of the hollow fiber membrane during treatment can be utilized, and the treatment effect can be made more reliable. The processing time varies depending on the temperature, solvent, processing agent, etc., but at room temperature, when using benzene:dimethyl sulfoxide = 9:1 system as the solvent, from 5 seconds to 30 minutes,
More preferably, the time is from 1 minute to 20 minutes, and when a 9:1 chloroform:dimethylsulfoxide system is used as the solvent, the time is from 5 seconds to 2 hours, preferably about 10 seconds to 1 hour.

The hollow fiber membrane dialyzer 1 is then sterilized before use.

For sterilization, known methods such as ethylene oxide gas sterilization and autoclave sterilization are used. When performing autoclave sterilization, the inside of the dialyzer (dialysate chamber and blood chamber) is filled with a liquid that is harmless to living organisms (e.g., physiological saline, sterile water), and the openings (dialysate inlet and outlet,
This is done by sterilizing in an autoclave while the blood inlet and blood outlet are sealed using an elastic member. In the hollow fiber membrane dialyzer of the present invention, even when filled with liquid for autoclave sterilization, the hollow fiber membrane for dialysis in the portion that contacts the partition wall contains a hydrophobic substance or is coated with a hydrophobic substance. In addition, the part of the hollow fiber membrane that comes into contact with the partition wall has a polar group that the hollow fiber membrane for dialysis has,
or treated with a substance having a reactive group that reacts with the polar group of the substance contained in the hollow fiber membrane for dialysis,
The inner surface of that part is a part that is practically difficult to absorb water, so even if the hollow fiber membrane in that part comes into contact with liquid, it will not be impregnated with water, and therefore the wall thickness of the hollow fiber membrane will not expand. Therefore, it is possible to prevent the inner diameter of the partition wall portion of the hollow fiber membrane from decreasing regardless of whether before or after liquid filling and autoclave sterilization.

In the above explanation, the hollow fiber membrane type liquid treatment device of the present invention was explained using an example in which it was applied to an artificial dialysis machine. can.

Next, an example of a method for manufacturing the hollow fiber membrane type artificial dialyzer of the present invention will be briefly described.

First, a cylindrical housing having a dialysate inlet and a dialysate outlet on its side wall is created, and a hollow fiber membrane bundle consisting of a large number of hollow fiber membrane bundles for dialysis is inserted into the housing. After the hollow fiber membranes at both ends of the hollow fiber membrane bundle are uniformly dispersed, a container filled with a filler is fitted onto both ends of the hollow fiber membrane bundle, and this container is then placed at the end of the housing. be fixed to the section. Furthermore, the potting agent is centrifugally injected from the dialysate inlet and dialysate outlet of the housing, each end of the hollow fiber membrane bundle is fixed to the housing, and after removing the container, the potting agent portion is sliced. , forming respective partition walls. When using a hydrophobic substance, such as a liquid hydrophobic resin, or when the hydrophobic resin is not liquid, or when the hydrophobic resin alone has a high viscosity, it is necessary to dissolve the hydrophobic resin and use a hollow fiber membrane for dialysis. The above partition wall portion is immersed in a hydrophobic resin liquid dissolved in a solvent that does not easily dissolve the botting agent (it may be a solvent that slightly dissolves the hollow fiber membrane), and the inside of the hollow fiber membrane at the partition wall portion is soaked. Fill with hydrophobic resin liquid. In addition, if the hydrophobic resin liquid does not flow into the hollow fiber membrane by dipping alone, block the dialysate inlet and outlet, attach a suction device to the opposite partition wall, and drain the inside of the hollow fiber membrane. It may also be caused to flow in by suction.

Then, it is pulled up from the hydrophobic resin liquid, a gas supply device is attached to the partition wall on the opposite side, and gas (e.g., air) is injected into the inside of the hollow fiber membrane, and it adheres to the inner surface of the end of the hollow fiber membrane. Remove excess hydrophobic resin liquid. Note that a device having both functions may be used as the gas supply device and the suction device. If the hydrophobic resin liquid does not adhere to the hollow fiber membrane sufficiently in the above one operation, perform the above operation multiple times as appropriate.
Then, dry the area to which the hydrophobic resin liquid has been applied,
A hydrophobic resin is present in the hollow fiber membrane. If sufficient coating cannot be achieved with one coating of the hydrophobic resin, the above operation is repeated multiple times.

When gas is injected into the inside of the hollow fiber membrane to remove excess hydrophobic resin, some of the removed resin may adhere to the end surfaces of the partition walls, causing the resin to adhere unevenly to the end surfaces. It is preferable to remove it using a smooth plastic sheet or rubber sheet.
1. Then, by performing the same operation on the opposite partition wall, the inner surface of the hollow fiber membrane of each partition wall is coated with hydrophobic resin. After that, a flow path is formed on the outside of each partition wall. By attaching the members, the hollow fiber membrane type artificial dialyzer of the present invention can be created.

In addition, the method is not limited to the above method. For example, a hollow fiber membrane bundle is created by bundling hollow fiber membranes for dialysis, and the ends of the hollow fiber membrane bundle are soaked in a treatment solution of a hydrophobic substance or a substance having a reactive group. The hollow fiber membrane bundle is immersed in water, pulled out of the treatment solution, air is flowed through the end opposite to the treated side of the hollow fiber membrane bundle, the treatment solution inside the hollow fiber membrane is removed, and the hollow fiber membrane is washed with a cleaning solvent. After treating the opposite end of the membrane bundle in the same way and drying the hollow fiber membrane bundle, the hollow fiber membrane bundle subjected to the above treatment was inserted into the housing, and the end was treated with polyurethane as a potting agent. It may also be manufactured by fixing it to form a partition wall.

Next, examples of the present invention will be described.

:Example] :Example 1) Length 198xm, end inner diameter 44x*, middle inner diameter 32z
Z polycarbonate housing with an inner diameter of approximately 200μ
L Approximately 7,100 hollow fiber membranes for dialysis made of copper ammonia cellulose and having a wall thickness of approximately 12 μm were inserted, and their ends were fixed using polyurethane as a botting agent to form a partition wall. The longest part of the bulkhead (the part that contacts the housing)
The length was 15ix.

Then, reactive silicone (manufactured by Toshiba Silicone Corporation, NCT-91150%, isopropyl alcohol 10%, toluene 40%) was used as the hydrophobic resin, and trifluoroethane (manufactured by Mitsui Chlorochemical Company, Ltd., trade name: Freon) was used as the solvent. TF) at a concentration of 5% by weight.
A silicone solution was prepared. Pour this silicone solution into an IH container, and place approximately 15 g from the end of the partition into the container.
After immersing the membrane for 15 minutes and pulling it up, compressed air was flowed inside the hollow fiber membrane for 30 minutes at a flow rate of 30Q,/11in, using a gas supply device attached to the partition wall on the opposite side.
Excess silicone solution adhering to the inner surface of the end of the hollow fiber membrane was removed. Then, the same operation was performed on the partition wall portion on the opposite side. Thereafter, drying was carried out day and night at room temperature. After repeating this process three times, by attaching a polypropylene cap-shaped flow path forming member to the outside of each partition wall, a hollow fiber membrane type artificial dialyzer of the present invention having the structure shown in FIG. It was created.

The membrane area of this hollow fiber membrane dialyzer was approximately 0.81.

[Comparative Example 1] Length 198 cm, end inner diameter 44 mm, middle inner diameter 32 shoulder π
Polycarbonate housing with an inner diameter of approximately 200 μy
i. Wall thickness: approximately 12 μX [Approximately 7,100 hollow fiber membranes made of ammonia cellulose for dialysis were inserted, and their ends were fixed using polyurethane as a potting agent to form a partition wall. The longest part of the bulkhead (the part that contacts the housing)
The length was 15xx. A hollow fiber membrane type artificial dialyzer was created by attaching a flow path forming member made of polypropylene to the outside of each partition wall and used as a comparative example. The membrane area of this hollow fiber membrane dialyzer is approximately 0.8
It was "m".

(Example 2) Length 198xm, end inner diameter 44xm, middle inner diameter 321
1 polycarbonate housing with an inner diameter of approximately 200μ
About 7,100 cuprammonium cellulose dialysis hollow fiber membranes having a wall thickness of about x2 μM were inserted, and their ends were fixed using polyurethane as a botting agent to form a partition wall. The longest part of the bulkhead (the part that contacts the housing)
The length was 15xm. As a substance having a reactive group, diphenylmethane diisocyanate (containing castor oil, TP-0001, manufactured by Nippon Polyurethane Industries Co., Ltd.)
A treatment solution containing 20% of the above substance was prepared using acetone as a solvent. As the hollow fiber membrane, a hollow fiber membrane bundle was prepared by bundling approximately 7,100 hollow fiber membranes for dialysis made of copper ammonium cellulose, and one end of this hollow fiber membrane bundle was stirred with a magnetic stirrer. 2 from the end of
c111 was immersed in the above treatment solution. After immersing it at room temperature for 20 minutes, it was pulled out of the treatment solution and 1.0K g/c! was applied from the opposite end of the hollow fiber membrane bundle to the treated side. Air was flowed under 2 pressures to remove the processing solution inside the hollow fiber membrane.

Thereafter, methylene chloride was washed and solvent washing was performed.

For cleaning, the treated end of the hollow fiber membrane bundle is immersed in the cleaning solvent, and after confirming that the cleaning solvent has been sucked up inside the treated part of the hollow fibers, it is immediately pulled out of the cleaning solvent and the hollow fibers are removed. From the opposite end of the membrane bundle to the treated side, 1.0 K
The cleaning solution inside the hollow fiber membrane is removed by flowing air at a pressure of g/cm'. This was repeated three times while changing the washing solution.

After the opposite end of the hollow fiber membrane bundle was treated in the same manner, the hollow fiber membrane bundle was dried in a 60°C oven. Then, the hollow fiber membrane bundle subjected to the above treatment was inserted into a polycarbonate housing having a shape as shown in FIG. It was fixed using polyurethane to form a partition wall. The length of the longest part of the septum was approximately 151 shoulders. Further, the length of the hollow fiber membrane in the portion treated with the above substance was approximately 4 cm. A hollow fiber membrane type artificial dialyzer was then produced by attaching a flow path forming member made of polypropylene to the outside of each partition wall. The membrane surface area of this hollow fiber membrane type artificial dialyzer was approximately 0.8 m'.

(Example 3) As a treatment solution, carbodiimide-modified methyl diisocyanate was used as a substance having a reactive group, and benzene/
It was produced in the same manner as in Example 2, except that dimethyl sulfoxide (benzene/dimethyl sulfoxide-9:l) was used as a solvent and a treatment solution containing 10% of the above substance was used.

(Example 4) As a treatment solution, carbodiimide-modified methyl diisocyanate was used as a substance having a reactive group, chloroform/dimethyl sulfoxide (chloroform/dimethyl sulfoxide - 9:1) was used as a solvent, and 10% of the above substance was used.
It was produced in the same manner as in Example 2, except that the containing treatment solution was used.

(Example 5) Length 198cm, end inner diameter 44mm, middle inner diameter 32ux
Polycarbonate housing with inner diameter of approximately 200μm
Approximately 7,100 hollow fiber membranes for dialysis made of copper ammonia cellulose having a wall thickness of approximately +2 μl were inserted, and the ends thereof were fixed using polyurethane as a botting agent to form a partition wall. The longest part of the bulkhead (the part that contacts the housing)
The length of is 15jlj! Met.

A treatment solution containing io% of the above substance was prepared using diphenylmethane diisocyanate as a substance having a reactive group and a mixed solution of dimethyl sulfoxide/dioxane/freon=2:3:5 as a solvent. This treatment solution is poured into a glass petri dish to a depth of about 5zx, and the module is immersed vertically in this glass petri dish for 1 minute and then pulled out.The treatment solution inside the hollow fibers is removed and the remaining on the partition wall surface is removed. The treated solution was wiped off, and the same operation was performed on the partition wall on the opposite side. Thereafter, it was dried overnight at room temperature.

After drying, a polypropylene cap-shaped channel forming member is attached to the outside of each partition wall, and dioxane/water =
A mixed solution of 3 Nia was used as a cleaning liquid and was circulated for 30 minutes, and then water was circulated for 10 minutes to clean the inside of the fiber.

(Example 6) Using diphenylmethane diincyanate as a substance having a reactive group, dimethyl sulfoxide/benzene-
A treatment solution containing 10% of the above substance was prepared using a 1:9 mixed solution as a solvent.

As the hollow fiber membrane, a hollow fiber membrane bundle was prepared by bundling approximately 7,100 hollow fiber membranes for dialysis made of copper ammonium cellulose, and one end of the hollow fiber membrane bundle was stirred by magnetic starcy. About 2 cm from the end was immersed in the above treatment solution. After immersing it at room temperature for 20 minutes, it was pulled out of the treatment solution and 1.0
Air was flowed at a pressure of K g/cx' to remove the processing solution inside the hollow fiber membrane. Then, using methylene chloride as a cleaning solvent, the treated end of the hollow fiber membrane bundle is immersed in the cleaning solvent,
After confirming that the cleaning solvent has been sucked up into the hollow fibers of the treated part, immediately pull it out of the cleaning solvent and apply 1.0 K 9 from the opposite end of the hollow fiber membrane bundle to the treated side.
The cleaning solution inside the hollow fiber membrane was removed by flowing air at a pressure of 7 cm''. This was repeated three times while exchanging the cleaning solution.

After the opposite end of the hollow fiber membrane bundle was treated in the same manner, the hollow fiber membrane bundle was dried in a 60'C oven overnight.

Then, the hollow fiber membrane bundle subjected to the above treatment is inserted into a polycarbonate housing having a shape as shown in FIG. It was fixed using polyurethane as a coating agent to form partition walls. The length of the longest part of the septum was approximately 15xz. Further, the length of the hollow fiber membrane in the portion treated with the above substance was approximately 4 cm.

A hollow fiber membrane type artificial dialyzer was then produced by attaching a flow path forming member made of polypropylene to the outside of each partition wall. The membrane area of this hollow fiber membrane type artificial dialyzer was approximately 0.8 m''.

(Example 7) As a treatment solution, diphenylmethane diisocyanate was used as a reactive substance, a mixed solution of dimethyl sulfoxide/dioxane/freon-2:4:4 was used as a solvent, and a treatment solution containing 10% of the above substance was used. A sample was prepared in the same manner as in Example 1, except that 5% of triethanolamine was contained as an additive.

(Comparative example 2) Length 198xm, end inner diameter 44rxx, middle inner diameter 32
About 7,100 hollow fiber membranes for dialysis made of copper ammonium cellulose were inserted into the polycarbonate housing of ZX, and the ends were fixed using polyurethane as a potting agent to form a partition wall. The length of the longest part of the bulkhead is approximately 1
It was 5xm. A hollow fiber membrane type artificial dialyzer was prepared as a comparative example by attaching a flow path forming member made of polypropylene to the outside of each partition wall. The membrane surface area of this hollow fiber membrane type artificial dialyzer was approximately 0.81''.

[Experiment 1] Two hollow fiber membrane type artificial dialyzers of Example 1 and Comparative Example 1 were each produced. Using the dialyzers of Example 1 and Comparative Example 1, one dry dialyzer and one wet dialyzer were prepared. Then, the partition wall portion of each dialyzer in a dry state was sliced to a thickness of about 5xx, and the inner diameter and wall thickness of the hollow fiber membrane when dry were measured at 40 locations.

Furthermore, the moist state is created by filling droplets of distilled water inside the dialyzer, performing autoclave sterilization at 121°C for 190 minutes, and discharging the distilled water. The thickness of the partition wall of the dialyzer is approximately F.
)) The inner diameter and wall thickness of the hollow fiber membrane at 18 min. were measured at 40 locations, respectively, by tx slicing.

For measurement, a universal projector UP- manufactured by Olympus Corporation was used.
350 was used. The results were as shown in Table 1.

Table 1 [Experiment 2] The partition walls of the hollow fiber membrane type artificial dialyzers of Example 1 and Comparative Example 1 were sliced to a thickness of approximately 513 mm. A staining test was conducted using them. As a dye, a basic dye (toluidine blue, Mw: 305
．． 8) to prepare a 0.04 w/v% toluidine blue solution and slice it at the partition wall part above.
The sample was immersed for a minute, then thoroughly washed with water, and observed using a universal projector UP-350 manufactured by Olympus Corporation. In the case where the partition wall portion of the dialyzer of Comparative Example 1 was sliced, the entire hollow fiber membrane was dyed blue, but in the case where the partition wall portion of the dialyzer of Example 1 was sliced, the entire surface of the hollow fiber membrane (sliced) was dyed blue. It was also confirmed that the silicone had flowed into the inside of the hollow fiber membrane.

[Experiment 3] The partition wall portion of the hollow fiber membrane type artificial dialyzer of Example 1 and Comparative Example 1 was sliced to a thickness of about 5 zm, and
The surface condition of the end face of the partition wall was examined using a scanning electron microscope (JSM).
803. (manufactured by JEOL Ltd.).

As a result, in Comparative Example 1, roughness due to slicing was observed on the partition wall end face, whereas in Example 1, the surface was smooth. In addition, in Example 1, no uneven silicone or roundness at the ends of the hollow fiber membrane was observed.

[Experiment 4] Two hollow fiber membrane type artificial dialyzers of Examples 2 to 7 and Comparative Example 2 were each produced. And Example 2, 3.4
Using the dialyzer of Comparative Example 2, one dry dialyzer and one wet dialyzer were prepared. Then, the partition wall portion of each dialyzer in the dry state was sliced to a thickness of about 5xx, and the inner diameter and wall thickness of the hollow fiber membrane in the dry state were measured at 30 locations. Furthermore, a wet version is created by filling droplets of distilled water inside the dialyzer, sterilizing it in an autoclave for 190 minutes at 12 Pcs, and then discharging the distilled water. The partition wall portion of each dialyzer was sliced to a thickness of approximately 5 Il [jI], and the inner diameter and wall thickness of the hollow fiber membrane when wet were measured at 30 locations. The measurement was performed using an optical microscope (0PTIPHOT-1'OL, manufactured by Nikon Corporation). The results are shown in Table 2, and it was confirmed that Examples 2 and 3.4 suppressed expansion during swelling and suppressed narrowing of the inner diameter of the hollow fiber membrane.

Table 2 n=30 (Experiment 5) An extracorporeal circulation experiment was conducted using two adult mongrel dogs (weight L1:9 and L1:9). Under general anesthesia, the right (or left) common arteriovenous vein was dissected, taking care not to damage nerves, branch vessels, and surrounding tissues.

Furthermore, an indwelling catheter filled with physiological saline was inserted and ligated and fixed.

Using the dog prepared in this manner, an experiment was conducted using an experimental circuit as shown in FIG. The sterilized hollow fiber membrane type artificial dialyzer having a membrane area of 0.8e obtained in Example 3 and Comparative Example 2 was used in the experiment, and the experimental circuit was as shown in FIG. circuit 34 in the artery of the dog 33
A circuit 39 was connected to the vein of the patient. Hollow fiber membrane type artificial dialysis machine
Manometer 36 on the inlet side, manometer 3 on the outlet side
7 was placed. The dialysate inlet/outlet of the hollow fiber membrane type artificial dialyzer 1 and the dialyzer 32 were connected by tubes 40, 41.

The circuit thus constructed and the hollow fiber membrane type artificial dialyzer I were first primed and washed with 1 g of physiological saline.

The extracorporeal circulation experiment was conducted with blood flow set at 1501 (!/min), dialysate flow rate 5 oolc/min (39°C).As for the experimental conditions, anticoagulants such as heparin were not administered. The changes in the pressure difference before and after the hollow fiber membrane type artificial dialyzer were measured over time using manometers attached before and after the hollow fiber membrane type artificial dialyzer.The results are shown in Figure 7. In the hollow fiber membrane type artificial dialyzer of Comparative Example 2, the pressure difference increased significantly approximately 45 minutes after the start of circulation, and circulation became impossible.In the hollow fiber membrane type artificial dialyzer of Example 3 of the present invention, The pressure rose only slightly.

[Operation of the Invention] The operation of the hollow fiber membrane type liquid treatment device of the present invention will be explained using the hollow fiber model artificial dialyzer shown in FIG.

The hollow fiber membrane type artificial dialyzer of the present invention is installed in an extracorporeal circulation circuit, and after priming the extracorporeal circulation circuit and the inside of the dialyzer 1, the blood inflow lower of the hollow fiber membrane type artificial dialyzer l is connected to the artificial dialyzer. Blood flows into 1. The blood that has flowed in comes into contact with the inner surface of the hollow fiber membrane 3 for dialysis, and the dialysate flows into the dialyzer 1 through the dialysate inlet 11 and comes into contact with the outside of the hollow fiber membrane 3. At this time, excess water in the blood,
Waste products such as urea nitrogen, uric acid, and creatinine are transferred to the dialysate, and electrolyte concentrations such as KSNa, CI, and P in the blood are adjusted, and the blood flows out from the blood outlet 8. Hydrophobic resin 4 is present in the hollow fiber membrane 3 for dialysis in the part that contacts the partition wall, and the inner surface of that part has a hydrophobic surface. Even if the hollow fiber membrane comes into contact with water, water does not easily impregnate the hollow fiber membrane in that area, so the wall thickness of the hollow fiber membrane does not expand and maintains its original inner diameter.

[Effects of the Invention] The liquid treatment device of the present invention comprises a nozzing, a hollow fiber membrane bundle consisting of a large number of hollow fiber membranes for liquid treatment inserted into the nozzing, and both ends of the hollow fiber membrane bundle. a partition wall liquid-tightly fixing a part to both ends of the housing; and a partition wall provided near both ends of the housing and communicating with a space formed by the outer surface of the hollow fiber membrane, the inner surface of the nozzle housing, and the partition wall. A hollow fiber model liquid processor having a first liquid inlet and an outlet that communicate with each other and a second liquid inlet and an outlet that are attached to both ends of the housing, the hollow fiber membrane being connected to the The part that comes into contact with the partition wall is a part that does not easily swell when it comes into contact with moisture, so the hollow fiber membrane for liquid treatment in the part that comes into contact with the partition wall can be Even if it comes into contact with the liquid in step 2, the hollow fiber membrane in that part will not be impregnated with water, so the wall thickness of the hollow fiber membrane will not expand and the original inner diameter can be maintained. The inner diameter of the hollow fiber membrane does not change, and it is possible to prevent the flow of the second liquid from becoming poor in the partition wall portion, which would lead to an increase in pressure loss in the liquid treatment device.

Further, the hollow fiber membrane type artificial dialyzer of the present invention includes a housing, a hollow fiber membrane bundle consisting of a large number of hollow fiber membranes for dialysis inserted into the housing, and both ends of the hollow fiber membrane bundle. partition walls fixed liquid-tightly to both ends of the housing;
A dialysate inlet and a dialysate outlet are provided near both ends of the housing and communicate with the space formed by the outer surface of the hollow fiber membrane, the inner surface of the housing, and the partition wall, and the dialysate outlet is provided at both ends of the housing, respectively. In a hollow fiber membrane type artificial dialyzer having an attached blood inlet and a blood outlet, the portion of the hollow fiber membrane for dialysis that comes into contact with the partition wall has a substantially lower diameter than the other portion that does not come into contact with the partition wall. Therefore, even if the part of the hollow fiber membrane for dialysis that comes into contact with the septum comes into contact with saline during brimming or even with blood, the hollow fiber membrane in that part will not absorb water. Since the hollow fiber membrane is not impregnated with water, the wall thickness of the hollow fiber membrane does not expand and the original inner diameter can be maintained.The inner diameter of the hollow fiber membrane that is in contact with the partition wall does not change, and the flow of blood at the partition wall remains unchanged. This can prevent the occurrence of blood clots, clogging, residual blood, and increased pressure loss in the dialyzer.

[Brief explanation of the drawing]

FIG. 1 is a partial sectional view of an embodiment in which the hollow fiber membrane type liquid treatment device of the present invention is applied to a hollow fiber membrane type artificial dialyzer.
This figure is an enlarged cross-sectional view of the partition wall portion of the hollow fiber membrane type artificial dialyzer shown in FIG. 1, and FIG. 3 is a blood boat portion of another embodiment of the hollow fiber membrane type liquid treatment device of the present invention. FIG. FIG. 4 is a schematic diagram of the extracorporeal circulation experimental circuit used in the experiments of the present invention, and FIG. 5 is a diagram showing changes in pressure difference before and after the hollow fiber membrane type artificial dialyzer in the experiments of the present invention. ,
Figure 6 is an enlarged sectional view of the partition wall of a conventional hollow fiber membrane type artificial dialyzer, and Figure 7 is the state of the partition wall when blood and dialysate are passed through the conventional hollow fiber membrane type artificial dialyzer. This is an enlarged cross section showing. 1... Hollow fiber membrane type artificial dialyzer, 2... Housing, 3... Hollow fiber membrane for dialysis, 4... Hydrophobic resin, 5, 6... Bulkhead 1
11! 12) Misfortune

Claims (9)

[Claims] (1) A housing, a hollow fiber membrane bundle consisting of a large number of hollow fiber membranes for liquid treatment inserted into the housing, and a partition wall that liquid-tightly fixes both ends of the hollow fiber membrane bundle to both ends of the housing. and a first liquid inlet and an outlet, which are provided near both ends of the housing and communicate with a space formed by the outer surface of the hollow fiber membrane, the inner surface of the housing, and the partition wall, and both ends of the housing. A hollow fiber membrane type liquid treatment device having a second liquid inlet and a second liquid outlet respectively attached to the partition wall, wherein the hollow fiber membrane is difficult to swell when a portion in contact with the partition wall comes into contact with moisture. A hollow fiber membrane type liquid treatment device characterized by having two parts. (2) Claim 1, wherein the hollow fiber membrane is a hollow fiber membrane for dialysis.
A hollow fiber membrane type liquid treatment device described in . (3) The portion of the hollow fiber membrane that comes into contact with the partition wall is treated with a substance having a reactive group that reacts with a polar group possessed by the hollow fiber membrane or a polar group possessed by a substance contained in the hollow fiber membrane. The hollow fiber membrane type liquid treatment device according to claim 1 or 2. (4) Hollow fiber membrane type liquid treatment according to claim 3, wherein the polar group possessed by the hollow fiber membrane or the polar group possessed by the substance contained in the hollow fiber membrane is any one of a hydroxyl group, an amino group, and a carboxyl group. vessel. (5) The hollow fiber membrane type liquid treatment device according to claim 3 or 4, wherein the reactive group is any one of an isocyanate group, an epoxy group, a thiocyanate group, an acid chloride group, and an aldehyde group. (6) A housing, a hollow fiber membrane bundle consisting of a large number of hollow fiber membranes for liquid treatment inserted into the housing, and partition walls that liquid-tightly fix both ends of the hollow fiber membrane bundle to both ends of the housing. and a first liquid inlet and an outlet, which are provided near both ends of the housing and communicate with a space formed by the outer surface of the hollow fiber membrane, the inner surface of the housing, and the partition wall, and both ends of the housing. A hollow fiber membrane type liquid treatment device having a second liquid inlet and a second liquid outlet respectively attached to the parts, the hollow fiber membrane in the part that comes into contact with the partition wall is smaller than the other part that does not come into contact with the partition wall. do,
A hollow fiber membrane type liquid treatment device characterized by having a portion that is substantially difficult to absorb moisture. (7) a housing, a hollow fiber membrane bundle consisting of a large number of hollow fiber membranes for dialysis inserted into the housing, and a partition wall that fixes both ends of the hollow fiber membrane bundle to both ends of the housing in a fluid-tight manner; , a dialysate inlet and a dialysis outlet that are provided near both ends of the housing and communicate with the space formed by the outer surface of the hollow fiber membrane, the inner surface of the housing, and the partition wall; In a hollow fiber membrane type artificial dialyzer having a blood inlet and a blood outlet respectively attached, the hollow fiber membrane for dialysis in the portion that contacts the partition wall has a lower diameter than the other portion that does not contact the partition wall. ,
A hollow fiber membrane type artificial dialysis machine characterized by a part that is substantially difficult to absorb water. (8) The hollow fiber membrane type artificial dialyzer according to claim 7, wherein the hollow fiber membrane for dialysis is a hydrophilic hollow fiber membrane for dialysis. (9) The hollow fiber membrane for dialysis in the portion that contacts the partition wall has a hydrophobic surface on the inner surface of the hollow portion of the portion and the end face located on the partition wall surface.
The hollow fiber membrane type artificial dialyzer described in .