JP2010046587A - Hollow fiber membrane module - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hollow fiber membrane module preventing channeling in the hollow fiber membrane module while suppressing the occurrence of quality defective products like flattening or clogging of hollow fiber membranes, thereby developing stable and high permeability. <P>SOLUTION: In the hollow fiber membrane module in which hollow fiber membranes imparted with a crimp are filled, (a) an average of channeling values expressed by CL2000-CL500 is less than 7 ml/min wherein CL500 denotes a urea clearance measured at a dialysate solution flow rate of 500 ml/min using five hollow fiber membranes with a membrane area of 1.5 m<SP>2</SP>on an inner diameter basis, and wherein CL2000 denotes a urea clearance obtained by converting a urea clearance measured at a dialysate solution flow rate of 2,000 ml/min into a value at the dialysate solution flow rate of 500 ml/min via an overall coefficient of mass transfer, and (b) an average of the channeling values after reverse pressure cleaning using a chemical solution is less than 13 ml/min. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a hollow fiber membrane module. More specifically, by effectively suppressing the dialysis fluid drift (channeling) in the hollow fiber membrane module, the dialysis efficiency is excellent, the dialysis performance is excellent in washing resistance, and there are restrictions on the spinning process and cost increases. Further, the present invention relates to a hollow fiber membrane module excellent in assemblability of the hollow fiber membrane module.

  Compared to flat membranes, hollow fiber membranes that can accommodate a large membrane area in a small module are superior in volumetric efficiency and are used in various fields related to liquid processing, especially in the field of blood purification treatment Occupy its mainstream.

  The hollow fiber membrane for blood purification is housed in a housing called a module in a bundle of 1000 to 20000, and assembled as a hollow fiber membrane module for blood purification. The performance of the hollow fiber membrane module for blood purification depends on the permeation performance of the hollow fiber membrane itself, but the influence of its structure cannot be ignored.

  When the hollow fiber membrane module for blood purification is used, blood flows inside the hollow fiber membrane, and the dialysate flows outside the hollow fiber membrane, that is, through the gap between the hollow fiber membranes. A mechanism is used to remove unnecessary substances in the blood through the membrane to the dialysate side. At this time, if the dialysate, which is the external reflux liquid, does not flow uniformly between all the hollow fiber membranes, but flows only to a certain part, the hollow fiber membranes in the part where the dialysate does not flow are not effectively used. The permeability performance as a hollow fiber membrane module for blood purification is not sufficiently exhibited. This phenomenon is called drifting or channeling, and it is known to have a great adverse effect on the ability to remove low-molecular substances such as urea.

  On the other hand, the hollow fiber membrane bundle in which the gap between the hollow fiber membranes is not sufficient as described above also has a problem that the adhesiveness at the time of assembling the module is likely to be poor. That is, in the module assembling process, when the hollow fiber membrane end and the module end are bonded with resin, if the gap between the hollow fiber membranes is insufficient, the resin does not enter between them and a space is created, causing a minute leak or Adhesion failure called slip-out occurs. Therefore, many attempts have been made so far to avoid the drift phenomenon and adhesion failure as described above.

  For example, a technique is disclosed in which a plurality of fins are formed in the longitudinal direction on the outer side of the hollow fiber membrane to prevent the hollow fiber membranes from sticking to each other, thereby maintaining the gap between the hollow fiber membranes. (See Patent Document 1). In addition, a technique for securing a gap between hollow fiber membranes by winding a spacer yarn around a hollow fiber membrane and utilizing the spreading force of the spacer yarn is shown. (For example, see Patent Document 2). However, the former technique requires a special die, restricts the operation surface and spinning conditions, and makes it difficult to express the permeation performance as a perfect circular hollow fiber membrane, which is not realistic. Further, the latter technique has a problem that not only is the cost high because a step of winding the spacer yarn is required, but also a compact module cannot be obtained because the bulkiness is increased.

  Therefore, there are few restrictions on the operation surface and spinning conditions, and as a method of preventing drift phenomenon and adhesion failure simply at low cost, the hollow fiber membranes are crimped to provide close contact between adjacent hollow fiber membranes. Techniques for preventing this are disclosed. (For example, refer to Patent Document 3). In the technique disclosed in this document, a hollow fiber membrane that is spun is wound around a bobbin at a specific twill angle so that the hollow fiber membranes that overlap each other are in point contact. By corrugating the wound cheese, the corrugated shape (crimp) with the point-contacted portion as a fulcrum can be fixed to the hollow fiber membrane. This method is certainly an effective technique, but in order to heat-fix the crimp, a process for heat treatment under special conditions is necessary after spinning, and the required time and cost associated therewith cannot be ignored. Moreover, it is limited to the treatment in a bobbin winding state, and there is a problem that it cannot be applied to a hollow fiber membrane in which bobbin winding cannot be performed. Furthermore, since it is difficult to make the number of crimps per unit length the same in the inner layer and the outer layer of the bobbin, the module manufactured using only the hollow fiber membrane of the bobbin outer layer part and the hollow fiber of the bobbin inner layer part There is a problem that a performance difference occurs between a module manufactured using only the membrane.

  In recent years, the effect of the above crimp has been reconfirmed, and attempts have been made to impart crimp to hollow fiber membranes manufactured in forms other than bobbin winding. In recent years, a hollow fiber membrane having an asymmetric structure having a dense skin layer inside the hollow fiber membrane has attracted attention. The asymmetric structure membrane is manufactured using a liquid having a coagulation property with respect to a polymer, particularly an aqueous solution, as a core liquid in order to form a skin layer inside the hollow fiber membrane. When such a hollow fiber membrane is wound around a bobbin, a core liquid containing water is contained, so that when the heat treatment is performed for crimp fixation, the membrane is crushed due to the influence of surface tension accompanying water evaporation.

  As a method of applying a crimp to a hollow fiber membrane having an asymmetric structure, it is attempted to perform a process of mechanically forming a wave in the hollow fiber membrane by passing the hollow fiber membrane while meandering between opposing gears. Has been. However, in such a mechanical treatment, an effective crimp has not been provided so far, especially for delicate hollow fiber membranes used for blood purification. This is because in order to give an effective strong crimp, it is necessary to apply a stronger mechanical external force to the hollow fiber membrane, so that the hollow fiber membrane may be deformed or blocked, or the membrane may be damaged. This is because there is a very high possibility of falling.

  Therefore, in the prior art, only a wave having a large wave waving structure with a long pitch between crimps can be used as a product so as not to damage the hollow fiber membrane as much as possible. However, in such a wave waving structure, the effect of ensuring the gap between the adjacent hollow fiber membranes is not sufficient, so this alone cannot completely avoid the drift, such as improvement of the module housing structure, etc. The reality is that it is supported by using it together with other technologies.

  For example, in Patent Document 4, the above problem is solved by applying a crimp with a wavelength of 10 mm or more and an amplitude of 0.2 mm or more. However, there is a problem in the stability of the drift suppression effect, and many modules were manufactured. In some cases, modules that cannot express the original transmission performance may be mixed.

  Patent Document 5 discloses a technique capable of exhibiting an extremely excellent drift prevention effect due to a synergistic effect of fins and crimps by applying a loose specific crimp to a hollow fiber membrane having fins. However, in order to form fins in the hollow fiber membrane, a special die is required, and if crimping is further applied, it is subject to considerable restrictions in terms of manufacturing conditions, so even if drift can be suppressed, it is high. It is even more difficult to manufacture a hollow fiber membrane having a permeation performance, and there is a great concern that problems such as an increase in manufacturing cost and a decrease in yield will occur. Further, when a module is produced using such a hollow fiber membrane, the hollow fiber membrane bundle becomes bulky, and there is a problem that the module case needs to be enlarged in order to obtain a predetermined membrane area. .

  In Patent Document 6, the hollow fiber membrane with fins as described in Patent Document 1 has a non-symmetric structure with a dense layer on the outside, thereby suppressing permeation of dialysate and lowering permeation performance due to increased film thickness. A technique that achieves both avoidance is disclosed. In the examples, it is described that the drift value, which is the difference between the phosphorus clearance when the dialysate flow rate is 500 ml / min and the converted value of the phosphorus clearance when the dialysis flow rate is 2000 ml / min, was 15 to 16. ing. However, even in this technique, there is no change in the restrictions on the spinning conditions, and since there is a dense layer on the outside of the hollow fiber membrane, clogging occurs from the inside to the outside of the hollow fiber membrane when actually subjected to hemodialysis. There is a great concern that the transmission performance will gradually deteriorate as a result.

Patent Document 7 discloses a hemodialysis module in which hollow fibers having 20 to 40 crimps per 10 cm in length and hollow fibers having less than 20 crimps per 10 cm are mixed at a specific ratio. Thus, a technique for suppressing the drift of the dialysate and achieving both compactness of the module is disclosed. However, with this technology, in order to obtain hollow fibers with different crimp numbers, it is necessary to manufacture hollow fiber fibers separately under different winding tensions and heat treatment conditions, and then identify each hollow fiber. Therefore, a process for producing a hollow fiber bundle by mixing them at a ratio of 1 to 5 is required.
JP 61-119274 A Japanese Patent Laid-Open No. 05-041979 JP 58-182722 A JP 2005-348784 A JP 09-266947 A JP 09-276400 A JP 2003-79721 A

  Therefore, in view of the problems of the prior art, the present invention can prevent the occurrence of poor quality of the hollow fiber membrane and prevent the drift of the external reflux liquid, and can exhibit a high permeation performance safely and stably. A hollow fiber membrane module is provided.

The hollow fiber membrane module of the present invention capable of solving the above-described problems has the following configuration.
(1) A hollow fiber membrane module filled with a hollow fiber membrane provided with a crimp,
(A) Using five hollow fiber membrane modules with an inner diameter reference membrane area of 1.5 m ² , the urea clearance when measured at a dialysate flow rate of 500 ml / min is CL500, and when measured at a dialysate flow rate of 2000 ml / min When the urea clearance converted from the urea clearance to the value at a dialysate flow rate of 500 ml / min through the overall mass transfer coefficient is CL2000, the average of the drift value represented by CL2000-CL500 is less than 7 ml / min,
(B) A hollow fiber membrane module, wherein the average of the drift value after back pressure washing with a chemical solution is less than 13 ml / min.
(2) Crimp index expressed as A x X ² / D, where the crimp amplitude is A (mm), the number of crimps is X (pieces / cm), and the outer diameter of the hollow fiber membrane is D (mm) The hollow fiber membrane module according to (1), wherein
(3) The amplitude (A) of the crimp of the hollow fiber membrane is 0.1 to 1.0 mm, the number of crimps per hollow fiber membrane length (X) is 0.5 to 2.0 pieces / cm, and the outer diameter is 0.1 to 0.5 mm (1 ) Or the hollow fiber membrane module according to (2).
(4) The hollow fiber membrane module according to any one of (1) to (3), wherein a filling rate of the hollow fiber membrane is 45 to 75%.
(5) The hollow fiber membrane module according to any one of (1) to (4), wherein the retention rate of the crimp index of the hollow fiber membrane before and after back pressure washing using a chemical solution is 70% or more.
(6) The hollow fiber membrane module according to any one of (1) to (5), wherein the chemical solution contains one or more selected from hydrogen peroxide, peracetic acid, and acetic acid.

  The hollow fiber membrane module of the present invention suppresses the occurrence of defective products such as flatness, blockage, and breakage of the hollow fiber membrane when mechanically imparting crimps during the production of the hollow fiber membrane, and when modularized By effectively reducing the contact between the hollow fiber membranes, it is possible to obtain a hollow fiber membrane that can exhibit stable and high permeation performance with a high yield. In addition, when applying the crimping mechanically during the production of the hollow fiber membrane, consideration is given to concentrating stress on each point of the hollow fiber membrane. There is also an effect that mitigation and disappearance can be minimized.

  The hollow fiber membrane module of the present invention will be described below.

  The present inventors investigated and examined in detail the cause of the fact that a sufficient number of crimps cannot be firmly imparted to the hollow fiber membrane by conventional crimp imparting techniques other than the heat setting method.

  First, in the hollow fiber membrane module, a critical crimp element for securing a gap between the hollow fiber membranes and preventing a drift of the fluid flowing through the gap was examined. It is a wave shape or a similar shape imparted to the hollow fiber membrane, and the one that retains the wavy shape to the extent that the hollow fiber membrane is hung down vertically is called a crimp. It is evaluated by the number of crimps (the number existing per unit length of the hollow fiber membrane) and the amplitude (size of the hollow fiber membrane swinging perpendicular to the length direction). When both were examined, it was found that the number of crimps per unit length was more important than the amplitude of the crimps. That is, a module composed of hollow fiber membranes having a relatively small number of crimps is likely to cause channeling of the external perfusate because the contact between the hollow fiber membranes increases. On the other hand, in the case of a hollow fiber membrane having a crimp with a relatively large amplitude, the effect of reducing the contact between the hollow fiber membranes increases, but the size of the module must be increased because the diameter of the bundle of hollow fiber membranes increases. Sometimes. As a result of intensive studies by the present inventor, it was found that even if the amplitude is relatively small, contact between the hollow fiber membranes can be effectively suppressed by making the number of crimps within a specific range, which is effective for preventing drift. . Furthermore, the crimp that is not heat-fixed may lose its shape and function due to tension or other external force applied to the hollow fiber membrane in the post-process after crimping or modularization process, but the more the number of crimps, Since the influence of external force applied to one crimp is reduced, there is also an advantage that the crimp shape and function can be easily maintained.

  Therefore, when the crimping device was examined, the conventional device as shown in FIG. 8 has a pitch effective for increasing the number of crimps due to technical problems such as machining accuracy, assembly accuracy, and play of operation. It turned out to be difficult to narrow. Further investigations and investigations have been carried out, and it has succeeded in securing an effective pitch in terms of equipment by the method shown in FIG. 7, but particularly for hollow fiber membranes having a thin film thickness and relatively low strength. An effective crimp could not be given. Further, if the crimping is forcibly applied, there is a fatal problem that the hollow fiber membrane is flattened or blocked, and further, the membrane is damaged, and the quality and function of the hollow fiber membrane are lost.

As a result of a detailed investigation of the disappearance and relaxation of the crimp, one of the reasons is that the hollow fiber membrane is slipped at the portion sandwiched by the gear of the crimping device because the hollow fiber membrane is pulled in the step behind the crimping step. I found out that That is, the stress applied to the hollow fiber membrane is not concentrated in one point, but is dispersed in the length direction of the hollow fiber membrane, so that the crimps that appear to be applied are taken up, bundled, washed, dried, bundled It was found that the crimps were stretched during the storage period, and the production yield of the hollow fiber membrane module was lowered, and the performance of the hollow fiber membrane module could not be fully expressed.
Another reason is that slippage of the hollow fiber membrane cannot be avoided even when the hollow fiber membrane is sandwiched between the gears and rolls of the crimping device. In particular, when the hollow fiber membrane has traveled more freely than in the previous process, the slip at the biting portion becomes larger, the stress is not concentrated on one point, and the crimp is not fixed to the hollow fiber membrane. it was thought.
Then, as a result of earnestly examining the slip prevention of the hollow fiber membrane in the crimping device, the present inventors have determined that the hollow fiber membrane is formed on the outer peripheral surface of the roll before and after the hollow fiber membrane is sandwiched between at least a pair of rolls. By moving the rod along a certain distance or more, slipping between the rod and the hollow fiber membrane is suppressed, and by concentrating the pressure of the rod on one point of the hollow fiber membrane, it is extremely possible without adding energy such as heat. The inventors have found that a good crimp can be fixed to the hollow fiber membrane, and finally completed the present invention.

  The crimping in the present invention is preferably performed by sandwiching a hollow fiber membrane in an engagement portion between at least a pair of rolls provided with a large number of rods on the outer peripheral surface. At least a pair of rolls rotate at a constant speed, and a large number of rods are arranged on the outer peripheral surface of the roll, and the rods on the roll can be engaged with each other in a gear shape. It is configured not to touch. A crimp can be applied by sandwiching a hollow fiber membrane between the rolls. The rods are preferably arranged in parallel, but even if they are not geometrically completely parallel, if the gap can be provided so that the hollow fiber membrane is not crushed when the roll is bitten, Deviation may be acceptable. In the present invention, the crimp is imparted to the hollow fiber membrane by passing the pair of rolls once in a substantially S-shape, but the hollow fiber membrane may be run in an 8-shape using a pair of rolls. In addition, it is within the scope of the present invention to use a combination of three or more rolls and sequentially pass the meshing portions along the rotation of the rolls.

  In the present invention, the diameter of the roll is not particularly limited, but if it is too large, not only the equipment cost increases, but also the workability when passing the hollow fiber membrane between the rolls and the slackness of the hollow fiber membrane during running Thread breakage may occur. Moreover, if it is too small, it will be difficult to provide a sufficient number of rods on the roll, and not only the slip of the hollow fiber membrane may not be suppressed, but also the condition setting of the crimp imparting portion may be too sensitive. . Therefore, for example, assuming that crimping is applied to a hollow fiber membrane having an outer diameter of 0.1 to 0.5 mm, a roll outer diameter of about 10 to 50 cmφ is appropriate. Two or more such rolls are used in combination for crimping.

  The number of rods or protrusions varies depending on the size of the roll and what kind of wavelength and amplitude crimp is obtained, and is not particularly limited. However, when the number is extremely small, it is difficult to physically sandwich the hollow fiber membrane. Therefore, there is a possibility that an effective crimp cannot be given. On the other hand, when the number is extremely large, not only the equipment becomes enormous, but also operational problems such as loosening of the hollow fiber membrane and thread breakage may occur. Accordingly, the number is preferably 20 or more and 1000 or less, more preferably 50 or more and 300 or less.

  In the present invention, the rod provided on the outer peripheral surface of the roll is not particularly limited as long as the rod portion of the other roll can be engaged with the groove portion between the rods of the one roll in a gear shape. A large number of rods may be arranged in parallel on the outer peripheral surface, or a plurality of grooves and protrusions may be formed in parallel by scraping the outer peripheral surface of the roll instead of the rod. However, since the outer peripheral part of the protrusion formed by the rod or shaving is in direct contact with the hollow fiber membrane, the rod arranged on the outer peripheral surface is preferably cylindrical so that the hollow fiber membrane is not damaged, or the protrusion is It is preferable that it is formed in an arc shape along the traveling direction of the hollow fiber membrane. The surface of the rod and projection that contacts the hollow fiber membrane is preferably mirror-finished so that the hollow fiber membrane is not damaged by contact with the hollow fiber membrane and the hollow fiber membrane does not slip. Further, in the case of a rod, it is more preferable that the rod is designed to rotate along the travel of the hollow fiber membrane because damage to the hollow fiber membrane is further reduced. The material of the rod and the protrusion is not particularly limited, but is preferably made of stainless steel or aluminum from the viewpoint of workability and availability, and stainless steel is more preferred from the viewpoint of durability. Further, it is also within the scope of the present invention to use a material whose surface has been subjected to a coating treatment for improving corrosion resistance, anti-slip and abrasion resistance.

  In the present invention, the pitch between the rods or protrusions provided in the crimp applying device may be appropriately set according to the target number of crimps, but it is preferable that the pitch is as narrow as possible in order to ensure an effective number of crimps. However, if it is too narrow, it becomes difficult to secure a gap for sandwiching the hollow fiber membrane because of a decrease in workability and durability. is there. It is more convenient for manufacturing and maintenance that the pitch between the rods or the projections is equal, but the spacing may be changed intentionally as long as they can be engaged with each other in a gear shape. In addition, it is convenient for manufacturing and maintenance that the rod or the protrusion is arranged in parallel to the rotation axis of the cylindrical portion, but this may be changed intentionally as long as it can be engaged with each other in a gear shape. If it is changed too much, operational inconvenience may occur, but by arranging it slightly shifted from parallel to the rotation axis of the cylindrical part, the phase of the crimp is adjusted when simultaneously running a plurality of hollow fiber membranes in parallel. Since a shifting effect is expected, a higher drift prevention effect can be expected.

  If the diameter of the protrusion formed by cutting out the rod or groove is too large, it is difficult to ensure the above pitch, and if it is too small, the risk that the hollow fiber membrane breaks increases. Although it depends on the strength and elongation of the hollow fiber membrane, it is preferably 0.5 to 8.0 mmφ, more preferably 1.5 to 6.0 mmφ.

  In the present invention, when crimping the hollow fiber membrane, it is important to run the hollow fiber membrane along the outer peripheral surface of the roll (rod) before and after the biting portion of the roll. By adopting such a running configuration, the hollow fiber membrane is gripped without slipping at the biting portion of the roll, and the stress of the rod or protrusion is concentrated at one point of the hollow fiber membrane, so that an effective crimp can be imparted. As a result of further studies on this point, a certain interval is required from when the hollow fiber membrane contacts the crimp applying device until it passes through the meshing portion between the rolls and leaves the crimp applying device. When the preferred section is expressed by an angle around the rotation axis of the crimping device that travels while the hollow fiber membrane is in contact, it can be said that a total of 90 ° or more is sufficient. It is more preferable to take 45 ° or more before and after biting. When there are few sections that run while in contact, the hollow fiber membrane that passes through the meshing portion between the rolls may slip due to the tension received from winding or the subsequent process, and an effective crimp cannot be obtained. Sometimes. In addition, the yarn path where the section running in contact exceeds 720 ° is not only complicated, but also the workability when passing the hollow fiber membrane through the crimping device, the slackness of the thread, the thread breakage, etc. Operational risks may increase. Therefore, the section in which the hollow fiber membrane travels along the outer peripheral surface of the crimping device of the present invention is preferably 90 ° or more and 720 ° or less, more preferably 180 ° or more and 540 ° before and after the gear biting portion. ° or less.

Conventionally, hollow fiber membranes that have only been mechanically crimped without being heat-set may be loosened or lost during subsequent washing and drying processes, module production, and storage. The generation of problems could not be suppressed. Although the details of this reason are not known, when the hollow fiber membrane that has traveled for free enters the meshing portion of the gear or belt of the crimping device, the slip of the hollow fiber membrane at the meshing portion increases. When slip occurs in this way, stress is not concentrated on one point of the hollow fiber membrane, so that it is considered that a phenomenon occurs in which the crimp is relaxed in the external force that the hollow fiber membrane receives later or in post-processing.
In the present invention, by applying consideration to prevent slipping when the hollow fiber membrane enters the meshing portion of the crimping device, it is possible to provide a crimp that is strong and has good crimp retention for a long time without heat fixing. I guess it was possible.

  In the present invention, the number of crimps per 1 cm of the hollow fiber membrane is preferably 0.50 or more. In the prior art of the present inventors, the drift suppression effect of a hollow fiber membrane module produced using a hollow fiber membrane that has been crimped by bobbin winding and heat setting has a track record in clinical practice. The number of crimps of this bobbin wound product was targeted, and the lower limit of the number of crimps was within the above range. 0.60 piece / cm or more is more preferable, and 0.65 piece / cm or more is more preferable. A large number of crimps does not cause a particularly big problem, but if it is too large, the hollow fiber membrane bundle becomes bulky, and the compactness of the hollow fiber membrane module is lost. Considering the manufacturing cost, technical difficulty, and the effect obtained, it can be said that a sufficient effect is obtained when the actual number of crimps is 2.0 pieces / cm or less.

  The amplitude of the crimp applied to the hollow fiber membrane of the present invention is preferably 0.1 mm or more, more preferably 0.15 mm or more. When the amplitude of the hollow fiber membrane is too small, the module assemblability deteriorates due to the displacement of the hollow fiber membrane in the module assembly process, or the small molecular weight such as urea due to the close contact between the hollow fiber membranes and the drift of the dialysate during use. Decreased material permeation performance may occur. On the other hand, there is no merit if the amplitude of the crimp becomes too large, and the surface of the hollow fiber membrane is damaged due to the increased resistance when the bundle of hollow fiber membranes is inserted into the module case in the module assembly process. The possibility of occurrence of a leak increases, and the meandering is large, so that more hollow fiber membrane raw material is required, resulting in an increase in cost. In some cases, the module case must be enlarged. Therefore, the amplitude of the crimp is preferably 1.0 mm or less, more preferably 0.7 mm or less, still more preferably 0.5 mm or less, and even more preferably 0.3 mm or less.

Further, as a result of intensive studies, the present inventor has found that the crimp strength can be determined by using the following crimp index as an index. In other words, when the amplitude of the crimp applied to the hollow fiber membrane is A (mm), the number of crimps is X (pieces / cm), and the outer diameter of the hollow fiber membrane is D (mm), the crimp index is A × X ^It was expressed by ² / D, and when this crimp index was small, it was confirmed that an effective crimp could not be imparted. Therefore, the crimp index in the present invention is preferably 0.30 or more, more preferably 0.35 or more, still more preferably 0.40 or more, and even more preferably 0.45 or more. A stronger crimp can be obtained by increasing the crimp index, but if it is too large, the hollow fiber membrane bundle may become too bulky when assembling the module, which may cause leaks. If the length becomes longer, problems such as an increase in raw material costs occur. Further, considering the technical technical difficulty and the manufacturing cost, 10 or less is appropriate, preferably 5 or less, more preferably 3 or less, and further preferably 2 or less.

The hollow fiber membrane module produced using the hollow fiber membrane of the present invention has an average urea clearance measured using five hollow fiber membrane modules of 170 ml / min / m ² and a standard deviation of less than 10.0. It is. That is, the permeation performance of the hollow fiber membrane can be exhibited without loss due to the high drift current suppressing effect, which means that high urea clearance can be expressed and there is little variation. If the average value of urea clearance is below 170 ml / min / m ² , for example, when hemodialysis is performed, the small molecule substance that is to be removed cannot be efficiently removed, and the clinical effect may be reduced. There is concern about the burden on patients. The average value of urea clearance is more preferably 175 ml / min / m ² . In addition, when the standard deviation is 10.0 or more, the variation increases, so there are modules that can exhibit high urea clearance and some modules that have very low urea clearance, for example, clinical effects during hemodialysis Since it is very difficult to predict in advance, there is a possibility of hindering actual use. The standard deviation is more preferably less than 8.0, and even more preferably less than 7.0. FIG. 10 shows a general tendency in the relationship between the aforementioned crimp index and the average value and standard deviation of urea clearance.

  In the present invention, it is preferable that the retention ratio of the crimp index of the hollow fiber membrane before and after back pressure washing with a chemical solution is 70% or more. The crimp index after chemical cleaning is 70% or more of that before cleaning. In other words, the degree of disappearance of crimp even when external force is applied by various treatments such as washing with water, filling with chemicals, washing, and rinsing. This means that the hollow fiber membrane is provided with a strong and highly permanent crimp. This is preferable because the hollow fiber membrane has a sufficient crimp even after back-pressure washing with a chemical solution, and can retain high permeability even when the hollow fiber membrane module is reused. If the retention ratio of the crimp index is less than 70%, the crimp is relaxed or lost by back pressure washing with a chemical solution, and when the hollow fiber membrane module is reused, the permeation performance decreases due to drift. As a result, there is a possibility that the variation in performance of each hollow fiber membrane module becomes large. The retention ratio of the crimp index is more preferably 75% or more, and further preferably 80% or more.

As an example of the cleaning method in the present invention, cleaning in a process as shown below using a chemical solution consisting of 17% by weight of hydrogen peroxide, 9% by weight of peracetic acid, 7% by weight of acetic acid and 67% by weight of water is given. It is done.
1) Wash the outside of the hollow fiber membrane with 250 ml of sterile water.
2) The inside of the hollow fiber membrane is washed with sterile water for 20 seconds at a flow rate of 6 L / min.
3) Backwash with a chemical diluted to 2% by weight for 35 seconds.
4) Rinse the inside of the hollow fiber membrane with a chemical solution diluted to 2% by weight.
5) Fill the hollow fiber membrane with a drug solution diluted to 2% by weight for 120 seconds.
6) Rinse the outside of the hollow fiber membrane with sterile water at a flow rate of 1 L / min for 15 seconds.
7) Rinse the inside of the hollow fiber membrane with sterile water at a flow rate of 6 L / min for 30 seconds.
8) Rinse the inside of the hollow fiber membrane with sterile water at a flow rate of 1 L / min for 40 seconds.
9) Drain sterile water.
10) Rinse the outside of the hollow fiber membrane with sterile water at a flow rate of 1 L / min for 15 seconds.
11) Rinse the inside of the hollow fiber membrane with sterile water at a flow rate of 6 L / min for 6 seconds.
12) Rinse the outside of the hollow fiber membrane with 700 ml of a chemical solution diluted to 3.25% by weight.
13) Rinse the inside of the hollow fiber membrane with 700 ml of a chemical solution diluted to 3.25% by weight.

  If the retention ratio of the crimp index after washing is 70% or more, the average urea clearance after washing can be kept at 170 ml / min or more. FIG. 11 shows the relationship between the crimp index retention after cleaning and the average of urea clearance using the data of the present example and the comparative example. From FIG. 11, it can be seen that if the retention rate of the crimp index after washing is high, the average urea clearance can be kept high. This keeps the average of the drift value after washing low, leading to a reduction in performance variation among the hollow fiber membrane modules, and even between different hollow fiber membrane modules even by washing. This will lead to the performance.

  In the present invention, the roundness of the hollow fiber membrane is preferably 0.75 or more. When the roundness of the hollow fiber membrane is lowered, useless pressure loss occurs when the liquid to be treated flows into the hollow portion, and the performance as a hollow fiber membrane module may be deteriorated. Therefore, the higher the roundness, the better, and 0.80 or more is more preferable.

  The number of collapses of the hollow fiber membranes observed on the end surface of the hollow fiber membrane module of the present invention is preferably 1.0% or less of the total number. If the hollow fiber membrane is crushed, not only the wasteful pressure loss described above will occur, but in severe cases, the liquid to be treated will hardly pass through the hollow part, which may cause significant membrane performance degradation and residual blood. There is. Therefore, it is preferable that the hollow fiber membrane is less crushed.

  The diameter and film thickness of the hollow fiber membrane in the present invention are appropriately selected depending on the module design, membrane material, etc. If the diameter is too large, it is difficult to ensure the clearance between the rods of the crimping device, and the diameter is too small. The outer diameter is preferably 0.1 mm or more and 0.5 mm or less, more preferably 0.15 mm or more and 0.3 mm or less, and further preferably 0.2 mm or more and 0.3 mm or less. mm or less.

  Also, if the film thickness is made too thin, it will be difficult to provide effective crimping and maintain the quality of the hollow fiber membrane even if the present invention is applied. Conversely, if it is made too thick, the raw material cost will be increased and the performance as a membrane module will be reduced. Therefore, the preferable film thickness is 10 μm or more and less than 150 μm, more preferably 15 μm or more and less than 100 μm, still more preferably 15 μm or more and less than 70 μm, and still more preferably 20 μm or more and less than 40 μm.

  Regarding the structure of the hollow fiber membrane in the present invention, the ratio of the pore diameters on the inside and outside of the hollow fiber membrane represented by (outside pore diameter) / (inside pore diameter) is preferably 2 or more. That is, an asymmetric membrane with different pore diameters on the outside and inside is generally difficult to produce in the form of cheese because an aqueous solution is generally used as the core liquid, and it has been difficult to impart an effective crimp with the prior art. Since the effect of invention is acquired more highly, it is preferable.

  In the present invention, the ratio of the true length of the hollow fiber membrane expressed by (true length) / (apparent length) to the apparent length is 1.0 or more and 1.2 or less. Since the hollow fiber membrane meanders by applying the crimp, the true length is substantially slightly longer than the apparent length. However, when a crimp with a large meandering is applied so that the length ratio exceeds 1.2, it becomes too bulky and causes problems such as leak generation at the time of assembling the module, and the raw material cost increases.

In the present invention, using five hollow fiber membrane modules with an inner diameter reference membrane area of 1.5 m ² , the urea clearance when measured at a dialysate flow rate of 500 ml / min is CL500, and when measured at a dialysate flow rate of 2000 ml / min. When the urea clearance converted from the urea clearance to the value at a dialysate flow rate of 500 ml / min via the overall mass transfer coefficient is CL2000, the average of the drift value represented by CL2000-CL500 may be less than 7 ml / min. preferable. The drift value is an index for seeing the deviation (stagnation) of the flow of the dialysate. When the dialysate flow rate is increased, the linear velocity of the dialysate flowing between the hollow fiber membranes is increased, so that the flow is less likely to occur. For this reason, the approximate drift state can be known by comparing the clearance at the normal dialysate flow rate (500 ml / min) with the converted value of the clearance when the dialysate flow rate is increased. When the dialysate causes a drift, even if the performance of the hollow fiber membrane itself is high, the performance cannot be sufficiently exhibited, and the permeability of the substance to be removed having a low molecular weight is significantly affected.
FIG. 12 shows the relationship between the drift value and the variation in urea clearance between the hollow fiber membrane modules using the data of the present embodiment example and the comparative example. It can be seen that the variation in performance among the hollow fiber membrane modules tends to decrease as the drift value decreases. If the drift value is less than about 7 ml / min, the dispersion in performance among the hollow fiber membrane modules is concentrated in a very small set, and it is easy for such a drift value to have a critical significance. Understandable.

  In the present invention, the depth of the meshing portion where the crimp applying device sandwiches the hollow fiber membrane is the diameter of the rod or the projection, or their pitch, and further the strength and elongation of the hollow fiber membrane, the outer diameter, the desired crimp. What is necessary is just to set suitably by the amplitude of this. If the depth of the meshing portion is too shallow, an effective crimp cannot be imparted, and conversely if too deep, problems such as flatness of the hollow fiber membrane, loosening during running, and thread breakage may occur. The depth of the mating portion is not less than 0.5 mm and not more than 5.0 mm.

  In addition, since an effective crimp cannot be imparted when the hollow fiber membrane is completely relaxed, it is necessary to apply an appropriate tension to the crimp imparting portion, but the strength of this is also the strength of the crimp imparting device. An appropriate strength is appropriately selected according to the diameter of the rod or the protrusion, or their pitch, the strength and elongation of the hollow fiber membrane, the outer diameter, and the like. It can be adjusted according to the rotation speed and the biting depth of the crimping device, and in order to impart the crimp effectively, it is preferable to set so that the most deformed portion is higher than the yield strength of the film and less than the breaking strength. . Specifically, it is preferable to give a tension of 0.5 to 50 gf per hollow fiber membrane.

  In the present invention, the speed of the hollow fiber membrane that runs through the crimping device is not particularly limited as long as it is a speed that does not cause a problem in winding of the hollow fiber membrane. Considering the impact on the environment, 5 ~ 200m / min is appropriate.

  Further, in the present invention, a plurality of hollow fiber membranes that pass through the crimping device may be run together, but if there are too many bundles, the apparent diameter increases, The gap between the rods is not sufficiently secured, and flattening and blockage are likely to occur. Moreover, even if crimps are applied in a collective state, the crimp phase is synchronized, so that it is difficult to break, and the effects of the present invention may not be obtained. Therefore, when collecting the hollow fiber membranes when the crimping device is run, the number is preferably 10 or less, more preferably 4 or less. It is more preferable to run with a single yarn without putting them together.

  The material of the hollow fiber membrane in the present invention is not particularly limited, and examples thereof include cellulose derivatives or polysulfone or polyacrylonitrile polymers, polyamides, polymethyl methacrylate, ethylene vinyl alcohol copolymers, etc. A cellulose derivative or a polysulfone-based or polyacrylonitrile-based polymer has a high effect of the present invention and can be suitably used because it can exhibit permeation performance.

  Further, the hollow fiber membrane obtained by the present invention is assembled as a hollow fiber membrane module in a bundle of 1000 to 20000, but an appropriate number is selected depending on the housing diameter of the module and the outer diameter of the hollow fiber membrane. The When the filling rate is defined as (hollow fiber membrane outer shape) × (number of hollow fiber membranes) / (module housing end inner diameter) × 100 (%), the preferred filling rate is 30% to 75%. When the filling rate is smaller than 30%, an effective membrane area cannot be obtained for the module size, which is inefficient and the effect of the present invention is also small. On the other hand, when the filling rate increases to exceed 75%, the hollow fiber membranes in the module housing are in close contact with each other, and it is difficult not only to physically obtain a gap between the hollow fiber membranes, but also to be inserted into the case. This may cause other problems such as damage to the film due to contact. The filling rate is more preferably 40 to 70%, further preferably 45 to 70%, and still more preferably 52 to 65%.

  Hereinafter, preferred embodiments of the present invention will be described with reference to Examples. However, the present invention is not limited by these.

(Measurement method of hollow fiber membrane inner diameter and film thickness)
A sample of the cross section of the hollow fiber membrane can be obtained as follows. For the measurement, it is preferable to observe in a form in which the hollow fiber membrane is dried after washing and removing the core liquid. There is no limitation on the drying method. However, when the shape changes remarkably by drying, it is preferable to clean and remove the hollow forming material and then completely replace with pure water, and then observe the shape in a wet state. The inner diameter, outer diameter, and film thickness of the hollow fiber membrane are cut through a razor on the upper and lower surfaces of the slide glass so that the hollow fiber membrane does not fall out into the 3mmφ hole in the center of the slide glass. Then, after obtaining a hollow fiber membrane cross-section sample, it is obtained by measuring the short diameter and long diameter of the hollow fiber membrane cross section using a projector Nikon-12A. Measure the short axis and long axis in two directions for each cross section of hollow fiber membrane, and calculate the arithmetic average value of each as the inner diameter and outer diameter of one hollow fiber membrane cross section. The film thickness is calculated as (outer diameter-inner diameter) / 2. did. The same measurement was performed on five cross sections, and the average value was defined as the inner diameter and film thickness.

(Measurement method of the number of crimps)
The number of crimps imparted to the hollow fiber membrane is the reciprocal of the crimp wavelength (length from the crest to the crest), and was measured as follows. When the hollow fiber membrane is cut out about 20cm and placed so that the length direction of the hollow fiber membrane is vertical, the number of peaks on the wavy part is counted (the number of valleys is not counted) The number per unit length was calculated from the length of the cut hollow fiber membrane. The same measurement was performed on five hollow fiber membranes, and the average value was taken. At this time, the apparent length when the hollow fiber membrane is hung vertically downward is used as the length of the hollow fiber membrane.

(Crimping amplitude measurement method)
The amplitude of the crimp applied to the hollow fiber membrane was measured as follows. The hollow fiber membrane was cut out by 10 to 30 cm, and the wobbling portion was measured with respect to the length direction of one crest and the next trough, and a half value was calculated. The same measurement was performed on five hollow fiber membranes, and the average value was taken.

(Measurement method of roundness of hollow fiber membrane)
In order to evaluate the flatness of the hollow fiber membrane, the roundness of the hollow fiber membrane was measured. The roundness is the ratio of the minor axis / major axis of the inner diameter of the hollow fiber membrane in the cross section of the hollow fiber membrane. For example, the circularity is 1 for a perfect circle. Using an image analysis software “Image-Pro Plus” (Media Cybernetics), measurement was performed by image analysis on an arbitrary 100 cross-sections of hollow fiber membranes in the module end face, and the average value was obtained.

(Measurement method of hollow fiber membrane crushing)
In order to evaluate the blockage of the hollow fiber membrane, the collapse of the hollow fiber membrane was measured. Hollow fiber membrane crushing is defined as the extreme flatness of the minor axis / major axis ratio of the hollow fiber inner diameter in the hollow fiber membrane cross section being less than 1/3 or the hollow part being substantially collapsed. The number present in the end face was counted, and the existence ratio was determined from the total number of hollow fiber membranes contained in the end face.

(Measurement method of the ratio of the true length of the hollow fiber membrane to the apparent length)
The ratio of the true length of the hollow fiber membrane to the apparent length was measured as follows. The hollow fiber membrane was cut out by 10 to 30 cm, allowed to stand in a straight line without applying tension, enlarged at a magnification of 10 to 100 times, and printed on A4 paper. Next, hit the yarn along the hollow fiber membrane printed on A4 paper, and from the length of the yarn and the straight length of the measured part, the true length of the hollow fiber membrane and the apparent length Ratio. When the yarn was applied along the hollow fiber membrane, the measurement was performed so that the yarn was applied to the center in the radial direction of the hollow fiber membrane.
(True length) / (appearance length) = (length of yarn along hollow fiber membrane) / (straight length)
The magnification is suitably set according to the diameter of the hollow fiber membrane, and it is desirable that there are five or more crimp peaks in the paper.

(Measurement method of urea clearance of hollow fiber membrane module)
The urea clearance of the hollow fiber membrane module was measured according to the dialyzer performance evaluation standard published by the Japanese Society for Dialysis Medicine and converted to a value per membrane area of 1.0 m ² .
It was dissolved in dialysate (Kindaly diluted solution) at a concentration of 1.0 g / L of urea to obtain a measurement solution. A 37 ° C measurement solution (hereinafter referred to as B solution) is introduced at a rate of 200 ml / min from the blood side inlet of the module, and a dialysis solution (hereinafter referred to as D solution) maintained at 37 ° C from the dialysate side inlet is 500 ml / min. It was introduced countercurrently to the B liquid at min. B liquid inlet and outlet pressure (P _Bi and P _Bo respectively) and D liquid inlet and outlet pressure (P _Di and P _Do respectively) are measured, and the transmembrane pressure difference (TMP) 100mmHg shown in Equation 1 Measurements were made at
TMP = (P _Bi + P _Bo ) / 2− (P _Di + P _Do ) / 2 (Formula 1)
While confirming that there was no flow rate change during the measurement, the liquid at the inlet and outlet of the liquid B and the liquid at the outlet of the liquid D were sampled. The concentration of the sampling solution was determined using Urea Nitrogen Test Wako B manufactured by Wako Pure Chemical Industries, and clearance (CL) was calculated from these values using Equation 2.
CL = (C _Bi × Q _Bi −C _Bo × Q _Bo ) / C _Bi (Formula 2)
Where C _Bi is the B solution inlet solute concentration (g / ml), Q _Bi is the B solution inlet flow rate (ml / min), C _Bo is the B solution outlet solute concentration (g / ml), Q _Bo is the B solution outlet Flow rate (ml / min). For these values, those with a mass balance error (MBE) of 5% or less were adopted. MBE was calculated from Equation 3 below.
MBE = (Q _Bi x C _Bi- Q _Bo x C _Bo- Q _Do x C _Do ) / (Q _Bi x C _Bi- Q _Bo x C _Bo ) (Formula 3)
Here, Q _Do is the D solution outlet flow rate, and C _Do is the D solution outlet concentration.

(Measurement method of module drift value)
The drift value of the hollow fiber membrane module was measured by the following method. As for the drift value, the clearance C2 of urea (molecular weight 60) is measured under a high dialysate flow rate condition (2000 ml / min), and the overall mass transfer coefficient K _O is calculated by Equation 4. Calculate the urea clearance C3 at 500 ml / min using Equation 5 from the overall mass transfer coefficient K _O. Then, the urea clearance C1 of 500 ml / min is actually measured, and the difference from the calculated value is compared. If there is a biased flow, dialysate flow rate high conditions of overall mass transfer coefficients K _O from the calculated urea clearance is higher than the measured value of a low dialysis flow conditions. That is, the drift value is defined as C3−C1. The smaller the drift value, the less the stagnation of the dialysate and the higher the dialysis efficiency.
Q _B , Q _D : Blood flow, dialysate flow (ml / min)
K _O : Overall mass transfer coefficient (cm / min)
S: Membrane area (inside diameter)

In addition, clearance measurement conforms to dialyzer performance evaluation standard (Japanese Society for Artificial Organs 1982), blood side is urea 100mg / dl physiological saline solution, dialysate is physiological saline, temperature 37 ℃ ± 1 ℃, It measured on the conditions which do not produce filtration. The clearances C1 and C2 were measured at a blood flow rate of 200 ml / min and a dialysate flow rate of 500 ml / min and 2000 ml / min. Using the value of C2, the overall mass transfer coefficient K _O was determined from Equation 4. Solute clearance C in the blood when the blood and dialysate are allowed to flow alternatingly is expressed by Equation 5. The clearance C3 at the dialysis flow rate of 500 ml / min was calculated by substituting the overall mass transfer coefficient K _O obtained from Equation 4 using the value of C2 into Equation 5.

Example 1
Polyethersulfone (Sumitomo Chemtec Co., Ltd. Sumika Excel (registered trademark) 4800P) 18.0 mass%, Polyvinylpyrrolidone (BASF Kollidon (registered trademark) K-90) 3.0 mass%, non-solvent 5.5 mass% water, dimethyl solvent A solution in which 73.5% by mass of acetamide was uniformly dissolved was used as a spinning dope, and a 44.0% by mass aqueous dimethylacetamide solution was used as a core solution. Using a spinneret with a double-pipe structure, a spinning stock solution was discharged from the outside, and a core solution was discharged from the inside in a vertically downward direction to form a hollow fiber membrane. After passing through a steam atmosphere of 600 mm in length, it is immersed in a coagulation bath, passed through a washing bath and a hot water bath, then passed through a crimping device with a single yarn, and wound with a casserole at a winding speed of 40 m / min. It was. At that time, the yarn path passing through the crimping device is S-shaped as shown in FIG. 4 (the angle at which the hollow fiber membrane runs along the roll before and after the roll biting portion of the crimping device: about 180 before biting. And about 180 ° after biting), and at a middle part, the crimping device was sandwiched between φ2.0 mm rods arranged at a pitch of 7.9 mm with a biting depth of 2.5 mm. The tension in the crimping device was 1.0 gf per hollow fiber membrane.
A bundle of 10,000 wound hollow fiber membranes was inserted into a polyethylene pipe, cut into a predetermined length to obtain a bundle, and dried. The hollow fiber membrane was taken out from the dried bundle, and the crimp was measured. Moreover, the bundle after drying was assembled in the module, and crush evaluation and urea clearance measurement were performed.
The results are shown in Tables 1 and 2.

(Example 2)
A hollow fiber membrane was formed in the same manner as in Example 1, and wound with a cassette at a winding speed of 75 m / min. As shown in FIG. 5, the yarn path passing through the crimping device has a saddle shape (the angle at which the hollow fiber membrane runs along the roll before and after the roll biting portion of the crimping device: about 90 ° before biting, biting After that, it was sandwiched between the φ2.0 mm rods arranged at a pitch of 4.8 mm in the middle part of the crimping device with a biting depth of 1.0 mm. The tension in the crimping device was 1.6 gf per hollow fiber membrane.
A bundle of 10100 wound hollow fiber membranes was inserted into a polyethylene pipe, cut into a predetermined length to obtain a bundle, and dried. The hollow fiber membrane was taken out from the dried bundle, and the crimp was measured. Moreover, the bundle after drying was assembled in the module, and crush evaluation and urea clearance measurement were performed.
The results are shown in Tables 1 and 2.

(Example 3)
As the spinning dope, 19.2% by mass of cellulose triacetate manufactured by Daicel Chemical Industries, 68.7% by mass of N-methyl-2-pyrrolidone, and 12.1% by mass of triethylene glycol were mixed and dissolved at 180 ° C. This was discharged vertically downward from the outer annular part of the spinneret with a double pipe structure. At the same time, water was supplied to the inner tube as a core liquid to form a hollow fiber membrane. After passing through a 35 mm steam atmosphere, this hollow fiber membrane was passed through a coagulation bath and a water washing bath, then passed through a crimping device with a single yarn, and wound with a casserole at a winding speed of 60 m / min. At that time, the yarn path passing through the crimping device is S-shaped as shown in FIG. 6 (the angle at which the hollow fiber membrane runs along the roll before and after the roll biting portion of the crimping device: about 210 ° before biting) , About 210 ° after biting), and between the rods of φ2.0 mm arranged at a pitch of 7.9 mm in the middle portion of the crimping device, the biting depth was 3.5 mm. The tension in the crimping device was 1.3 gf per hollow fiber membrane.
A bundle of 10800 wound hollow fiber membranes was inserted into a polyethylene pipe, cut into a predetermined length to obtain a bundle, and dried. The hollow fiber membrane was taken out from the dried bundle, and the crimp was measured. Moreover, the bundle after drying was assembled in the module, and crush evaluation and urea clearance measurement were performed.
The results are shown in Tables 1 and 2.

Example 4
A hollow fiber membrane was formed in the same manner as in Example 1, and wound with a cassette at a winding speed of 45 m / min. The yarn path passing through the crimping device was formed in an S shape as shown in FIG. 4, and the hollow fiber membrane was sandwiched between φ3.5 mm rods with a depth of 3.0 mm. The pitch between the rods was 7.9 mm. The tension in the crimping device was 0.9 gf per hollow fiber membrane.
A bundle of 10100 wound hollow fiber membranes was inserted into a polyethylene pipe, cut into a predetermined length to obtain a bundle, and dried. The hollow fiber membrane was taken out from the dried bundle, and the crimp was measured. Moreover, the bundle after drying was assembled in the module, and crush evaluation and urea clearance measurement were performed.
The results are shown in Tables 1 and 2.

(Example 5)
Polyethersulfone (Sumitomo Chemtec Co., Ltd. Sumika Excel (registered trademark) 4800P) 16.5% by mass, Polyvinylpyrrolidone (BASF Koridone (registered trademark) K-90) 3.0% by mass, non-solvent 6.0% by mass water, dimethyl solvent A solution in which 74.5% by mass of acetamide was uniformly dissolved was used as a spinning dope, and a 43.0% by mass dimethylacetamide aqueous solution was used as a core solution. Using a spinneret with a double-pipe structure, a spinning stock solution was discharged from the outside, and a core solution was discharged from the inside in a vertically downward direction to form a hollow fiber membrane. After passing through a 500 mm long steam atmosphere, immersed in a coagulation bath, passed through a washing bath and hot water bath, passed through a crimping device with a single yarn, and wound with a casserole at a winding speed of 40 m / min. It was. At that time, the yarn path passing through the crimping device is S-shaped as shown in FIG. 4 (the angle at which the hollow fiber membrane runs along the roll before and after the roll biting portion of the crimping device: about 180 before biting. And about 180 ° after biting), and at a middle portion, the crimping device was sandwiched between φ2.0 mm rods arranged at a pitch of 4.8 mm with a biting depth of 1.0 mm. The tension in the crimping device was 1.0 gf per hollow fiber membrane.
A bundle of 10100 wound hollow fiber membranes was inserted into a polyethylene pipe, cut into a predetermined length to obtain a bundle, and dried. The hollow fiber membrane was taken out from the dried bundle, and the crimp was measured. Moreover, the bundle after drying was assembled in the module, and crush evaluation and urea clearance measurement were performed.
The results are shown in Tables 1 and 2.

(Example 6)
A hollow fiber membrane was formed in the same manner as in Example 3, and wound with a skein at a winding speed of 60 m / min. At that time, the yarn path passing through the crimping device is S-shaped as shown in FIG. 4 (the angle at which the hollow fiber membrane runs along the roll before and after the roll biting portion of the crimping device: about 180 before biting. And about 180 ° after biting), and at a middle portion, the crimping device was sandwiched between φ2.0 mm rods arranged at a pitch of 4.8 mm with a biting depth of 1.0 mm. The tension in the crimping device was 1.3 gf per hollow fiber membrane.
A bundle of 9600 wound hollow fiber membranes was inserted into a polyethylene pipe, cut into a predetermined length to obtain a bundle, and dried. The hollow fiber membrane was taken out from the dried bundle, and the crimp was measured. Moreover, the bundle after drying was assembled in the module, and crush evaluation and urea clearance measurement were performed.
The results are shown in Tables 1 and 2.

(Comparative Example 1)
A hollow fiber membrane was formed in the same manner as in Example 1, and wound with a cassette at a winding speed of 40 m / min. As a crimping device, a belt-like facility having a number of rods on the upper and lower sides as shown in FIG. 7 was used, and the hollow fiber membrane was sandwiched between φ4.5 mm rods and sandwiched at a depth of 4.5 mm. The pitch between the rods was 20.0 mm. The tension in the crimping device was 2.6 gf per hollow fiber membrane.
A bundle of 10100 wound hollow fiber membranes was inserted into a polyethylene pipe, cut into a predetermined length to obtain a bundle, and dried. The hollow fiber membrane was taken out from the dried bundle, and the crimp was measured. Moreover, the bundle after drying was assembled in the module, and crush evaluation and urea clearance measurement were performed.
The results are shown in Tables 1 and 2.

(Comparative Example 2)
A hollow fiber membrane was formed in the same manner as in Example 3, and wound with a cassette at a winding speed of 60 m / min. The yarn path passing through the crimping device was straight as shown in FIG. 8, and the crimping device was sandwiched between φ2.0 mm rods arranged at a pitch of 7.9 mm with a biting depth of 4.0 mm. The tension in the crimping device was 1.3 gf per hollow fiber membrane.
A bundle of 10800 wound hollow fiber membranes was inserted into a polyethylene pipe, cut into a predetermined length to obtain a bundle, and dried. The hollow fiber membrane was taken out from the dried bundle, and the crimp was measured. Moreover, the bundle after drying was assembled in the module, and crush evaluation and urea clearance measurement were performed.
The results are shown in Tables 1 and 2.

(Comparative Example 3)
A hollow fiber membrane was formed in the same manner as in Example 3, and wound with a cassette at a winding speed of 60 m / min. At that time, the yarn path passing through the crimping device is curved at the crimping portion as shown in FIG. 9 (the angle at which the hollow fiber membrane runs along the roll before and after the roll biting portion of the crimping device: biting At about 30 ° before and about 30 ° after biting), the crimping device was sandwiched between the φ2.0 mm rods arranged at a pitch of 7.9 mm at a middle depth of 3.5 mm. The tension in the crimping device was 1.2 gf per hollow fiber membrane.
A bundle of 10800 wound hollow fiber membranes was inserted into a polyethylene pipe, cut into a predetermined length to obtain a bundle, and dried. The hollow fiber membrane was taken out from the dried bundle, and the crimp was measured. Moreover, the bundle after drying was assembled in the module, and crush evaluation and urea clearance measurement were performed.
The results are shown in Tables 1 and 2.

(Comparative Example 4)
A hollow fiber membrane was formed in the same manner as in Example 5, and wound with a cassette at a winding speed of 40 m / min. The yarn path passing through the crimping device is also S-shaped as in Example 5 (the angle at which the hollow fiber membrane runs along the roll before and after the roll biting portion of the crimping device: about 180 ° before biting, biting 180mm after insertion), and in the middle part, it was sandwiched between φ2.0mm rods arranged at a pitch of 4.8mm respectively in the crimping device, but the biting depth at that time was as shallow as 0.4mm Set. The tension in the crimping device was 1.0 gf per hollow fiber membrane.
A bundle of 10800 wound hollow fiber membranes was inserted into a polyethylene pipe, cut into a predetermined length to obtain a bundle, and dried. The hollow fiber membrane was taken out from the dried bundle, and the crimp was measured. Moreover, the bundle after drying was assembled in the module, and crush evaluation and urea clearance measurement were performed.
The results are shown in Tables 1 and 2.

(Comparative Example 5)
A hollow fiber membrane was formed in the same manner as in Example 3, and wound with a skein at a winding speed of 60 m / min. As a crimping device, a belt-like equipment having a large number of upper and lower rods as shown in FIG. 7 was used, and the hollow fiber membrane was sandwiched between φ4.5 mm rods with a depth of 6.0 mm. The pitch between the rods was 20.0 mm. The tension in the crimping device was 2.3 gf per hollow fiber membrane.
A bundle of 9600 wound hollow fiber membranes was inserted into a polyethylene pipe, cut into a predetermined length to obtain a bundle, and dried. The hollow fiber membrane was taken out from the dried bundle, and the crimp was measured. Moreover, the bundle after drying was assembled in the module, and crush evaluation and urea clearance measurement were performed.
The results are shown in Tables 1 and 2.

  As apparent from Examples 1 to 6 and Comparative Examples 1 to 5, by using the present invention, it is possible to prevent poor adhesion at the time of module assembly, and to suppress poor quality of the hollow fiber membrane such as flatness and blockage. It can be seen that both stable and high dialysis efficiency can be achieved.

  According to the method for producing a hollow fiber membrane of the present invention, it is possible to provide an effective crimp for reducing adhesion failure when assembling a hollow fiber membrane module and preventing drift when the module is used, so that stable and high permeation performance can be expressed. It becomes possible to obtain a hollow fiber membrane with a high yield. In addition, when crimping is mechanically applied, the risk of flattening, crushing, and breakage of the hollow fiber membrane has been a big problem in the past, but the production method of the present invention suppresses the occurrence frequency of such defective products. Is possible. Furthermore, the energy required for heat fixing is not required, which is effective for cost saving and simplification of equipment. Therefore, it is suitable as a method for producing a hollow fiber membrane that is particularly required to maintain its quality, and can greatly contribute to the industry.

It is a schematic diagram which shows the amplitude and wavelength of a crimp in this invention. It is an example which shows the whole hollow fiber membrane manufacturing process of this invention. It is an enlarged view which shows one example of the crimp provision apparatus of this invention. It is a schematic diagram which shows an example of the positional relationship of a pair of roll, and the travel path | route of a hollow fiber membrane. It is a schematic diagram which shows another embodiment of this invention. It is a schematic diagram which shows another embodiment of this invention. 6 is a schematic diagram showing an embodiment of Comparative Example 1. FIG. 6 is a schematic diagram showing an embodiment of Comparative Example 2. FIG. 10 is a schematic diagram showing an embodiment of Comparative Example 3. FIG. It is the figure which showed the average value and standard deviation of urea clearance with respect to a crimp index | exponent. The schematic diagram which shows the relationship between the crimp index retention in this invention, and the post-washing drift value. The schematic diagram which shows the relationship between the drift value and performance standard deviation in this invention.

Explanation of symbols

1: Rod 2: Pitch between rods 3: Biting depth

Claims (6)

A hollow fiber membrane module filled with a hollow fiber membrane provided with a crimp,
(A) Using five hollow fiber membrane modules with an inner diameter reference membrane area of 1.5 m ² , the urea clearance when measured at a dialysate flow rate of 500 ml / min is CL500, and when measured at a dialysate flow rate of 2000 ml / min When the urea clearance converted from the urea clearance to the value at a dialysate flow rate of 500 ml / min through the overall mass transfer coefficient is CL2000, the average of the drift value represented by CL2000-CL500 is less than 7 ml / min,
(B) A hollow fiber membrane module, wherein the average of the drift value after back pressure washing with a chemical solution is less than 13 ml / min. When the crimp amplitude is A (mm), the number of crimps is X (pieces / cm), and the outer diameter of the hollow fiber membrane is D (mm), the crimp index represented by A × X ² / D is 0.30 ~ The hollow fiber membrane module according to claim 1, wherein the hollow fiber membrane module is 10.   The amplitude (A) of the crimp of the hollow fiber membrane is 0.1 to 1.0 mm, the number of crimps per hollow fiber membrane length (X) is 0.5 to 2.0 pieces / cm, and the outer diameter is 0.1 to 0.5 mm. The hollow fiber membrane module described in 1.   The hollow fiber membrane module according to any one of claims 1 to 3, wherein a filling rate of the hollow fiber membrane is 45 to 75%.   The hollow fiber membrane module according to any one of claims 1 to 4, wherein the retention rate of the crimp index of the hollow fiber membrane before and after back pressure washing with a chemical solution is 70% or more.   The hollow fiber membrane module according to any one of claims 1 to 5, wherein the chemical solution contains one or more selected from hydrogen peroxide, peracetic acid, and acetic acid.