JPH06296860A - Porous support and adsorption material - Google Patents

Abstract

PURPOSE:To provide a porous support for an adsorption material which allows an easy attachment of ligands and has an outstanding adsorption capability. CONSTITUTION:The object porous support consists of a solid fibrous film-like porous substance support which is composed of an organic high-molecular material having fine pores with an average pore diameter of 0.01-10mum, a total surface area of 3-500m<2>/g, and a pore diameter of 0.01-10mum. The volume of these fine pores is equivalent to, at least, 40% of the total fine pore volume.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION Adsorbents are used to adsorb components in solutions, especially body fluids. The present invention relates to a solid fiber membrane-like porous support useful for this adsorbent.

[0002]

2. Description of the Related Art In order to adsorb a substance dissolved in a solution, an adsorbent in which a molecule having an affinity for the substance is insolubilized on the surface of a porous support is used in the fields of medicine, industry, analysis, etc. Widely used in the field of basic research. As the porous support, a spherical or bead-shaped porous support made of a material such as cellulose, dextran, chitosan, or styrene / divinylbenzene is often used. Particularly in the field of medicine, a molecule that selectively binds to a disease-related substance such as a pathogen, that is, an adsorbent obtained by insolubilizing a ligand on the surface of a porous support is used to remove blood or plasma of a patient taken out of the body. It is used in a treatment method such as extracorporeal circulation treatment in which a body fluid such as the above is brought into contact with an adsorbent to adsorb and remove a disease-related substance in blood and then returned to the patient. For example,
Examples thereof include those in which dextran sulfate is covalently bonded to a bead-shaped porous support made of cellulose, and those in which tryptophan is covalently bonded to a bead-shaped porous support made of polyvinyl alcohol.

These bead-shaped porous supports have problems that it is difficult to densely pack them and the priming volume is large. For the purpose of solving this problem, a fibrous porous adsorbent is known (JP-A-60-24676).
5). The fibrous porous adsorbent shown in the invention has solved the problem of the adsorbent using the above bead-shaped support, but according to the studies by the present inventors, it functions as a support. Was insufficient and was not satisfactorily used as an adsorbent. The adsorption amount of the adsorbed substance per unit volume of the adsorbent, that is, the adsorption performance is determined by how much surface area of the porous support the contactable / adsorbable of the adsorbed substance is. The surface area is the sum of the external surface area and the internal surface area of the adsorbent carrier. In the conventional bead-shaped carrier, the pore diameter is increased or the number of pores is increased in order to increase the internal surface area. Unlike the present invention, the pores obtained by the carrier do not substantially penetrate, and become smaller from the surface to the inside, so that they are blocked by the adsorbed substance adsorbed in the pores, and body fluid containing more adsorbed substances is There is a problem that the body fluid containing the substance to be adsorbed that cannot flow in or enters the inside is limited due to diffusion. Further, if the particle diameter of the bead-shaped carrier is reduced for the purpose of increasing the external surface area, the liquid resistance becomes large, and further, the particles may flow out of the column, which is dangerous. In other words, there is a limit to the increase in surface area that can be effectively used.

[0004]

DISCLOSURE OF THE INVENTION Problem to be Solved by the Invention
In order to obtain an adsorbent in the form of a solid fiber membrane, which is even better than the fibrous porous adsorbent of 46765, the present invention has been accomplished as a result of earnest research on the porous support of the adsorbent.
According to the research conducted by the present inventors, when a solid fibrous membrane having uniform through holes is used in the fibrous porous body of JP-A-60-246765, the body fluid containing the substance to be adsorbed also freely enters and leaves the pores. It was found that the internal hole area can be effectively used and at the same time, it can be operated without resistance to liquid passage. Further, the solid fiber membrane is a material suitable for attaching a ligand. That is, an object of the present invention is to provide a porous support for an adsorbent, which is easy to attach a ligand and has excellent adsorption ability.

The gist of the present invention is as follows. Pore having an average pore size of 0.01 μm or more and 10 μm or less, a total surface area of 3 m ² / g or more and 500 m ² / g or less, and a volume of pores having a pore size of 0.01 μm or more and 10 μm or less is 40% or more of the total pore volume. A solid fiber membrane-like porous support made of an organic polymer material having Average pore size is 0.01 μm or more 1
Pore size of 0 μm or less and total surface area of 3 m ² / g or more 50
On the surface of a solid fiber membrane-like porous support made of an organic polymer material having a pore volume of 0 m ² / g or less and a pore diameter of 0.01 μm or more and 10 μm or less of 40% or more of the total pore volume,
An adsorbent made by insolubilizing a ligand. The present invention will be described below item by item.

Definition of internal surface area: The total surface area of all pores in a porous carrier.

Pore size The pore size and pore volume of the solid fibrous membrane-like porous support can be obtained from the mercury pressure curve by the mercury intrusion method. It is preferable that the pores referred to here have a value in a state as close to practical use as possible, and a value when used as an adsorbent. Also, if the shape changes due to the drying process during measurement with the mercury porosimetry, the change in the diameter of the solid fiber membrane porous support is measured, and the surface area is the rate of change in the diameter of the solid fiber membrane porous support. , And the pore volume is corrected by multiplying the diameter of the solid fibrous membrane-like porous support by the cube of the diameter. That is, the diameter of the solid fiber membrane porous support is 1 /
When it becomes X times, the surface area is 1 / X ² times and the pore volume is 1 /
Suppose that the number has increased by ³ times. The average pore size of the solid fibrous membranous porous support is determined by dividing the total pore volume by the total pore surface area, assuming that the pores are cylindrical. When the average pore diameter is less than 0.01 μm, the substance to be adsorbed does not sufficiently penetrate into the inside of the solid fibrous membrane-like porous support, and sufficient adsorption ability cannot be obtained. The risk of lowering and deforming increases,
In addition, the total surface area becomes small and sufficient adsorption capacity cannot be obtained, which is not preferable in practice. The preferred average pore size is 0.0
It is 1 μm or more and 10 μm or less. It is more preferably at least 0.05 μm, and most preferably at least 0.1 μm. It is more preferably 2 μm or less, and most preferably 1 μm or less.

Pore shape The pores are circular, elliptical, strip-shaped, star-shaped, polygonal, amorphous,
It may have any other shape, but it may be circular, oval,
The strip shape is more preferable in terms of the ease with which the substance to be adsorbed enters the support. Of these, the strip shape is most preferable. Further, it is highly preferable that the pores are through-holes regardless of the shape of the pores, because the ligand can be uniformly insolubilized even inside the support, and the substance to be adsorbed can easily enter the inside of the adsorbent.

Pore size distribution In the solid fiber membrane-like porous support of the present invention, more uniform pores can be obtained from the fiber surface to the central portion, and it is easy to effectively utilize the inside to be adsorbed. Unlike the quality support, an attempt to make a broad pore size distribution and effectively utilize the inside is not particularly important. In the case of a solid fibrous film-like porous support, it is more preferable to have a sharp pore size distribution because a larger effective surface area can be secured per unit volume of the adsorbent. Therefore, the volume of pores having a diameter of 0.01 μm or more and 10 μm or less is preferably 40% or more of the total pore volume, and more preferably 70% or more. Furthermore, 0.05 μm
More preferably, the volume of pores having a diameter of 5 μm or less is 40% or more of the total volume. More preferable when 70% or more,
It is most preferable that the distribution is very sharp, especially 80%.

Total Surface Area The total surface area, based on dry weight, of the solid fiber membrane-like porous support of the present invention is particularly preferably 1 m ² / g or more, more preferably 5 m ² / g or more, further preferably Is 10 m ² / g or more. Obviously, the larger the total surface area, the higher the adsorption capacity, but when used as a porous support for an adsorbent for extracorporeal circulation treatment, if the total surface area becomes too large, substances other than the adsorption target substance The risk of non-specific adsorption also increases. Particularly when used for blood or body fluid, many useful trace proteins coexist, and it is not preferable that the nonspecific adsorption amount of these proteins increases. Therefore, it is preferably 500 m ² / g or less, more preferably 300 m ² / g or less, and most preferably 150 m ² / g or less.

Method of Measuring Pore Size, Pore Size Distribution, Surface Area The pore size and pore size can be determined by mercury intrusion curve and mercury intrusion curve. The surface area can also be calculated from the amount of adsorption using a gas such as nitrogen,
(BET method) Since the surface area can be obtained in comparison with the pore size distribution, it is preferable to determine it by the mercury intrusion method like the pore size. The specific pore diameter, pore diameter distribution, and surface area can be measured using a mercury porosimeter (manufactured by Shimadzu Corporation, Micromeritics Pore Size 9320). Pore Plot System (Shimadzu Corporation, 9320)
-PC2 (V1.0)) to analyze the pore size, pore size distribution,
The surface area can be determined. At this time, the pressure range of mercury was 1 to 30,000 psia.

Pore Volume The total pore volume of the solid fiber membrane-like porous support is 0.1 ml / g when expressed as the total amount of the pore volume per dry weight of the solid fiber membrane-like porous support. It is preferably not less than 50 ml / g. If the total pore volume is less than 0.1 ml / g, the surface area that works effectively in practice will be small, and sufficient adsorption capacity cannot be obtained. The total pore volume is 50 ml
If it exceeds / g, the strength of the solid fiber membrane-like porous support becomes low, which is not preferable in use. A more preferable range of the total pore volume of the solid fiber membrane-like porous support is 0.5
ml / g or more and 30 ml / g or less, more preferably 1 ml / g or more and 10 ml / g or less.

Definition of solid fiber membrane-like porous support The solid fiber membrane-like porous support in the present invention means that a molecule having an affinity for a target substance, that is, a ligand is insolubilized on the surface. For the adsorbent, a porous support having a large number of pores opened on the surface, which has a sufficiently long length in the longitudinal direction with respect to the thickness, a filamentous or fibrous material, The shape of the cross section may be any shape such as a circle, an ellipse, a polygon, and a star. Furthermore, the central portion of the cross section does not have a hole penetrating in a substantially same shape along the longitudinal direction. The hole penetrating in the central part of the cross section along the longitudinal direction with substantially the same shape is separated by the membrane from the outside of the hollow fiber, which the hollow fiber membrane has, for example, is continuously formed during spinning. Refers to the internal space, etc., and does not refer to those formed irregularly by the continuity of pores.

Length and Thickness of Solid Fiber Membrane Porous Support The length of the solid fiber membrane porous support in the longitudinal direction is
That is, it suffices that the diameter is substantially longer than the diameter, and no particular regulation is required, but in terms of handleability, it is preferably 50 mm or more. If the diameter is too thin, the solid fibrous membrane-like porous support will be easily cut, resulting in poor handleability.If it is too thick, the substance to be adsorbed will probably be difficult to penetrate into the solid fibrous membrane-like porous support, so adsorption Since the ability becomes low, the diameter when the cross-sectional area is converted into a circle is preferably 1 μm or more and 10 mm or less, more preferably 10 μm or more and 1 mm or less. Particularly preferably, it is 50 μm or more and 300 μm or less.

Material The solid fibrous membrane porous support has excellent stability of the support itself, no eluate, little change in shape between dry and wet states, and easy ligand immobilization on the surface of the support. In addition, an organic synthetic polymer material is preferable because it can be efficiently performed. Specific materials include nylon resin such as nylon 6 and nylon 66, polyacetal resin, polycarbonate resin, modified polyphenylene oxide resin, polybutylene terephthalate, polyethylene terephthalate, polyphenylene sulfide, diallyl phthalate, polyimide, polyamideimide, polymethylpentene, poly Sulfone, polyether fluphone, polyacrylate, polyether ester ketone, polytetrafluoroethylene, polyethylene, polypropylene, polyvinyl chloride, polystyrene, phenol, epoxy, polyurethane, polyvinyl acetal, biscol, ABS, ethylene vinyl alcohol, rubber urea resin, Cellulose, cellulose acetate, polymethylmethacrylate, etc. or this Copolymers can be mentioned including, it is particularly preferably a synthetic polymer material from the point of view of stability during insolubilization and sterilization operations of the ligand. Among them, polyolefins such as polyethylene and polypropylene, polysulfone, and polymethylmetaacrylate are easy to form into a solid fiber membrane and easy to form preferable pores, and also from the viewpoint of flexibility. Further, a polymer material containing cellulose as a component is more preferable, and a polyolefin polymer material such as polyethylene or polypropylene is particularly preferable because a strip-shaped through hole can be obtained.

Production Method 1 The production of the solid fibrous membrane-like porous support is carried out by a foaming agent decomposition method using an organic or inorganic foaming agent which decomposes at a specific temperature to generate nitrogen gas, carbon dioxide gas or the like, and evaporation. Mold solvent is added and mixed at the raw material stage, and the solvent vaporization method is used to vaporize and foam the solvent during synthesis, the gas mixing method is used to mechanically mix and foam the gaseous foaming agent in the normal state, and the gas generated in the polymerization process is used. Chemical reaction method, elution method in which soluble substance is dispersed in polymer material and then eluted, sintering method in which powder particles are bonded to each other by a sintering action below melting temperature, wet phase conversion method, melt phase separation method, melt spinning A stretching opening method or the like can be used. Among them, the wet phase conversion method, the melt phase separation method, and the melt spinning draw opening method are preferable because a support having a preferable fiber diameter is easily obtained.
In particular, it is easy to obtain a fibrous shape, and since no solvent or other additives are used in the polymer material, there is no problem of residual solvent, so after melt-spinning the crystalline polymer into a fibrous shape. A stretch-opening method is particularly preferable in which the crystal lamellae are cleaved by cold stretching and the pore size is expanded by hot stretching to form a porous structure composed of a stacked lamella and microfibrils. When the pores have a porous structure composed of stacked lamellae and microfibrils, the flow resistance of the solution into the porous structure is small, so that the ligand can be fixed inside the fibrous porous support uniformly to the inside. It is particularly preferable because it can be effectively used as an adsorbent even inside.

Production Method 2 A production example of the porous support of the present invention will be described by taking a polyethylene material as an example. High-density polyethylene (density 0.6 or more, melt index value 4 or more and 7 or less) spinning diameter 5 m
For example, using a circular spinneret of m or more and 50 mm or less, the spinneret temperature is 130 ° C. or more and 200 ° C. or less, and the polyethylene discharge amount is 2
Melt spinning is performed at g / min or more and 30 g / min or less and a winding speed of 50 m / min or more and 1,000 m / min or less. The tension at the time of winding at this time is 0.5 gf or more and 50 gf or less. The obtained polyethylene yarn is cold-stretched at a temperature of 80 ° C. or less to 1.1 times or more and 3.0 times or less, and then thermally stretched at a temperature of 100 ° C. or more to 1.2 times or more and 10 times or less and stretched. By forming pores, a polyethylene porous support having a solid fiber membrane-like porous structure can be obtained. The total draw ratio is 1.5 times or more and 20 times or less.

Kind of Ligand The solid fiber membrane-like porous support can be used by insolubilizing a substance having an affinity for the adsorption target substance, that is, a ligand, on its surface. As the ligand, a known synthetic compound having an affinity for the adsorption target substance or a natural substance can be used. For example, anti-low density lipoprotein antibody, tryptophan, acetylcholine receptor-derived polypeptide, phenylalanine,
Torpedo-derived polypeptide, blood group (A type, B type) antigen, protein A, trimethylammonium group, dimethylammonium group, aspartame, polymyxin B,
Anti-immunoglobulin antibody, anti-leukocyte differentiation antigen antibody such as anti-CD8 antibody and anti-CD4 antibody, anti-cytokine antibody such as anti-cancer necrosis factor antibody, anti-endotoxin antibody, single-stranded or double-stranded DNA and the like. Further, of these, two or more kinds of ligands may be insolubilized. The molecular weight of these ligands may be any molecular weight, but from the practical point of view, 1,000,000 or less is easily available.

Ligand Immobilization Method The ligand can be insolubilized in the solid fiber membrane-like porous support by dipping in a liquid in which the ligand is dissolved or by spraying the liquid, chemically or A method of covalently bonding to the surface of the solid fiber membrane porous support by a grafting method using radiation or electron beam, or a covalent bond via a functional group on the surface of the solid fiber membrane porous support by a chemical method. There are ways to do it. Among them, the grafting method and the covalent bonding method via a functional group are preferable because there is no risk of ligand elution during use. As an example of a method for obtaining a functional group on a solid fiber membrane-like porous support, a cyanogen halide method, an epichlorohydrin method, an epibromhydrin method, a bisepoxide method, a bromoacetyl bromide method, a tresyl chloride method, promoacetamide The law is known. Specific examples include an amino group, a carboxyl group, a hydroxyl group, a thiol group, an acid anhydride group, a succinylimide group, a chlorine group, an aldehyde group, an amide group, an epoxy group and a tresyl group. Among these, epoxy groups derived from the epichlorohydrin method and the epibromhydrin method are particularly preferable because of their stability during heat sterilization.

Fixed amount of ligand The amount of the ligand to be introduced is not particularly specified, but if it is too small, the adsorption capacity is low, and if it is too large, the ligand may be released during use. 1 ng / ml or more per volume including the pore volume of the quality support 10
It is preferably 0 mg / ml or less. Furthermore, the more preferable range is 1 μg / ml or more and 100 μg / m or more.
1 or less.

Uses The solid fibrous membrane-like porous support is used for adsorbing a dissolved substance in water or an organic solvent, and particularly for proteins, sugars, nucleic acids, hormones, lipids, cytokines and the like in body fluids such as blood. Suitable as a support for adsorbents. Most preferably, it can be used as a support for a selective or specific adsorbent for clinical extracorporeal circulation treatment. Clinically, the use of selective or specific adsorption for extracorporeal circulation treatment includes bile acid, amyloid precursor protein A, cancer necrosis factor, bilirubin, bilirubin-conjugated albumin, endotoxin, anti-cardiolipin antibody, anti-acetylcholine receptor antibody, low density and / or Or very low density lipoprotein, sulfatide adhesion protein,
Activated complement component, amyloid protein A, immune complex, anti-blood group antibody, anti-platelet antibody, auto-antibody such as anti-DNA antibody and rheumatoid factor, and / or immunity B producing the auto-antibody
Cells, T cells, immunoglobulin L chains, blood coagulation VII
Examples include factor I, blood coagulation factor IX, β ₂ microglobulin and the like.

Method of Use The adsorbent obtained by insolubilizing the solid fiber membrane-like porous support with the ligand can be used as it is, or cut into short pieces, or made into cotton and packed in a container to be used as a column. Alternatively, the adsorbent that has been processed into a woven or non-woven fabric can be used as a column by, for example, stacking the woven or non-woven fabric into a flat plate or rolling it into a cylinder and filling the container. Alternatively, a part of the adsorbent obtained by insolubilizing the ligand on the solid fiber membrane porous support may be fixed to the container with an adhesive or the like before use. Further, two or more kinds of adsorbents may coexist in layers or randomly. The container may have an inflow port and an outflow port for the solution to be adsorbed, and may have a structure in which the adsorbent does not substantially flow out. At this time, the ratio of the adsorbent volume to the total internal volume of the container is preferably 20% or more and 90% or less,
Taking a more preferable range, 40% or more and 80% or less is particularly excellent. In actual use, blood may be directly perfused, or plasma obtained by previously separating by a centrifugation method or a membrane method may be perfused. At this time, blood or plasma may be continuously perfused or intermittently perfused. In particular, the adsorbent obtained by insolubilizing the ligand on the fibrous porous support of the present invention is a bundle of fibers and both ends of the bundle are kept in a bundle shape by using urethane or silicone adhesive, When it is fixed in a container, it has excellent platelet passage properties and can be preferably used for the purpose of directly perfusing blood. At this time, the bundle may be fixed to the container by the adhesive, or may be fixed by a physical method using the container structure.

[0023]

The solid fiber membrane-like porous support of the present invention comprises:
Since the effective surface area is increased, many ligands can be easily and stably fixed on the surface, and moreover, it is stable in a wet state, and it is excellent as a versatile adsorbent support.

[0024]

Example 1 High-density polyethylene (density 0.968, M
I value of 5.5, trade name Hi-Zex 2208J) using a circular spinneret with a spinneret diameter of 35 mm, spinning temperature 150 ° C., polyethylene discharge rate 16 g / min, spinning distance 5 m, spinning cooling temperature 20 ° C., winding tension 10 gf , Winding speed 400
Melt spinning was performed at m / min. The draft ratio at this time is 24,
It was 000. After spinning, it was annealed at 115 ° C. for 2 hours. The obtained polyethylene yarn at room temperature (22 ° C),
Primary roller speed 3.75 m / min, secondary roller speed 5
Cold drawing was performed at m / min. The cold draw ratio at this time was about 1.3 times. Next 108 ° C, 119 ° C, 122 ° C continuously
Roller speed of 15m /
Min., 19.5 m / min, and 21.8 m / min, and drawn at a drawing speed to draw holes to obtain a polyethylene porous support having a solid fiber membrane-like porous structure. The total draw ratio of the porous support was 5.8 times, the yarn diameter was 176 μm, and the winding length was 15 km. The porous support has a mean pore size of 0.20 μm, a total pore volume of 3.6 ml / g, and a porosity of 7 according to the mercury porosimetry.
7.8%, total surface area 71.03 m ² / g, pore size 0.01
The volume of pores having a size of μm to 10 μm is 84 of the total pore volume.
%Met. Porous support (length 12 cm, 1,000
Electron beam of 200 kGy in a nitrogen atmosphere. Immediately after the irradiation, it was immersed in a methanol solution in which 10% glycidyl methacrylate was dissolved and reacted at 40 ° C. for 10 minutes. Graft ratio calculated from weight change is 98.2%
Therefore, a large amount of epoxy groups could be introduced. Diethylamine was reacted in an aqueous solution of 10% diethylamine dissolved in this epoxy group-introduced porous support at pH 10.0 to obtain an adsorbent having a diethylamino group on the surface. The total ion exchange capacity at the time of adsorption was 1.8 meq / g. . Next, 700 adsorbents (filling rate 35%)
The adsorbent was inserted side by side in the lengthwise direction of the container into a cylindrical container made of polycarbonate having an inner diameter of 8 mm and a length of 10 cm, and both ends of the adsorbent were bonded and fixed together with the container by urethane. At this time, both ends of the container were sealed with urethane. The container had separate inlets and outlets on the side. The inlet and outlet were not blocked by urethane at both ends, and were provided at positions farthest from each other. The adsorber was obtained as described above. 16 ml of a solution prepared by dissolving bilirubin in a physiological saline solution containing 0.3% bovine albumin at a concentration of 20 mg / dl was added to the obtained adsorber.
Was perfused at 0.2 ml / min and the bilirubin concentration in the effluent of the adsorber was measured to determine the bilirubin adsorption rate. The adsorption rate at this time was 64%, which was a very excellent adsorption property. Then, the obtained adsorber was used to evaluate the direct perfusion of blood. Normal human blood was collected in the presence of ACD-A1 / 9 as an anticoagulant. When 40 ml of this blood was perfused into the adsorber at 1.2 ml / min and the number of platelets in the adsorber effluent was measured, the reduction rate of platelets was as small as 12.3%.

[0025]

[Example 2] In Example 1, the amount of polyethylene discharged during spinning was 8 g / min, the winding tension was 8.4 gf, the winding speed was 500 m / min, and the temperature conditions during hot drawing were 98 ° C and 104 ° C.
At 119 ° C., a polyethylene porous support having a solid fiber membrane porous structure was obtained (total draw ratio: 5.8 times, yarn diameter: 112 μm, winding length: 15 km). The porous support has an average pore diameter of 0.11 μm, a total pore volume of 2.7 ml / g, a total surface area of 102.3 m ² / g, and a volume of pores of 0.01 μm or more and 10 μm or less, which are determined by mercury porosimetry. It was 92% of the pore volume. Porous support (length 10 cm, 1
100 pieces) was immersed in a methanol solution in which 10% glycidyl methacrylate was dissolved, and 25 kGy in a nitrogen atmosphere.
Was irradiated with γ-rays. The graft ratio obtained from the change in weight was 8.3%. This epoxy group-introduced porous support was reacted with phenylalanine in a 0.1N sodium hydroxide aqueous solution to obtain an adsorbent having phenylalanine on its surface. The fixed amount of phenylalanine was 53 μ equivalents per 1 ml of the adsorbent. 100 ml of this adsorbent was filled in a 1 ml syringe, and 1 ml of rheumatoid arthritis patient plasma was perfused at 0.01 ml / min. The concentration of the immune complex in plasma before perfusion was 25.3 μg / ml, whereas the concentration of the immune complex after perfusion was 10.0 μg / ml or less, and the reduction rate of the immune complex due to adsorption was It showed an excellent immune complex adsorption capacity of 60.0% or more.

[0026]

Example 3 High density polyethylene (density 0.968, M
I value 5.5, trade name Hi-Zex 2208J) using a circular spinneret with a spinneret diameter of 10 mm, spinning temperature 150 ° C., polyethylene discharge rate 8 g / min, spinning distance 5 m, spinning cooling temperature 23 ° C., winding tension 3 gf , Winding speed 260m /
And melt-spun. The draft ratio at this time is 7,000
Met. After spinning, it was annealed at 115 ° C. for 2 hours.
The obtained polyethylene yarn was cold-drawn at room temperature (25 ° C.) at a primary roller speed of 1.5 m / min and a secondary roller speed of 2 m / min. The cold draw ratio at this time was about 1.3 times. Next, at three consecutive temperatures of 108 ° C., 119 ° C. and 122 ° C., roller speeds of 6 m / min and 7.8, respectively.
A polyethylene porous support having a solid fiber membrane-like porous structure was obtained by hot drawing at a drawing speed of m / min and 8.7 m / min for drawing and opening. The total draw ratio of the porous support is 5.8 times,
The yarn diameter was 162 μm and the winding length was 15 km. The porous support has an average pore diameter of 0.36 μm, a total pore volume of 4.8 ml / g, a porosity of 83.0%, a total surface area of 37.3 m ² / g, and a pore diameter of 0.01 μm or more and 10 μm or less by a mercury intrusion method. The volume of the pores was 81% of the total volume of the pores. A porous support (length 10 cm, 250 pieces) was used as a copolymer of hydroxyethyl methacrylate and diethylaminoethyl methacrylate 1.1 of 1.1 (molecular weight of about 13,000) 3.
It was immersed in 100 ml of a 50% ethanol aqueous solution in which 100% was dissolved, irradiated with 50 kGy of γ-rays, and radiation-grafted. The graft ratio obtained from the weight change was 28.3%. The adsorbent thus obtained was made into a cotton shape and filled in a polycarbonate container having an inlet and an outlet and each having a mesh for preventing leakage of the adsorbent and having an internal volume of 1 ml to obtain an adsorber. The adsorber was perfused with 3 ml of healthy human plasma containing 2 U / ml of heparin at a flow rate of 0.02 ml / min. Prealbumin concentration in plasma before perfusion was 28.7 mg / d
While the prealbumin concentration in the plasma discharged from the adsorber was 1.4 mg / dl, the prealbumin reduction rate due to adsorption was 95.1%, which was excellent.

Claims (2)

[Claims] 1. Pore having an average pore diameter of 0.01 μm or more and 10 μm or less, and a total surface area of 3 m ² / g or more and 500 m ² /
A solid fibrous membrane-like porous support made of an organic polymer material having a volume of g or less and a pore diameter of 0.01 μm or more and 10 μm or less of 40% or more of the total pore volume. 2. Pore having an average pore diameter of 0.01 μm or more and 10 μm or less and a total surface area of 3 m ² / g or more and 500 m ² /
The ligand is insolubilized on the surface of a solid fiber membrane porous support made of an organic polymer material having a volume of pores of g or less and a pore diameter of 0.01 μm or more and 10 μm or less of 40% or more of the total pore volume. An adsorbent made of.