JPS6352525B2 - - Google Patents

Description

BACKGROUND OF THE INVENTION Technical Field The present invention relates to a method for manufacturing a hollow fiber mass transfer device. More specifically, the present invention relates to a method for manufacturing a hollow fiber type mass transfer device that enables uniform dispersion of hollow fibers and prevents poor potting that causes leakage.

Prior Art Conventionally, medical hollow fiber mass transfer devices, such as oxygenators, have a cylindrical housing, a hollow fiber bundle consisting of a large number of hollow fiber membranes for gas exchange inserted into the housing, and an outside of the hollow fiber membranes. an oxygen chamber formed by a surface and an inner surface of the housing; an oxygen supply chamber and an oxygen outlet communicating with the oxygen chamber; and a partition wall supporting each end of the hollow fiber membrane and separating it from the oxygen chamber; A hollow fiber oxygenator is known which includes a blood inlet and an outlet that communicate with the internal space of each of the hollow fiber membranes (see Utility Model Application No. 138947-1980, Japanese Patent Application Publication No. 86171-1982, and Japanese Patent Application Publication No. 58-1989). - No. 86172). In addition, an artificial kidney (dialyzer) includes a cylindrical housing, a hollow fiber bundle consisting of a large number of hollow fiber membranes for dialysis inserted into the housing, an outer surface of the hollow fiber membranes, and an inner surface of the housing. A dialysis chamber to be formed, a dialysate supply port and a discharge port communicating with the dialysis chamber, partition walls that respectively support each end of the hollow fiber membrane and isolate it from the dialysis chamber, and an internal space of the hollow fiber membrane. A hollow fiber type artificial kidney is known, which consists of a blood inlet and an outlet communicating with the blood (Chemistry Review Vol. 21, "Chemistry of Medical Materials", No. 144-
146 pages, published by Gakkai Publishing Center Co., Ltd. on November 25, 1978).

However, the technique of sealing and potting a bundle of hollow fibers at both ends of a cylindrical housing has been considerably improved and mechanized in the manufacture of dialyzers, etc., but this is because the number of hollow fibers is small compared to the potting area. , processing was not that difficult. However, the hollow fibers were not completely uniformly dispersed, and there was a risk of blood leakage.

Furthermore, conventionally, in order to pot the hollow fibers at both ends of the cylindrical housing in an oxygenator, a sealing agent having the same composition as the potting agent is poured into the potting cup, and the ends of the hollow fiber bundle are placed in the sealing agent. It was soaked, sealed and potted at the same time. However, in the case of an oxygenator with a large membrane area, the number of hollow fibers is as large as tens of thousands, so it is difficult to maintain the hollow fiber bundle at a constant diameter and uniformly disperse the hollow fibers within that diameter range. Therefore, in the densely distributed portions of the hollow fiber bundle, the hollow fibers tend to adhere to each other, and the potting agent does not enter into these closely adhered portions, resulting in poor adhesion. Therefore, there is a need for a method of uniformly dispersing the hollow fibers during sealing so that the filler can easily enter between the hollow fibers.

OBJECT OF THE INVENTION Accordingly, an object of the present invention is to provide a method for manufacturing a novel hollow fiber type mass transfer device.
Another object of the present invention is to provide a method for manufacturing a hollow fiber type mass transfer device that allows uniform dispersion of hollow fibers and prevents poor potting that causes leakage.

These purposes include a plurality of hollow fiber membranes having a length greater than the cylindrical housing within a cylindrical housing having a first mass transfer fluid inlet and a first mass transfer fluid outlet near each end. a step of inserting a hollow fiber bundle consisting of a first hollow fiber bundle having one end fixed therein and an opening at the other end to such an extent that the hollow fiber bundle slightly protrudes from the end of the cylindrical housing; A split cup is fitted, the ends of the hollow fiber bundle are dispersed throughout the opening of the first split cup, and one end is closed in the opening of the first split cup, and an eye is inserted into the closed part. fitting a second split cup filled with a sealant and immersing the end of the hollow fiber bundle in the sealant to seal and fix the hollow fiber bundle; A first split cup having an opening such that the fiber bundle slightly protrudes from the end of the cylindrical housing is fitted, and the end of the hollow fiber bundle is inserted into the entire opening of the first split cup. The hollow fiber bundle is dispersed in the opening of the first split cup, and a second split cup with one end closed and filled with a sealant is inserted into the opening of the first split cup. immersing the ends of the hollow fibers to seal and fix them; and injecting a potting agent through the first mass transfer fluid supply port and the first mass transfer fluid discharge port to fix the hollow fiber ends in the housing. This is achieved by a method for manufacturing a hollow fiber type mass transfer device characterized by comprising a step of fixing to the end portion, and a step of slicing the potting surface to open the end portion of the hollow fiber bundle.

Further, the present invention is a hollow fiber mass transfer device that is a hollow fiber oxygenator. Furthermore, the present invention provides the first
The outer surface of the tip of the split cup has a tapered shape, and the inner surface of the second split cup has a tapered shape corresponding to the outer surface of the first split cup. This is a method for manufacturing a type mass transfer device. Further, the present invention provides a first split cup and a second split cup when the second split cup is fitted onto the first split cup. This is a method for manufacturing a hollow fiber type mass transfer device in which a space is formed between the cup and the bottom surface. Furthermore, the present invention is a method for manufacturing a hollow fiber type mass transfer device in which the potting agent and the sealing agent used to form the partition walls are of the same material. Further, the present invention is a method for manufacturing a hollow fiber type mass transfer device in which the potting agent is polyurethane. moreover,
In the present invention, the polyurethane is a mixture of a prepolymer of 4,4'-diphenylmethane diisocyanate and a difunctional castor oil derivative, and a curing agent comprising a mixture of the difunctional castor oil derivative, a polyvalent polypropylene glycol, and an amino alcohol. This is a method for manufacturing a certain hollow fiber type mass transfer device. Further, the present invention provides a method for manufacturing a hollow fiber type mass transfer device, in which the dispersion of the hollow fiber bundle is performed by blowing gas. Furthermore, in the present invention, the step of fixing the hollow fiber end to the end of the housing includes injecting a potting agent from the first mass transfer fluid supply port to fix a portion of the hollow fiber to the end of the housing. A method for manufacturing a hollow fiber type mass transfer device comprising the steps of fixing the hollow fiber end to the end of the housing by injecting a potting agent from the first mass transfer fluid outlet. be.

Specific Configuration of the Invention Next, an embodiment of the present invention will be described with reference to the drawings. As shown in FIG. 1, a housing 1 is provided with a gas inlet port 10 forming a first mass transfer fluid supply port and a gas exhaust port 9 forming a first mass transfer fluid outlet near both ends thereof. A hollow fiber bundle 15 consisting of a large number of hollow fiber membranes 5 having a length longer than the cylindrical housing 2 is inserted into the cylindrical housing 2 . Note that it is preferable to provide the inner surface of the cylindrical housing 2 with a constriction restricting portion that is located at the center in the axial direction and projects. In this case, the restraint part 14 is formed integrally with the cylindrical housing 2 on the inner surface of the cylindrical housing 2,
The outer periphery of a hollow fiber bundle 15 made up of a large number of hollow fiber membranes 5 inserted into the cylindrical housing 2 is tightened. In this way, the hollow fiber bundle 15
is constricted at the center in the axial direction to form a constricted portion 16, as shown in FIG.

One end of the hollow fiber bundle 15 inserted in this manner is temporarily fixed, and the other end has an opening 37 to the extent that the hollow fiber bundle 15 slightly protrudes from the end of the cylindrical housing 2. Fit the first split cup 38. Inside this first split cup 38,
A sealing member such as an O-ring 40 is attached if necessary. The cylindrical housing 2 into which the hollow fiber bundle 15 has been inserted in this manner is erected so that its axis is substantially perpendicular, and one end is closed at the distal end 41 of the opening 37 of the first split cup 38. And by fitting the second split cup 44 filled with the sealant 43 into the inside 42 of the closed part, the sealant 43 is removed.
The ends of the hollow fiber bundles 15 are immersed in the filler to perform sealing, and the hollow fiber bundles 15 are uniformly dispersed and fixed in the filler. In this case, it is desirable that the end portion 41 of the opening 37 of the first split cup 38 be formed in a tapered shape, and that the inside of the second split cup 44 be also formed in a tapered shape corresponding to the tapered shape. Furthermore, when the second split cup 44 is fitted onto the first split cup 38, the first split cup 38 and the second split cup 44 are connected to the end of the first split cup 38 and the second split cup 44. It is desirable that a space be formed between the bottom surface of the split cup 44 and a burr formed in the space.

Next, by injecting a potting agent from one first mass transfer fluid supply port 10 of the cylindrical housing 2, the hollow fiber bundle 15 is fixed at the end of the cylindrical housing 2, and the partition wall 4 is fixed. Let it form. By performing the same operation on the other end, the hollow fiber bundle 15 is fixed to the cylindrical housing 2 at both ends, and the partition walls 3 and 4 are formed. Then, the first and second split cups 3
After removing 8 and 44, the end face of the partition wall formed by the potting is sliced to open the end of the hollow fiber, thereby forming a module of the mass transfer device. Further, in the above method, gas is blown onto the end of the hollow fiber bundle in the first split cup to uniformly disperse the hollow fibers, and then the hollow fibers are inserted into the opening of the first split cup until one end is closed and the hollow fibers are closed. A second split cup filled with a sealant is inserted into the closed part.

The hollow fiber membrane 5 is made of porous polyolefin resin such as polypropylene or polyethylene, and polypropylene is particularly suitable for use as an oxygenator. This hollow fiber membrane 5 for an artificial lung has a large number of pores communicating between the inside and outside of the wall. Its inner diameter is approximately 100 to 1000 μm, and the wall thickness is approximately 10 to 50 μm.
The average pore diameter is approximately 200~2000Å, and the porosity is approximately 20~
80%. When a hollow fiber membrane made of such a polyolefin resin is used, gas movement occurs as a volumetric flow, so the membrane resistance during gas movement is small, and the gas exchange performance is significantly improved. However, hollow fiber membranes made of silicone can also be used.

Furthermore, it is preferable that the porous polypropylene or polyethylene used as the material for the hollow fiber membrane 5 not be used as is in the oxygenator, but that the surface that comes into contact with blood should be coated with an antithrombotic material. For example, a material having excellent gas permeability such as polyalkylsulfone, ethyl cellulose, or polydimethylsiloxane is coated to a thickness of about 1 to 20 μm. In this case, if the membrane pores are covered to the extent that the gas permeability of the hollow fiber membrane 5 is not affected, water vapor evaporation in the blood can be prevented. Also, while the oxygenator is operating, the pressure on the blood side is usually higher than that on the oxygen side.
It may be reversed for some reason. In such a case, there is a risk that microbubbles may flow into the blood, but if the membrane pores are coated with an antithrombotic material as described above, this risk does not occur. Furthermore, needless to say, it is useful in preventing blood coagulation (occurrence of microclots).

Potting agents and sealants include polyurethane, silicone, epoxy resin, etc.
Particularly preferred is polyurethane.

As the polyurethane, any of prepolymer adhesives, polyisocyanate adhesives, and isocyanate-modified polymers can be used, but prepolymer adhesives are usually preferably used. Examples of prepolymer adhesives include 4,4'-diphenylmethane diisocyanate (hereinafter referred to as MDI) and bifunctional castor oil derivatives (for example, polypropylene glycol ester of ricinoleic acid, molecular weight 540).
Prepolymer with (NCO/OH=1:1~1.5)
and a mixture of a bifunctional castor oil derivative, a polyfunctional polypropylene glycol (molecular weight 2000-3000), and an amino alcohol (weight ratio 70-50:15-25:15-
25) There is a curing agent that is mixed at a weight ratio of 65:35 to 59:41 so that the number of functional groups almost matches. Excellent quality.

Castor oil derivatives whose main components are esters having two hydroxyl groups include ricinoleic acid and ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2 ,3-
It is obtained as an ester by reacting monomers or polymers such as butanediol, polyethylene glycol, polypropylene glycol, polybutylene glycol, etc. with diols.

Furthermore, a castor oil derivative containing an ester having two hydroxyl groups as a main component can be obtained by mixing castor oil with a diol made of the above monomer or polymer and transesterifying the mixture using sulfuric acid, sodium hydroxide, or potassium hydroxide as a catalyst.

Since this castor oil derivative contains about 10% organic acid without hydroxyl groups, the average number of hydroxyl groups is about 1.8, and the number of hydroxyl groups can be brought closer to 2 by refining.

These prepolymers having isocyanate groups at the ends made of castor oil derivatives and MDI have about 1.8 to about 2 isocyanate groups, which is about 0.9 more than the number of isocyanate groups of the prepolymers having isocyanate groups at the ends made of castor oil and toluene diisocyanate. It has a low viscosity of ~0.7 particles and is easy to flow, so it can easily flow between hollow fibers and between hollow fibers and support members, making it easy to cast, and air bubbles can be easily removed, resulting in high work efficiency.

The curing agent is a mixture of a bifunctional castor oil derivative mainly composed of an ester having two hydroxyl groups, a polyhydric alcohol having three or more hydroxyl groups, and an amino alcohol having three or more hydroxyl groups.

This castor oil derivative can be the same as that used for the above-mentioned prepolymer.

The polyhydric alcohol having three or more hydroxyl groups is pentaerythritol, glycerin, trimethylolpropane, sorbitol, sucrose, or an ether of these and alkylene oxide, preferably pentaerythritol or an ether of glycerin and propylene oxide.

Amino alcohols having three or more hydroxyl groups include N,N,N',N'-tetrakis[2-hydroxypropyl]-ethylenediamine, triethanolamine, etc.; -Hydroxypropyrel]-Ethylenediamine is preferred.

The hardness of the resin member can be increased by increasing the ratio of polyhydric alcohol to amino alcohol in the curing agent. Further, the hardness can be increased by selecting an alcohol with a higher number of hydroxyl groups from among polyhydric alcohols and amino alcohols. If you want to lower the hardness, the opposite is true. In addition, when promoting the reaction between the prepolymer and the curing agent while keeping this hardness approximately constant, select polyhydric alcohols and amino alcohols with approximately the same number of hydroxyl groups, and keep the ratio of castor oil derivatives in the curing agent constant. By doing so, the same hardness can be maintained, and by increasing the ratio of polyhydric alcohol to amino alcohol, the reaction is promoted, and by increasing the polyhydric alcohol, the reaction is delayed.

That is, the amino alcohol has a catalytic effect and also reacts with the prepolymer as a curing agent.

In this way, the hardness and reaction rate of the resin member can be easily determined by the composition ratio of the curing agent.

The composition ratio of the curing agent used in the present invention is desirably 70-50:15-25:15-25 in terms of weight ratio of castor oil derivative to polyhydric alcohol to amino alcohol. Also, the weight ratio with the prepolymer curing agent is
A ratio of 50 to 70 per 100 is desirable. Additionally, the desired range for cutting is 59 to 63 parts of curing agent to 100 parts of prepolymer.
It is. As a result, the prepolymer and curing agent gel at room temperature in about 10 minutes.

Partition walls 6 and 7 of the module manufactured by the above method
By attaching flow path forming members 11 and 12 to the outer surface of the artificial lung, an artificial lung as shown in FIG. 2 is formed. These flow path forming members 11 and 12 are respectively composed of liquid distribution members 17 and 18 and threaded rings 19 and 20, and the end surfaces of protrusions 21 and 22 are formed as annular convex portions provided near the peripheral edges of these liquid distribution members 17 and 18. are brought into contact with the partition walls 6, 7, respectively, and are fixed by screwing the screw rings 19, 20 onto the mounting covers 3, 4, respectively, thereby allowing the inflow chamber 23 and outflow chamber of the second mass transfer fluid, for example, blood. 24 are formed respectively. The flow path forming members 11 and 12 are respectively provided with an inlet 25 and an outlet 26 for blood, which is a second mass transfer fluid, and air vent holes 27 and 28.

At least two holes 2 communicating with the hollow portions of the partition walls 6 and 7 formed by the partition walls 6 and 7 and the flow path forming members 11 and 12 are provided in the hollow portions at the peripheral edges of the partition walls 6 and 7 and the flow path forming members 11 and 12.
By filling fillers 31 and 32 from one of the partition walls 9 and 30, the partition walls 6 and 7 are sealed in contact with each other. Alternatively, it may be sealed by an O-ring.

In addition, in Fig. 2, each opening has a cap 3.
3, 34, 35, and 36 are attached.

For example, in the case of an artificial lung, the first mass transfer fluid is an oxygen-containing gas such as air or blood, and when the first mass transfer fluid is a gas, the second mass transfer fluid is blood. , in the case of blood, the second mass transfer fluid is a gas.

Next, the method of the present invention will be explained in more detail with reference to Examples.

Example: Gas ports 9 and 10 at both ends as shown in Figure 1.
A hollow fiber bundle 15 consisting of approximately 38,000 polypropylene hollow fiber membranes having a length longer than that of the cylindrical housing 2 is inserted into the cylindrical housing 2 equipped with a cylindrical housing 2, and its upper end is temporarily fixed. A first breakable cup 38 slightly protruding from the other end was fitted onto the end. Then, inside, a prepolymer of MDI and polypropylene glycol ester of ricinoleic acid (molecular weight 540) (NCO/OH = 1:1.5), a mixture of a bifunctional castor oil derivative, a polyfunctional polypropylene glycol, and an amino alcohol (weight ratio:
50-70:15-25:15:25) in a weight ratio of 60:40 so that the number of functional groups is almost the same. The ends of the hollow fiber bundle 15 were sealed by abutting the cup 44 and dispersed. Next, the potting agent was injected through the gas port 10 and left for 20 minutes to form the partition walls 7. Such an operation was also performed on the other end to form the partition wall 6. Next, after removing the first and second split cups, the end faces of the partition walls 6 and 7 were sliced to open the ends of the hollow fiber membranes to form an oxygenator module. A flow path forming member was attached to this module as shown in FIG. 2 to obtain an oxygenator.

Specific Effects of the Invention As described above, the present invention provides a cylindrical housing that is longer than the cylindrical housing and has a first mass transfer fluid supply port and a first mass transfer fluid discharge port near both ends. a step of inserting a hollow fiber bundle consisting of a large number of hollow fiber membranes having a length; one end of the hollow fiber bundle is fixed, and the other end of the hollow fiber bundle slightly protrudes from the end of the cylindrical housing; A first split cup having an opening of about 100 liters is fitted, the ends of the hollow fiber bundle are dispersed throughout the opening of the first split cup, and one end is inserted into the opening of the first split cup. is closed and a second split cup filled with a sealant is fitted into the closed part, and the end of the hollow fiber bundle is immersed in the sealant to seal and fix it; A first split cup having an opening such that the hollow fiber bundle slightly protrudes from the end of the cylindrical housing is fitted onto one end of the hollow fiber bundle, and the end of the hollow fiber bundle is inserted into the first split cup. A second split cup with one end closed and a filler filled in the closed part is fitted into the opening of the first split cup, and a second split cup filled with a sealant is placed in the opening of the first split cup. immersing the ends of the hollow fiber bundle in a potting agent to seal and fix the bundle; and injecting a potting agent from the first mass transfer fluid supply port and the first mass transfer fluid discharge port. A method for manufacturing a hollow fiber type mass transfer device, comprising the steps of fixing the hollow fiber ends to the ends of the housing, and further slicing the potting surface to open the ends of the hollow fiber bundle. Because it is,
It is possible to uniformly disperse a hollow fiber bundle consisting of a large number of hollow fiber membranes, maintain the dispersed diameter of the hollow fiber membranes on the slicing surface, and maintain the dispersed state of the hollow fiber membranes, which makes it possible to fill the hollow fiber membranes on the slicing surface. The rate can be adjusted, and sealing can be performed with the hollow fiber membranes uniformly dispersed, so there is no sealing failure. This effect is particularly remarkable when the hollow fiber mass transfer device is an oxygenator. In addition, since the hollow fiber membranes can be uniformly dispersed, there is no defective adhesion of the hollow fiber membranes to the partition walls, and therefore no leakage occurs. Furthermore, since the hollow fiber membranes can be uniformly dispersed, there is no channeling on the gas flow path side. In addition, one-sided centrifugal potting is possible by utilizing the burrs of the filler generated during sealing. Furthermore, since it can be attached to a cylindrical housing, there is no leakage of potting agent during potting. Furthermore, the hollow fiber membranes are easy to disperse and can be easily mechanized.

Moreover, when the first split cup and the second split cup are fitted, the end of the first split cup and the bottom surface of the second split cup are connected. If a space is formed in between, burrs can be formed in the space.

Furthermore, if the outer surface of the tip of the first split cup is tapered and the inner surface of the second split cup is formed into a tapered shape corresponding to the outer surface of the first split cup, fitting is facilitated. Moreover, the sealing performance is good.

[Brief explanation of the drawing]

FIG. 1 is a cross-sectional view showing an example of the manufacturing process of an oxygenator according to the present invention, and FIG. 2 is a cross-sectional view showing an example of the artificial lung manufactured by the method. 2... Cylindrical housing, 5... Hollow fiber membrane, 6, 7...
Partition wall, 15... Hollow fiber bundle, 37... Opening of first split cup, 38... First split cup, 40... O ring, 41... End of opening, 42... Inside of closed part of second split cup , 43...filler, 44...second split cup.

Claims (1)

[Scope of Claims] 1. A plurality of hollow fibers having a length longer than the cylindrical housing within a cylindrical housing having a first mass transfer fluid supply port and a first mass transfer fluid discharge port near both ends thereof. a step of inserting a hollow fiber bundle made of a membrane; and a first step of fixing one end of the hollow fiber bundle and having an opening at the other end to such an extent that the hollow fiber bundle slightly protrudes from the end of the cylindrical housing. the ends of the hollow fiber bundle are dispersed throughout the opening of the first split cup, one end of which is closed in the opening of the first split cup, and the ends of the hollow fiber bundle are inserted into the opening of the first split cup. a step of fitting a second split cup filled with a filler and immersing the end of the hollow fiber bundle in the filler to seal and fix it; A first split cup having an opening such that the hollow fiber bundle slightly protrudes from the end of the cylindrical housing is fitted, and the end of the hollow fiber bundle is inserted into the entire opening of the first split cup. A second split cup with one end closed and a filler filled in the closed part is fitted into the opening of the first split cup, and the hollow fiber bundle is dispersed in the filler. immersing the ends of the hollow fibers to seal and fix them; and injecting a potting agent from the first mass transfer fluid supply port and the first mass transfer fluid discharge port to fix the hollow fiber ends to the housing. 1. A method for manufacturing a hollow fiber mass transfer device, comprising the steps of: fixing to the end of the hollow fiber bundle; and further slicing the potting surface to open the end of the hollow fiber bundle. 2. The method for manufacturing a hollow fiber mass transfer device according to claim 1, wherein the hollow fiber mass transfer device is a hollow fiber oxygenator. 3. The outer surface of the tip of the first split cup has a tapered shape, and the inner surface of the second split cup has a tapered shape corresponding to the outer surface of the first split cup. A method for manufacturing a hollow fiber mass transfer device according to claim 1 or 2. 4 When the first split cup and the second split cup are fitted, when the second split cup is fitted onto the first split cup, the end of the first split cup and the bottom surface of the second split cup are connected. A method for manufacturing a hollow fiber mass transfer device according to any one of claims 1 to 3, wherein a space is formed between the hollow fibers. 5. The method for manufacturing a hollow fiber mass transfer device according to any one of claims 1 to 4, wherein the potting agent and sealing agent used to form the partition walls are the same material. 6. The method for manufacturing a hollow fiber mass transfer device according to claim 5, wherein the potting agent is polyurethane. 7 Polyurethane is a patented mixture of a prepolymer of 4,4'-diphenylmethane diisocyanate and a difunctional castor oil derivative, and a curing agent consisting of a mixture of the difunctional castor oil derivative, polypropylene glycol, and amino alcohol. A method for manufacturing a hollow fiber mass transfer device according to claim 6. 8. The dispersion of the hollow fiber bundle is performed by blowing gas.
2. A method for manufacturing a hollow fiber mass transfer device according to any one of Items 1 and 2. 9. The step of fixing the hollow fiber end to the end of the housing includes injecting a potting agent from the first mass transfer fluid supply port to fix one end of the hollow fiber bundle to the end of the housing. and a step of fixing the other end of the hollow fiber bundle to the end of the housing by injecting a potting agent from the first mass transfer fluid outlet. 9. A method for manufacturing a hollow fiber mass transfer device according to any one of items 8 to 8.