JPS6231962B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention involves loading a plurality of hollow fibers into a predetermined loading area within a case, then fixing (potting) both ends of the plurality of hollow fibers with a solidifying liquid (potting material), and then fixing the fixed portions (potting material). The present invention relates to a method for manufacturing a hollow fiber type mass transfer device in which both ends of the plurality of hollow fibers are opened by cutting the plurality of hollow fibers. Conventionally, this type of device has been constructed between a hollow portion, which is the inside of the wall membrane of the hollow fibers, and an outside of the wall membrane of the hollow fibers.
Substances are moved through this wall membrane by dialysis, immersion, ultrafiltration, etc. Such a device is useful as a hemodialysis device used to treat patients with renal insufficiency, and as a blood oxygenation device in an artificial lung for exchanging oxygen and carbon dioxide. According to a conventionally known manufacturing method for a hollow fiber type mass transfer device, a large number of hollow fibers (approximately 10,000 fibers) are bundled, and an adhesive or an elastic body such as a rubber band or the like is used to prevent the bundle from coming apart. Fix both ends with a fixing device such as an annular ring and load it into the case.
Next, it is fixed (potted) to the case with a solidifying liquid (potting material) such as silicone, epoxy resin, or polyurethane, and then both ends are cut open. In this case, the hollow fiber bundle has one of the two forms shown in FIGS. 1 and 2. 1st
The hollow fiber bundle 6 shown in the figure is formed into a bundle by winding one or more continuous hollow fibers 5, for example, between two fulcrums in the required number, but both ends of the hollow fiber bundle 6 are Since it is composed of a plurality of continuous hollow fibers, it is in an unopened state. Further, in order to maintain the shape of the bundle, both ends are fixed at appropriate positions with rubber bands 71, as described above. 2nd A
The hollow fiber bundle 6 shown in the figure is composed of one or more continuous hollow fibers, such as the shackles 56 shown in FIG.
Wrap the required number of fibers around the hollow fiber winding frame 60 ~
Six hollow fiber bundles 6 at positions X-X' between 65
It is cut into pieces and fixed with rubber bands 71. In FIG. 2B, prior to cutting, an adhesive 70 is applied to the periphery of the cut portion to prevent the fiber bundle 6 from falling apart, thereby fixing the hollow fibers in a bundle. In either case, since the hollow fiber bundle 6 is cut, each hollow fiber 5 making up the bundle is open at both ends. Next, these fiber bundles 6 are loaded into a case,
Furthermore, a solidifying liquid is injected between the end of the fiber bundle 6 and the inner wall surface of the case to fix the fiber bundle 6 to the case in a liquid-tight state. In this case, if a bundle of hollow fibers with both ends open as shown in FIG. 2A or 2B is used as the hollow fiber bundle 6, the solidifying liquid will enter the hollow portion 10 of the hollow fiber 5 due to capillarity. This causes the hollow fibers 5 to become clogged, resulting in a fatal defect in that even if the fixed portion is cut after being fixed, the hollow fibers 5 will not open at the cut surface. In order to eliminate this defect, conventionally, the openings at both ends of the hollow fiber bundle 6 are first sealed with an adhesive, then the hollow fiber bundle 6 is loaded into a case, and then potted as described above. Therefore, when potting is performed using a bundle of hollow fibers with both ends open as shown in FIG. 2A or 2B, the openings at both ends of each hollow fiber are sealed with adhesive before loading into the case. There was a strong preconceived notion among those skilled in the art that it was necessary to seal the On the other hand, in the conventional technology as described above, the solidifying liquid moves from the ends of the hollow fibers toward the center by capillarity in the capillary space between the bundled hollow fibers 5, thereby fixing the hollow fibers 5. This has an undesirable drawback in that it adheres to areas other than those necessary for this purpose, substantially reducing the effective membrane area. As a way to eliminate these drawbacks,
A centrifugal molding method according to No. 5526 is known. According to this molding method, one or more continuous hollow fibers 5 as shown in FIG. As shown in the figure, the case 1 is loaded into the case 1, and the case 1 is fixed on the rotary plate 82 with the fixing member 83 via the casing member 80 and rotated, and in this state, the solidifying liquid 7 is sent to both ends and solidified. and seal both ends. In this case, the solidifying liquid 7 is prevented from moving through the capillary space between the hollow fibers 5 even with a centrifugal force several hundred times stronger than gravity. As described above, the centrifugal molding method disclosed in Japanese Patent Publication No. 44-5526 uses a hollow fiber bundle composed of a large number of loops of one or more continuous hollow fibers. As mentioned above, this seems to be because there was a strong preconception among those skilled in the art that a bundle of hollow fibers with both ends open could not be used unless the openings were sealed with adhesive. It can be done. However, when a hollow fiber bundle composed of a large number of loops is used as described above, first of all, it is troublesome to create the hollow fiber bundle. In addition, in such a hollow fiber bundle, it is difficult for each hollow fiber portion to be arranged in a straight line near both ends of the bundle, and the bundle is bent to some extent. Therefore, it is necessary to tightly tie both ends of the hollow fiber bundle with a rubber band or thread, and then store it in a case after straightening it, but even then, there is a risk that the hollow fibers will be localized and potted inside the case. For this reason, the hollow fibers are not evenly distributed over the entire loading area of the case, and if dialysis is performed using such a device, the dialysate will preferentially concentrate in areas where the density of the hollow fibers is low. So-called channeling, or perfusion, is likely to occur. Therefore, such a dialysis device has a serious drawback in that its performance is poor, and in particular, the performance varies widely between products. Furthermore, assuming that a bundle of hollow fibers with both ends open is sealed with an adhesive and then used in the centrifugal molding method described above, the result will be as shown in FIG. 5, for example. Fifth
In the figure, the openings at both ends are sealed with adhesive 70.
The bundle 6 of hollow fibers sealed with
The potting material 7 is fed into the casing member 80 in the same manner as shown in the figure, and both ends of the hollow fiber bundle 6 are potted into the case 1 using the centrifugal force generated by the drive of the rotary plate 82. However, in this method, the operation of sealing both open ends of a large number of about 10,000 hollow fibers 5 with adhesive 70 is extremely complicated, and the open ends of all hollow fibers 5 are completely sealed. It is difficult to contain the If the open ends are not sealed, when potting as described above, the potting material 7 is filled into the hollow portions 10 of the hollow fibers 5, as shown in FIG. 6A. In this case, since a large centrifugal force of several hundred times the gravity is acting, the liquid pressure of the solidifying liquid that is the potting material is extremely large, and there is a risk that a large amount of the solidifying liquid will enter the hollow portion 10. There is. On the other hand, when the adhesive 70 is applied to the open end, it enters the hollow portion of the hollow fiber 5 having an inner diameter of approximately 20μ by capillary action. If this is too severe, the adhesive 70 will rise above the cutting position indicated by Y-Y' after potting, as shown in FIG. 6B. In either case, even if the cutting is performed after potting at Y-Y', the hollow fiber 5 will not open, and the effective membrane area of the internal hollow part of the hollow fiber will decrease, resulting in a decrease in the mass transfer function. . Therefore, the operation of sealing both open ends of a hollow fiber bundle with adhesive must be carried out by highly skilled workers and requires a large amount of time, and even with such care, it is impossible to completely seal the ends. Moreover, it is extremely difficult to prevent damage to the hollow fibers during the adhesive application process. The present applicant has proposed an improved method for sealing the ends of the above-mentioned open hollow fibers in Japanese Patent Application No. 51
-96272 (Japanese Patent Publication No. 56-3772), a plurality of hollow fibers with both ends open are housed in a case, and the case is rotated to apply centrifugal force to both ends. sealing the openings at both ends of the hollow fiber by a potting operation;
Then, a predetermined amount of potting material is further supplied and solidified by a second potting operation,
A method for manufacturing a hollow fiber type mass transfer device has been proposed, which is characterized in that both ends of the hollow fiber are fixed to the case. In this method, by cutting after potting, all the hollow fibers are opened to form blood passage ports, and therefore a hollow fiber type dialysis device with excellent mass transfer efficiency can be easily and reliably produced. Although this is an excellent method that enables production and does not vary from production to production, it has the disadvantage that it requires two potting operations and the process operation takes a long time. Furthermore, according to a conventionally known manufacturing method, a large number of hollow fibers are tightly bundled, and both ends are fixed in a bundle with a solidifying liquid (adhesive), an elastic body such as a rubber band, or an annular ring. Since the bundle is housed in a case and fixed to the case in this state, the hollow fibers are extremely dense, especially in the center part of the bundle. Therefore, when this device is used for hemodialysis, etc., it is extremely difficult to uniformly perfuse the dialysate into the hollow fiber bundle, and it is preferable that there is no space between the outer periphery of the hollow fiber bundle and the inner wall of the dialysis case. It has been experimentally confirmed that the dialysis rate is extremely low in the center of the hollow fiber bundle because the amount of dialysate that passes through this gap is relatively large. has been done. The present applicant has filed Japanese Patent Application No. 51-88010.
No. 25853), in order to correct this drawback, a plurality of hollow fibers are loaded into a predetermined loading area in a case, and then the plurality of hollow fibers are not fixed as a hollow fiber bundle. A method has been proposed in which both ends of the hollow fibers are fixed to the case with a solidifying liquid, and then both ends of the plurality of hollow fibers are opened. According to this method, the hollow fibers are fixed in a substantially uniformly distributed state within the loading area, so that the fluid flowing outside the hollow fibers penetrates into the center of the hollow fiber bundle and passes through the entire hollow fiber. Fluid is perfused relatively uniformly, resulting in increased effective membrane area and improved mass transfer efficiency. However, this method also uses hollow fibers that are open at both ends.
It is necessary to seal the openings of the hollow fibers in advance, which causes the above-mentioned problems. The present inventors have discovered that when using a hollow fiber bundle to perform a potting operation while applying centrifugal force, the hollow fibers do not become clogged at the time of cutting and opening, and a hollow fiber mass transfer device with excellent dialysis performance can be easily and reliably produced. We worked hard to find a way to produce this product. As a result, surprisingly, by using hollow fibers with both ends open, the pressure of the air remaining in the hollow part of these hollow fibers and the centrifugal force are skillfully balanced. When the solidifying liquid is injected to a predetermined position and cut, for example, at the Y-Y' position shown in FIG. It has been found that a hollow fiber type mass transfer device having excellent dialysis performance can be easily and reliably manufactured without substantially reducing the effective membrane area due to adhesion of the solidifying liquid transferred by the method. An object of the present invention is to completely seal the open ends of a large number of hollow fibers in a case, which is easier even for an unskilled person than the conventional method described above, and without reducing the effective membrane area of the hollow fibers. The goal is to achieve a fixing method. Another object of the present invention is to easily open a large number of hollow fibers even by an unskilled person compared to the above-mentioned conventional method, without fixing a plurality of open hollow fibers as a hollow fiber bundle. The object of the present invention is to achieve a method of completely sealing the ends and fixing the hollow fiber to the case without reducing the effective membrane area at the same time. That is, in the present invention, a plurality of hollow fibers are housed in the case with both ends thereof being open, and the case is then opened approximately every minute.

[Formula] Above, almost Below (however, l ₀ is 1/2 of the distance between both outer end surfaces of the fixed part at both ends of the case when fixed by the solidifying liquid, and l ₁ is the distance between the outer end surfaces of the fixed part at both ends of the case when fixed by the solidifying liquid) The distance between the outer end surface and the inner end surface of the fixed portion, l ₂ is the distance between the outer end surface of the fixed portion and the cutting position, r is the radius of the hollow portion of the hollow fiber, and γ is the diameter of the solidifying liquid. surface tension, ρ
is the specific gravity of the solidifying liquid, g is the gravitational acceleration, and P ₀ is the atmospheric pressure. In addition, l ₀ , l ₁ , l ₂ , r, γ, ρ,
All units of g and P ₀ are cgs units. ) to apply centrifugal force to both ends of the case, and while this centrifugal force is acting, the predetermined amount of the solidifying liquid is simultaneously supplied to both ends of the plurality of hollow fibers at once. The method is characterized in that the air in the hollow portions of the plurality of hollow fibers is sealed and fixed. FIG. 7 shows a state in which a plurality of hollow fibers 5 with both ends open are loaded in the loading area 25 of the case 1, and FIG. 8 shows a casing member 80 in the case 1 loaded with a plurality of hollow fibers 5 with both ends open. is attached and fixed with a fixing member 83 on a rotating plate 82 having a rotating shaft 81, and the container 84 of the solidifying liquid 7 and the casing member 80 are connected via the solidifying liquid introduction pipe 86 and the piping 85. show. After this arrangement, a motor (not shown) is driven to rotate the rotating shaft 81 via the bearing 8, and the centrifugal force generated thereby causes the solidifying liquid 7 to be moved from the container 84 into the casing member 80. and move it to a predetermined position P-
The solidifying liquid 7 is injected up to P' and solidified by reaction,
Thereafter, the solidified liquid 7 is cut along with the hollow fibers 5 at the cutting position Y-Y', and the hollow fibers 5 are opened at the cut surface. The above-mentioned rotation may be performed on a vertical plane, for example as shown in FIGS. 8 and 9, or on a horizontal plane, as shown for example in FIGS. 4 or 5. In addition, in order to load the hollow fiber 5, the above-mentioned patent application 1973-
The method disclosed in No. 88010 (Special Publication No. 55-25853) may be adopted. That is, in the state shown in FIG. 7, each hollow fiber 5 is released from the bundle 6 by cutting the adhesive 70 with a sharp knife, for example, and is uniformly dispersed in the loading area 25 by applying appropriate vibration with, for example, a vibrator. After that, potting can be carried out. In this case, since the hollow fibers are fixed in a uniformly dispersed state by potting, the dialysate is uniformly perfused throughout the fiber bundle, improving efficiency. In this case, the solidifying liquid 7 does not enter the hollow portion of the hollow fiber 5 beyond the cutting position Y-Y', and the solidifying liquid 7 adheres to the outer surface of the hollow fiber 5, so that the potting position P- It is necessary not to reduce the substantially effective membrane area of the hollow fibers 5 located closer to the center of rotation than P'. This means that the air existing in the hollow portion 10 of the hollow fiber 5 is transferred to the hollow portion 10 of the hollow fiber 5, as shown in an exaggerated manner in FIGS. 9 and 10, which are examples in which the axis of rotation is horizontal. The rotation speed of the case 1 (i.e., centrifugal force) and the solidifying liquid 7 are controlled so that the solidifying liquid 7 is sealed at both ends, and then, in this state, the solidifying liquid 7 is injected to a predetermined potting position P-P'. It has been found that this can be achieved by skillfully controlling the temperature of That is, both bottom surfaces 88 of the two casing members 80
(i.e. approximately equivalent to the length of the hollow fiber 5)
2l ₀ , the distance from the bottom surface 88 of the casing member 80 to the predetermined potting position P-P' is l ₁ , the distance from the bottom surface 88 of the casing member 80 to the cutting position Y-Y' is l ₂ , the hollow of the hollow fiber 5 The height of the solidifying liquid 7 entering the portion 10 from the bottom surface 88 of the casing member 80 is h, and the hollow portion 10 of the hollow fiber 5 is
The radius of is r, the radius of the capillary space 11 created between the hollow fibers 5 is R, the height of the solidifying liquid 7 that rises in this space 11 and adheres to the outer surface of the hollow fiber 5 is H, and the potting operation The absolute temperature at which the solidifying liquid 7 starts is T _p , the absolute temperature at which the solidifying liquid 7 reacts and hardens and becomes non-fluid is T , and the solidifying liquid 7
When the specific gravity ρ is the surface tension of the solidifying liquid 7, γ is the rotational speed, and g is the gravitational acceleration, the following force balance can be considered. That is, the force per unit area (atmospheric pressure P _p ,
The force δ due to the surface tension of the solidifying liquid 7, the force G due to the gravity of the solidifying liquid 7, and the centrifugal force F of the solidifying liquid 7), and the invasion of the solidifying liquid 7 into the hollow portion 10 of the hollow fiber 5. Force per unit volume to prevent (air pressure P when the air sealed in the hollow portion 10 of the hollow fiber 5 is compressed by the intrusion of the solidifying liquid 7)
A force equilibrium occurs with. Note that gravity acts in the opposite way on the upper end, but due to the rotation described above, a point periodically occurs where both ends become the lower end.
Considering the lower end that produces a pushing force greater than 1 with respect to h, the following equation holds. P=P _p +δ+G+F……(1) On the other hand, the force δ due to the surface tension of the solidifying liquid 7 is expressed as δ=2γ/r(dyne/cm ² )……(2) _The ^force G due to the gravity of ) ² {(l ₀ −h) ² −(l ₀ −l ₁ ) ² /2}(dyne/cm ² ) ...(4) and is sealed in the hollow portion 10 of the hollow fiber 5. The pressure P of the air is P=P _p・T/T _p・l ₀ /l _p −h (dyne/cm ² )...
...It is expressed as (5). Therefore, the rotation speed is given by In addition, a capillary space 11 generated between the hollow fibers 5
The height H of the solidifying liquid 7 rising from the hollow fiber 5 is
The force δ' caused by the surface tension of the solidifying liquid 7 rising in the capillary space 11 generated during Determined by force balance. Note that gravity acts in the opposite way on the lower end, but as a result of the above-mentioned rotation, there periodically occurs a point in time when both ends become the upper end, so the upper end produces a rising force greater than 1 for h. Considering the end portion, the following equation holds true. That is, δ'=-G'+F'......(7) The force δ' due to the surface tension of the solidifying liquid 7 rising in the capillary space 11 generated between the hollow fibers is as follows: δ'=2γ/R(dyne /cm ² ) ......(8), and the gravity G' of the solidifying liquid 7 is expressed as G' = ρgH (dyne/cm ² ) ......(9), and the gravity G' of the solidifying liquid 7 is expressed as The acting centrifugal force F' is F'=ρ・(2πX/60) ²・(l ₀ −l ₁ ) ² −(l ₀ −l ₁ −H) ² /2(dyne/cm ² )……(10 ). Therefore, the rotation speed is given by Here, the radius R of the capillary space 11 is the space when the hollow fibers 5 are packed closest, and assuming that the capillary space 11 is a circle, the radius R is as follows. Therefore, the rotation speed It is required as. The present invention utilizes the air sealed in the hollow portion 10 of the hollow fiber 5 to reduce the height h from the bottom surface 80 of the casing member 80 of the solidifying liquid 7 entering the hollow portion 10 of the hollow fiber 5. The hollow fibers 5 are controlled by controlling the rotational speed shown in the above equation (6), and ascend through the capillary space 11 created between the hollow fibers 5 and adhere to the outer surface of the hollow fibers 5 to become substantially effective.
The object of the present invention is to easily and reliably manufacture a hollow fiber type mass transfer device having excellent dialysis performance by controlling the height H at which the membrane area is reduced by controlling the rotation speed shown in the above equation (13). For this reason, the rotational speed X that provides centrifugal force is approximately

[Formula] Above, almost It should be less than or equal to, preferably approximately

[Formula] Above, almost or less, more preferably approximately

[Formula] Above, It is as follows. The rotation speed

When the value is less than [formula], the solidifying liquid rising in the capillary spaces 11 between the hollow fibers 5 reduces the substantially effective membrane area of the hollow fibers, and the rotational speed If it exceeds this, when the potting portion is cut, the hollow fibers 5 will not open at the cut surface, which is not preferable. The present invention as explained above is preferably implemented within the following ranges for practical purposes. The height h of the solidifying liquid penetrating into the hollow fibers is at least 0.3 cm greater than the distance _l2 to the cutting position in order to obtain a good opening without clogging the hollow fibers with solidifying liquid by cutting after potting. Preferably, the length is shortened by 0.5 cm or more, more preferably 1 cm or more. However, in order to reliably seal the inner tip of the hollow fiber, it needs to be at least 0.5 cm higher than the bottom surface. Practically speaking, h is 0.5 to 3.5.
Preferably, it is carried out between cm. The distance l ₂ from the bottom surface to the cutting position varies depending on the length of the hollow fibers (2l ₀ ) and the number of converged fibers.
If it is less than 0.8 cm, it is difficult to obtain a good opening in the hollow fiber by cutting, and it is difficult to make a good potting.
2 cm or more is preferable. On the other hand, the length is preferably 4.5 cm or less in order to ensure the effective membrane area and to reduce the loss of hollow fibers due to cutting. The distance l ₁ from the bottom of the casing to the potting position on the outer surface of the hollow fibers is such that the hollow fiber bundles can be potted in a confidential manner, have mechanical strength, and are not damaged during dialysis.
l ₂ +1cm or more is required. On the other hand, in order to ensure the effective membrane area, it is preferable that l ₂ +4 cm or less. The length 2l ₀ of the hollow fibers varies depending on the number of converged fibers, but is preferably in the range of about 25 to 40 cm for practical purposes. This is because if the length is less than 25 cm, the dialysis efficiency will be poor, and if it is more than 40 cm, the performance will deteriorate due to pressure loss during dialysis. The height H of the solidifying liquid adhering to the outer surface of the hollow fiber can be determined by effectively securing the effective membrane area.
It must be 0.5 cm or less, and may be 0. Further, as the solidifying liquid, polyurethane, epoxy resin, etc. are used, and polyurethane is preferable. The apparatus according to the present invention is manufactured within the preferred range of the above conditions, but when polyurethane is used as the solidifying liquid and the process is carried out at room temperature, it is preferable to carry out the process at a rotational speed of 300 to 900 rpm. . In addition, as mentioned above, when determining the rotation speed
= 0.5 (cm), h = l ₂ -0.3 (cm), T = T _p , and to make it a more preferable value, h = l ₂ -0.5 (cm),
h=l ₂ -1 (cm). The temperature T is often set higher than T _p in order to increase the solidification reaction rate of the solidification liquid _. The liquid level height h from the bottom surface of the potting frame is secondarily controlled by the expansion pressure of the air confined in the hollow portion of the hollow fiber. For example, temperature T _p
Even if the height h of the solidifying liquid that has entered the hollow part of the hollow fiber is lowered by the temperature T, the inner wall surface of the hollow part of the hollow fiber will still have the height h at the temperature T _p . If the solidifying liquid is attached to the center of rotation than the cutting position, the inner diameter of the hollow fiber will be narrowed, making it difficult to use the dialysis device manufactured by this method as an artificial kidney. If used, it is undesirable as it may cause blood clotting. Therefore, the rotational speed X must be determined as T=T _p . Furthermore, when the height H of the solidifying liquid adhering to the outer surface of the hollow fiber becomes 0.5 (cm) or more, the effective membrane area of the hollow fiber decreases, resulting in a noticeable difference in dialysis performance. This is undesirable. Furthermore, if the height h from the bottom of the casing member of the solidifying liquid entering into the hollow portion of the hollow fiber is greater than the height l ₂ from the bottom of the casing member to the cutting position, then the cutting position Y-Y Even if the hollow fibers are cut after fixing at 1, the hollow fibers do not open at the cut surface, which is not preferable. Therefore, the height h must be smaller than the height _l2 . Therefore, the height h
The rotational speed X is smaller than the height l ₂
However, in practice, the yarn length of the hollow fiber may be slightly shorter than the distance between the bottom surfaces of the casing member, or it may not be possible to cut accurately at the predetermined cutting position Y-Y'. It is preferable to specify the rotation speed X so that the difference between the height l ₂ and the height h is about 0.3 cm, preferably about 0.5 cm, and more preferably about 1 cm. Therefore, it is preferable that h=l ₂ -0.3 (cm), more preferably h=l ₂ -0.5 (cm), h
= l ₂ -1 (cm). In addition, in the present invention, it is important that the absolute temperature T when the solidifying liquid 7 reacts and hardens to become non-fluid and the absolute temperature T _p at the start of injection are 358〓 or less, preferably 343〓 or less. It is. The temperature T _p
If T exceeds 358〓, the structure of the hollow fibers will change and its performance will deteriorate, which is not preferable. Furthermore, the ratio T/T _p between the temperature T and the temperature T _p at the time of starting the potting operation is approximately [ρ{l ₀ ² −(l ₀ −l ₁ ) ² }/2・(2πX/6
0) ² +P _p +2γ/r+ρ gl ₁ ]・1/P It is important that it is less than or equal to _p . That is, when the temperature ratio T/T _p becomes larger than the above ratio, the air sealed in the hollow portion 10 of the hollow fiber 5 expands and diffuses outside the hollow portion, and at this time, air bubbles are generated in the potting material. Undesirable. When T/T _p becomes smaller than 1, the volume of the air sealed in the hollow part of the hollow fiber contracts and the solidifying liquid is sucked up into the hollow part of the hollow fiber. If the solidifying liquid adheres to the hollow portion of the hollow fiber located closer to the center of rotation than the cutting position, for example when used as an artificial kidney, phenomena such as blood clotting may occur, which is undesirable. Furthermore, when T/T _p becomes larger than the value shown by the above formula, the air sealed in the hollow portion of the hollow fiber expands and diffuses outside the hollow portion, creating air bubbles in the potting material. In some cases, pinholes are generated due to the continuation of air bubbles existing in the fixed portion, resulting in leakage, and the product becomes defective and cannot be used. Therefore, T/T _p must be less than or equal to the value expressed by the above formula, preferably less than or equal to the value expressed by the above formula, and must be 1 or more. As detailed above, in the present invention, a solidifying liquid is simultaneously supplied to both ends of the hollow fiber, each of which is open at both ends, to seal the air in the hollow portion of the hollow fiber. Therefore, according to the present invention, even if there is a defect in the hollow fiber used, such as a cut point or pinhole in the middle part, the solidifying liquid is automatically prevented from flowing deep into the hollow part of the hollow fiber. is filled with. That is, if there is a cut point or pinhole in the middle part of the hollow fiber, air will not be contained in the hollow part of the hollow fiber, and air will leak from the cut point or pinhole. The solidifying liquid penetrates deep into the hollow portion and fills the hollow portion of the hollow fiber having the above-described defects.
Note that conventionally, there is no effective method for selectively filling the hollow portions of hollow fibers with the above-mentioned defects, and products with such hollow fibers are defective, resulting in low product yields. This was a major cause of the problem. However, according to the present invention, since the hollow portions as described above are automatically filled, it is possible to dramatically improve the yield of products. Next, an embodiment in which the present invention is applied to a hemodialysis apparatus for an artificial kidney will be described. Example 1 Using the hollow fiber winding device shown in FIG.
1, and guide rollers 52, 5 configured to control the fiber tension by a load (not shown).
3, and the shackles 5 are driven by a motor 55 while dispersing the hollow fibers evenly by a traver 54.
6, the fiber bundle is wound into a flat shape in accordance with the loading area 25 of the hollow fiber bundle 6 of the case 1 having a flat cross section shown in FIG. Next, at a position indicated by
6 hollow fiber bundles 6 consisting of 8000 hollow fibers 5
Cut into. In this case, in order to prevent the hollow fibers from falling apart, a band of adhesive 70 is applied to the inside of the cut portion in advance to fix the hollow fibers into a bundle. Next, as shown in FIG. 7, this hollow fiber bundle 6 is loaded into a case 1 having a flat cross section and having a dialysate inlet tube 2 and an outlet tube 3, and a casing member 80 is inserted into the case as shown in FIG. It is applied to the flange portions 40 at both ends and is fixed using a fixing member 83 to a rotating plate 82 fixed to a rotating shaft 81 and rotating in the direction of gravity. Next, each of the two containers 84 of the solidifying liquid 7 installed on both sides of the case 1 closer to the center of rotation than the predetermined potting position P-P' is filled up to the predetermined potting position P-P'. A sufficient amount of potting material 7 is injected. Next, the rotary shaft 81 is driven using a motor, and the solidifying liquid 7 contained in the container 84 is passed through the piping 85 and the solidifying liquid introduction pipe 86 provided in the casing member 80 to the casing member 80 on both sides. were simultaneously injected into the interior of the chamber by centrifugal force, and a predetermined rotation speed and temperature were maintained. As a result, the solidifying liquid 7 is filled into the inside of the casing member 80 and the hollow portion 10 of the hollow fiber 5 up to the M-M' position (the distance from the bottom surface 88 of the casing member 80 to the M-M' position is h), And a liquid level P-P' was formed. Further, a predetermined rotation speed and temperature were maintained to cause reaction and solidification. In this example, the solidifying liquid 7 has a surface tension determined by the capillary method at 25°C.
11dyne/cm ² , specific gravity at 25℃ is 1.05g/cm ³
A polyurethane composition manufactured by NL was used. Further, the amount of solidifying liquid 7 sufficient to fill up to the predetermined position P-P' was 100 c.c. Further, the distance between the bottom surfaces 88 of the two casing members 80 (i.e., the length of the hollow fiber) 2l ₀ is 30 cm, and the bottom surface 88 of the casing member 80
Distance l ₁ from to predetermined potting position P-P'
was 5 cm, and the height _l2 from the bottom surface 88 of the casing member 80 to the predetermined cutting position Y-Y' was 3.0 cm. The rotating shaft 81 is also driven to transfer the solidifying liquid 7 contained in the container 84 to the pipe 85 and the inlet pipe 86.
The temperature T _p was 323〓 when the injection into the casing member 80 by centrifugal force was started, and this temperature was maintained. Therefore, the reaction temperature T was also 323°, and 475 revolutions per minute was used as the predetermined rotation speed X to make the height h 1.5 cm. In this way, the air present in the hollow portion 10 of the hollow fiber 5, which is open at both ends, is confined within the hollow portion, and all of the air is compressed by the volume compression pressure caused by the entry of the polyurethane composition 7 (potting material). The hollow fiber 5 is located at the position M-M' (i.e., the position where the height h from the bottom surface 88 of the casing member 80 is 1.5 cm)
It was completely sealed, and in this state it was fixed to the case 1 at the position P-P'. Further, the adhesion height of the polyurethane composition to the outer surface of the hollow fibers 5 (the above-mentioned height H) was also about 2 mm. Next, the fixing member 8
3 and the casing member 80 are removed, and the solidifying liquid solidified at the position Y-Y' is cut together with the hollow fibers 5 using a cutting blade, thereby opening both ends of the hollow fibers 5, and cutting. The condition of the surface was observed. As a result, all the hollow fibers 5 were well opened at the cut surface, and there was no trace of the adhesive liquid 7 entering into the hollow portion 10 of the hollow fiber 5. Next, as shown in FIG. 11, the lids 17 and 18 having the blood introduction tubes 14 and 15 are attached, the hollow fiber type dialysis device 10 is assembled, and hemodialysis is performed in the usual manner to check the coagulation state and residual blood. We observed the condition and found that there were no hollow fibers in either case, which means that all the hollow fibers 5 are well opened at the cut surface and serve as blood passage holes, proving the advantage of the present invention. It is something to do. By manufacturing according to the method described above, the sixth
Compared to the conventional method shown in FIGS. A and 6B, cutting after potting allows all the hollow fibers to open to form blood passage ports, and furthermore, the present applicant's proposal Compared to the method of Japanese Patent Application No. 51-96272 (Japanese Patent Publication No. 56-3772), this hollow fiber type dialysis device can be manufactured easily and reliably with a single potting operation, and has excellent mass transfer efficiency. can be manufactured easily and reliably. Furthermore, it can be easily understood that there is no variation between manufacturing processes and that this method is superior to the conventional method when using hollow fibers in which both ends of the hollow fibers are open. Furthermore, among the products potted by the above method, there were no rejected products due to leakage of hollow fibers. Example 2 Hollow fibers 5 shown in FIG. 9 were potted in the same manner as in Example 1 except that the rotation speed was changed.
Intrusion height h of the solidifying liquid 7 into the hollow part 10,
and a capillary space 11 formed between the hollow fibers 5
The height H of the solidifying liquid 7 rising and adhering to the outer surface of the hollow fiber 5 was measured. The results are shown in the first section below.
As shown in the table and FIG. 12, the height h obtained from the above equation (6) and the height H obtained from the above equation (13) are shown in comparison.

[Table] As is clear from this result, the heights h and H obtained by the experiment, the calculated value h obtained from the above equation (6), and the calculated value H obtained from the above equation (13)
It can be seen that they match very well. Next, a predetermined cutting position Y-Y' (bottom surface 88 of the casing member
The open state of the hollow fibers 5 at the cut surface was observed at a height l ₂ =3.0 cm). As a result, the polyurethane composition did not penetrate into the hollow portions 10 of the hollow fibers 5 at all when the rotational speed was from 100 to 800 revolutions per minute, indicating a good open state. However, in the case where the rotation speed was 1000 revolutions per minute or more, all the hollow fibers were blocked at the cut surface, and it was not possible to form a blood passage hole. Next, the hemodialyzer 10 was assembled by attaching a lid having a blood inlet in the same manner as in Example 1, and in accordance with a conventional method, the clotted blood containing vitamin B ₁₂ was added to the blood side at a flow rate of 200 ml per minute. Distilled water was flowed through the dialysate side at a flow rate of 500 ml per minute, and the dialysance was measured. The results are shown in Table 2 below.

[Table] As is clear from this result, the height H of the polyurethane composition that ascends the capillary space 11 between the hollow fibers 5 and adheres to the outer surface of the hollow fibers 5 is 0.5 cm.
Exceeding this is not preferable because it is obvious that the effective membrane area will decrease and the dialysis performance will deteriorate. That is, from Tables 1 and 2 above, the preferred rotation speed in this embodiment is higher than the rotation speed at which the height H is 0.5 cm or less, and the rotation speed is higher than the rotation speed at which the height H is 0.5 cm or less, and the rotation speed is set at a predetermined cutting position Y- from the bottom surface 88 of the casing member 80. The distance l ₂ to Y' must be within a range smaller than the rotational speed that is greater than the height h of the potting material that ascends the hollow portion 10 of the hollow fiber 5, and considering the cutting after potting, l ₂ - h Practically preferred is ≧0.3 (cm). Therefore, from equations (6) and (13) above, the preferred rotation speed is

[Formula] Above, It can be expressed as below, and in the case of this example, every minute
300 rpm or more and 860 rpm or less. Furthermore, there were no rejected products even among the products potted using this method. Example 3 Potting was carried out in the same manner as in Example 1 except that the injection of the polyurethane composition was started by centrifugal force at 298 mm and then the temperature was raised. The results are shown in Table 3 below.

[Table] As is clear from this result, by increasing the reaction curing temperature T 〓 from the temperature T _p 〓 at which injection of the polyurethane composition was started, the amount of polyurethane penetrating into the hollow portion 10 of the hollow fiber 5 can be increased. It is possible to reduce the however,
If the ratio T/T _p of the reaction curing temperature T and the injection start temperature T _p is 1.201 or more, the air sealed in the hollow portion of the hollow fiber expands and desorbs into the polyurethane composition. In this case, the polyurethane composition is incorporated as bubbles and cured, resulting in the presence of bubbles in the potting area, which is undesirable. Furthermore, the temperature T at which reaction hardening occurs is
If it exceeds 398〓, cracks will occur due to volume contraction when the reaction-hardened solidifying liquid (polyurethane composition) is cooled, and in severe cases, leaks will occur, making it impossible to use it as a dialysis device. Undesirable. Next, in the same manner as in Example 1, vitamin
The dialysance of B ₁₂ was measured. The results are shown in Table 4 below.

[Table] As a result, it is clear that when the temperature T during reaction curing is 383〓 or higher, it has an adverse effect on the membrane performance of the hollow fiber 5, and when it is 358〓 or lower, especially 343〓 or lower, there is no such effect. Therefore, Tables 3 and 4 above
From the results in the table, the temperature T during reaction curing is 358〓
It should preferably be 343〓 or less. Furthermore, as is clear from the results in Table 3 above, when the height h of the solidifying liquid entering the hollow portion 10 of the hollow fiber 5 becomes 0, air bubbles may enter the potting material after reaction hardening. , cracks may occur, which is undesirable, but the height h is regulated by the ratio T/T p of the temperature T _p when the injection of the solidifying liquid is started and the temperature T at which reaction hardening is performed, and the height h is regulated by the ratio T/T _p of the above-mentioned temperature T p when the injection of the solidifying liquid is started and the temperature T at which the solidifying liquid is cured. It can be obtained by That is, T/T _p becomes h=0 [ρ{l ₀ ² −(l ₀ −l ₁ ) ² }/2・(2πX/6
0) ² +P _p +2γ/r+ρ gl ₁ ]・1/P _p or less. In this case, the rotational speed X must be within the range shown in Example 2 above. The relationship between the temperature ratio T/T _p and the rotational speed X is shown in FIG. Comparative Example The procedure was the same as in Example 1, except that the polyurethane composition was injected at a rotational speed of 1200 revolutions per minute, and then the reaction curing temperature T was raised to 363° before the time when the polyurethane composition became non-fluid. I did some potting. As a result, the hollow portion 1 of the hollow fiber 5
The height h of the solidifying liquid that entered into the tube was 2.5 cm. Next, a cutting opening was made in the same manner as in Example 1, and
The state was observed, and the hollow portion 10 of the hollow fiber 5
As schematically shown in FIG. 14, a solidifying liquid (polyurethane composition) 7 was deposited as a thin film inside the hollow fibers 5, reducing the inner diameter of the hollow fibers 5. Furthermore, when a hemodialysis apparatus was assembled and hemodialysis was performed in the same manner as in Example 1, a blood clotting phenomenon was observed. According to this comparative example, when the solidifying liquid is injected at 298〓, the solidifying liquid 7 that has entered the hollow portion 10 of the hollow fiber 5 as schematically shown in FIG.
The height h is once at the A-A' position, that is, the height from the bottom surface 88 of the casing member 80 due to the centrifugal force of 1200 rotations.
By raising the temperature T to 3.2 cm, the air trapped in the hollow portion 10 of the hollow fiber 5 expands, and the solidifying liquid 7 that has entered is moved to the B-B' position, that is, the casing. It is understood that the member 80 was pushed back to a height of 2.5 cm from the bottom surface 88, but at this time, the Y-
It is thought that the particles were attached to the hollow portion 10 of the hollow fiber 5 located closer to the center of rotation than the cutting position indicated by Y'. Therefore, in any case, the cutting position Y
It can be easily understood that it is necessary to avoid the solidifying liquid from adhering to the hollow portion 10 of the hollow fiber 5 located closer to the center of rotation than -Y'. As is clear from the above, according to the present invention, a hollow fiber bundle composed of hollow fibers with both ends open is fixed to a case by performing a potting operation with controlled rotation speed and temperature. As a result, a hollow fiber dialysis device with excellent dialysis performance and no manufacturing variation can be easily manufactured. The technical idea of the present invention is that in a method of fixing a hollow fiber bundle consisting of hollow fibers with open ends to a case using a potting material using centrifugal force, centrifugal force and temperature are skillfully controlled to By trapping air in the hollow portions of the fibers and controlling the pressure of the trapped air, we are able to solve defects that were not possible with traditional adhesive application methods, making all the hollow fibers fluid. The object of the present invention is to manufacture a hollow fiber type mass transfer device that can act as a passage port for the air and that has no variation between manufactures. Therefore, a hollow fiber bundle consisting of a large number of hollow fibers with both ends open can be obtained by cutting open a hollow fiber bundle consisting of one or more continuous hollow fibers as described above, or by opening both ends in advance. It may be formed into a bundle of open hollow fibers. Furthermore, the solidifying liquid used as the potting material can be arbitrarily selected from silicone rubber, epoxy resin, polyurethane, and the like. Note that the present invention is applicable not only to artificial kidneys but also to artificial lungs, juice concentrators, etc., and is extremely useful.

[Brief explanation of the drawing]

Figures 1 to 6 show conventional examples, and
Figure 1 is a perspective view of a bundle of continuous hollow fibers, Figure 2A is a perspective view of a bundle of multiple hollow fibers with both ends open, and Figure 2B is a perspective view of a bundle of multiple hollow fibers with both ends open. Perspective view in another state, 3rd
The figure is a perspective view of a hollow fiber winding device, Figure 4 is a partially cutaway front view of a device for centrifugal molding using a hollow fiber bundle consisting of continuous hollow fibers, and Figure 5 is a large number of hollow fibers with open ends. Partially cutaway front view of a device for centrifugal molding using a hollow fiber bundle made of fibers, Part 4
Figure A is a cross-sectional view of the potted part when adhesive is applied and potted using the method shown in Figure 5.
FIG. 6B is a sectional view showing another state of the potted portion when adhesive is applied and potted by the method shown in FIG. 5. Figures 7 to 15 are for explaining the present invention, with Figure 7 being a perspective view of the case with hollow fibers housed in it, and Figure 8 being a perspective view of the case shown in Figure 7 being rotated. 9 is a partially cutaway front view of the device for potting; FIG. 9 is a sectional view exaggerating the hollow fiber portion of the device in FIG. 8 during potting; and FIG. Fig. 11 is an exploded perspective view of the dialysis device when assembled after potting, and Fig. 12 shows the height h of the potting material entering the hollow portion of the hollow fibers and the distance between the hollow fibers. 13 is a graph showing the relationship between the height H of the potting material rising through the space and the rotation speed, and FIG. 13 shows the relationship between the ratio T/T _p of the potting material injection start temperature and reaction hardening temperature and the rotation speed. The graph and Figure 14 are cross-sectional views of the hollow fibers with potting material attached to their inner wall surfaces;
FIG. 15 is a sectional view during potting to explain the situation shown in FIG. 14. In addition, in the symbols used in the drawings, 1 is a case, 5 is a hollow fiber, 7 is a solidifying liquid or potting material, 10 is a hollow part, 11 is a space, and 80 is a
is a casing member, 82 is a rotating plate, and 84 is a container.

Claims (1)

[Claims] 1. Loading a plurality of hollow fibers into a predetermined loading area within a case, then fixing both ends of the plurality of hollow fibers with a predetermined amount of solidifying liquid, and then cutting the fixed portions. In the method for manufacturing a hollow fiber mass transfer device, the plurality of hollow fibers are housed in the case with both ends thereof open, and Next, this case is set to approximately [expression] or more every minute, approximately Below (however, l ₀ is 1/2 of the distance between both outer end surfaces of the fixed part at both ends of the case when fixed by the solidifying liquid, and l ₁ is the distance between the outer end surfaces of the fixed part at both ends of the case when fixed by the solidifying liquid) The distance between the outer end surface and the inner end surface of the fixed portion, l ₂ is the distance between the outer end surface of the fixed portion and the cutting position, r is the radius of the hollow portion of the hollow fiber, and γ is the diameter of the solidifying liquid. surface tension, ρ
is the specific gravity of the solidifying liquid, g is the gravitational acceleration, and p ₀ is the atmospheric pressure. Note that l ₀ , l ₁ , l ₂ , r, γ, ρ, g
and p ₀ are all in cgs units. ) to apply centrifugal force to both ends of the case,
The predetermined amount of the solidifying liquid is simultaneously supplied to both ends of the plurality of hollow fibers while the centrifugal force is applied to seal and fix the air in the hollow portions of the plurality of hollow fibers. How to do it.