WO2017195457A1 - Membrane de fibres creuses poreuse en résine de polyéthylène, membrane de séparation et procédé de fabrication desdites membranes - Google Patents

Membrane de fibres creuses poreuse en résine de polyéthylène, membrane de séparation et procédé de fabrication desdites membranes Download PDF

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WO2017195457A1
WO2017195457A1 PCT/JP2017/010112 JP2017010112W WO2017195457A1 WO 2017195457 A1 WO2017195457 A1 WO 2017195457A1 JP 2017010112 W JP2017010112 W JP 2017010112W WO 2017195457 A1 WO2017195457 A1 WO 2017195457A1
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hollow fiber
fiber membrane
porous hollow
polyethylene resin
molecular weight
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PCT/JP2017/010112
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English (en)
Japanese (ja)
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淳一 樋渡
志朗 中島
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旭化成メディカル株式会社
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Priority to CN201780029407.9A priority Critical patent/CN109070021B/zh
Priority to JP2018516368A priority patent/JP6792612B2/ja
Publication of WO2017195457A1 publication Critical patent/WO2017195457A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/26—Polyalkenes
    • B01D71/261—Polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08—Hollow fibre membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/26—Polyalkenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof

Definitions

  • the present invention relates to a porous hollow fiber membrane containing a polyethylene-based resin, and in particular, a separation membrane used for separating and eliminating a specific substance (particularly suitable for separating plasma from blood in plasma exchange therapy).
  • the present invention relates to a porous hollow fiber membrane that can be suitably used as a base material for a separation membrane used in the above and a production method thereof.
  • the melt-stretching and opening method is a method in which a crystalline polymer compound is melted and spun into a hollow fiber shape, and the wound hollow fiber is made porous by stretching to obtain a porous hollow fiber membrane. Since the porous hollow fiber membrane obtained by this method does not use a liquid component such as a solvent or a plasticizer in the production process, there is no fear of elution of the liquid component during use, and it is suitable for plasma separation.
  • the porous hollow fiber membrane When applying to plasma separation, if the porous hollow fiber membrane is made of a hydrophobic polymer, the porous surface is covered with a hydrophilic substance, etc., imparting hydrophilicity / low protein adsorption, and blood compatibility Sexuality is enhanced.
  • the pore diameter of the porous hollow fiber membrane is controlled in the range of 0.01 to 2 ⁇ m from the viewpoint of separation of blood cell components and plasma components from blood. Further, the porous hollow fiber membrane is sterilized from the viewpoint of safety before plasma separation.
  • the porous structure formed by the melt-stretching hole-opening method is such that a lamellar laminate of hollow fibers before stretching (hereinafter referred to as “hollow fibers before stretching”) is cleaved by cold stretching, and the resulting micropores are further expanded by hot stretching. Can be obtained.
  • the hollow fiber before stretching contains an insufficiently grown lamellar laminate
  • the porous hollow fiber membrane after stretching is not perforated by about 0.1 to 50 mm in the yarn length direction. A portion (hereinafter referred to as “unstretched portion”) is generated.
  • the unstretched portion Since the unstretched portion is not porous, it does not have a separation function, but it only constitutes a part of the porous hollow fiber membrane, so that it does not reach the original separation / permeability of the separation membrane. Absent. That is, the porous hollow fiber membrane including the unstretched portion does not cause a problem in terms of function as a separation membrane. However, when a porous hollow fiber membrane containing an unstretched part is used for plasma separation, there are therapeutic problems in the following points. That is, the hollow fiber before stretching has a translucent appearance, but the porous hollow fiber membrane after stretching is whitened due to irregular reflection of light by the pores. On the other hand, the unstretched portion having no pores reflects the appearance of the hollow fiber before stretching and remains translucent.
  • Patent Document 1 as a means for improving the homogeneity of a porous hollow fiber membrane obtained by a melt-stretching hole-opening method, a metal compound having a crystallization nucleation ability is formed on a crystalline polymer constituting the porous hollow fiber membrane. A method of adding 0.01% by weight or more is disclosed.
  • the porous hollow fiber membrane disclosed in Patent Document 1 is intended to improve the fine pore distribution spots in the hollow fiber length direction and the hollow fiber cross-sectional direction, which leads to the elimination of the unstretched portion. Not.
  • An object of the present invention is to provide a polyethylene resin porous hollow fiber membrane having few unstretched parts and excellent in homogeneity, which can be used as a base material for a separation membrane for plasma separation. It is to provide a separation membrane with less pseudo-leakage of blood using a porous hollow fiber membrane.
  • the present inventors have found that the ratio of the component having a molecular weight of 10,000 or less and the component having a molecular weight of 1,000,000 or more contained in the porous hollow fiber membrane is in a specific range, or a polyethylene resin used as a raw material.
  • the resin composition containing a polyethylene-based resin contains 1.0% by mass or more of a component having a molecular weight of 1000 or less
  • the melt flow rate measured by JIS K7210 (Code D) hereinafter, “MFR / D”
  • MFR / G melt flow rate measured in accordance with JIS K7210
  • a porous hollow fiber membrane comprising a polyethylene resin and having a plurality of microfibrils oriented in the yarn length direction, and a knot portion composed of a lamellar laminate connected to both ends of the microfibrils, having a molecular weight of 10,000
  • a polyethylene resin porous hollow fiber membrane having a mass fraction of the following components of 17.5% by mass or more and a mass fraction of a component having a molecular weight of 1 million or more of less than 1.5% by mass.
  • the olefin wax is a high density low molecular weight ethylene polymer having a density of 960 kg / m 3 or more, a low density low molecular weight ethylene polymer having a density of less than 940 kg / m 3 , a low molecular weight ethylene-propylene copolymer, and
  • [5] A polyethylene resin porous hollow fiber membrane according to any one of [1] to [4], and a hydrophilic polymer provided on at least a part of the surface of the polyethylene resin porous hollow fiber membrane. And a hydrophilic layer.
  • [7] The separation membrane according to [5] or [6], wherein a melt flow rate (MFR / D) measured by JIS K7210 (Code D) is 0.03 or more.
  • MFR / D melt flow rate measured by JIS K7210
  • a polyethylene resin porous material comprising a step of producing a hollow fiber from a polyethylene resin or a resin composition containing a polyethylene resin, and a step of forming a porous hollow fiber membrane by stretching the hollow fiber.
  • the olefin wax is a high density low molecular weight ethylene polymer having a density of 960 kg / m 3 or more, a low density low molecular weight ethylene polymer having a density of less than 940 kg / m 3 , a low molecular weight ethylene-propylene copolymer, and
  • [14] The method for producing a polyethylene resin porous hollow fiber membrane according to [13], wherein the olefin wax is a high density low molecular weight ethylene polymer having a density of 960 kg / m 3 or more.
  • a step of obtaining a polyethylene resin porous hollow fiber membrane by the production method according to any one of [9] to [14], and a hydrophilic polymer on at least a part of the surface of the porous hollow fiber membrane The manufacturing method of the separation membrane including the process of providing the hydrophilic layer containing.
  • a polyethylene resin porous hollow fiber membrane having a high degree of homogeneity with few unstretched portions that can be used as a base material for a separation membrane for plasma separation with less pseudo blood leakage. it can.
  • the present embodiment a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail.
  • this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.
  • the porous hollow fiber membrane of this embodiment contains a polyethylene resin.
  • the porous hollow fiber membrane can be used as a separation membrane as it is, but it is more suitable for plasma separation if at least a part of its surface is covered with a hydrophilic layer containing a hydrophilic polymer. It becomes. In addition, by performing sterilization treatment with radiation or the like, a separation membrane more suitable for plasma separation is obtained.
  • the mass fraction of the component having a molecular weight of 10,000 or less is 17.5% by mass or more
  • the mass fraction of the component having a molecular weight of 1,000,000 or more is less than 1.5% by mass. .
  • the porous hollow fiber membrane of the present embodiment is composed of a plurality of microfibrils oriented in the yarn length direction (short fibrous bodies composed of an assembly of molecular chains (however, the length is not limited)), and the microfibrils of the microfibrils It has a nodule part (a nodal connection part connecting the ends of microfibrils) made of a lamellar laminate connected to both ends, and has a plurality of slit-like pores formed between adjacent microfibrils ing.
  • the bundling portion connects, for example, end portions of oriented (or substantially parallel) microfibrils.
  • the structure composed of the knot part-the plurality of microfibrils-knot parts may be repeated in the yarn length direction to constitute a substantially mesh structure.
  • Such a structure is generally a structure found in a porous hollow fiber membrane obtained by a melt-stretch opening method, and is confirmed by observing the surface of the inner wall or outer wall of the hollow fiber with a scanning electron microscope or the like. Can do.
  • a specific example of this structure is shown in FIG.
  • the porous hollow fiber membrane is It is preferable to manufacture by the melt stretch opening method.
  • the porous hollow fiber membrane of this embodiment contains a polyethylene resin.
  • the content of the polyethylene resin in the porous hollow fiber membrane is not limited, but is preferably 70% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more. 95% by mass or more is particularly preferable. Moreover, 100 mass% may be sufficient.
  • the mass fraction of the component having a molecular weight of 10,000 or less in the porous hollow fiber membrane is 17.5% by mass or more, preferably 18.0% by mass or more, and particularly preferably 18% by mass or more and 20.0%. It is less than mass%.
  • the mass fraction of the component having a molecular weight of 1,000,000 or more of the porous hollow fiber membrane may be less than 1.5 mass%, may be 1.45 mass% or less, or is 1.35 mass% or less. May be.
  • the porous hollow fiber membrane is porous hollow so that the mass fraction of the component having a molecular weight of 10,000 or less is 17.5% by mass or more and the mass fraction of the component having a molecular weight of 1,000,000 or more is less than 1.5% by mass.
  • the mass fraction of the component having a molecular weight of 10,000 or less is preferably less than 20.0% by mass.
  • the component having a molecular weight of 1 million or more is preferably 1% by mass or more.
  • the mass fraction of the component having a molecular weight of 10,000 or less and the mass fraction of the component having a molecular weight of 1,000,000 or more of the porous hollow fiber membrane are the polyethylene resin or polyethylene resin that is the raw material of the porous hollow fiber membrane.
  • the mass fraction of the component having a molecular weight of 10,000 or less in the porous hollow fiber membrane can be easily made 17.5 mass% or more, and the mass fraction of the component having a molecular weight of 1,000,000 or more can be easily made less than 1.5 mass%. I understood.
  • the “resin composition containing a polyethylene resin” means a material other than a single type of polyethylene resin among the polyethylene resin-containing materials constituting the porous hollow fiber membrane of the present embodiment.
  • a mixture of a plurality of polyethylene resins for example, a mixture of a polyethylene resin and an olefin wax, which are main raw materials described later
  • a mixture of a polyethylene resin and other resins for example, a mixture of a polyethylene resin and other resins, and additives other than resins. And the like added.
  • a porous hollow fiber membrane may be produced while appropriately adjusting the molecular weight distribution, but the component having a molecular weight of 1000 or less as a raw material is generally in the range of 1.0% by mass or more without finely adjusting the molecular weight distribution of the raw material.
  • the mass fraction of the component having a molecular weight of 10,000 or less of the porous hollow fiber membrane is easily 17.5% by mass or more and the component having a molecular weight of 1,000,000 or more.
  • the mass fraction can be less than 1.5% by mass.
  • the MFR / D (melt flow rate measured by JIS K7210 (code D)) is 3.0 to 10.0
  • the MFR / G melt flow rate measured by JIS K7210 (code G)
  • the molecular weight of the porous hollow fiber membrane obtained therefrom is 10,000.
  • the mass fraction of the following components tends to be 17.5% by mass or more, and the mass fraction of a component having a molecular weight of 1 million or more tends to be less than 1.5% by mass.
  • the mass fraction of the component having a molecular weight of 10,000 or less in the porous hollow fiber membrane tends to increase as the proportion of the component having a molecular weight of 1000 or less in the raw material increases.
  • the component having a molecular weight of 1000 or less in the raw polyethylene resin or resin composition is preferably 3% by mass or less. It is more preferably at most mass%, further preferably at most 1.5 mass%.
  • a raw material polyethylene resin or resin composition having a mass fraction of a component having a molecular weight of 1000 or less of 1.0% by mass or more was used.
  • the component having a molecular weight of 1000 or less in the polyethylene resin or the resin composition acts as a plasticizer, and the crystallization rate of the polyethylene resin is reduced, thereby promoting the growth of the lamellar laminate. This is thought to lead to uniformization. Therefore, also from such a viewpoint, it is preferable to use a polyethylene resin or resin composition having a mass fraction of a component having a molecular weight of 1000 or less in a range of 1.0% by mass or more.
  • the component having a molecular weight of 10,000 or less in the porous hollow fiber membrane It becomes easy to make the mass fraction of the component having a mass fraction of 17.5% by mass or more and the molecular weight of 1 million or more less than 1.5% by mass. It tends to be more facilitated to make the lamellar laminate uniform in the yarn length direction and the film thickness direction, which is seen when a material having a mass fraction of 1.0% by mass or more is used.
  • the MFR / D of the polyethylene resin or the resin composition is more preferably 3.5 to 6.0, still more preferably 3.8 to 5.8, and the MFR / G is more preferably 160 to 270, and further Preferably, it is 170-200.
  • the polyethylene resin is an ethylene homopolymer or a copolymer of ethylene and other monomer components (the content of other monomer components is preferably 5 mol% or less).
  • a preferred specific example in this embodiment is high density polyethylene with high density and few branches.
  • the density of the high density polyethylene (according to JIS K7112: 1999) is preferably 950 kg / m 3 or more, more preferably 960 kg / m 3 or more.
  • a pre-stretch raw yarn obtained from high-density polyethylene having a density of less than 950 kg / m 3 has a low crystallinity, so that the pore size of the porous hollow fiber membrane obtained by stretching is desired (for example, suitable for plasma separation). D) It is difficult to adjust the stretching conditions for the range.
  • the porous hollow fiber membrane when used for plasma separation, preferably has a pore size of 0.01 to 2 ⁇ m, more preferably 0.1 to 0.6 ⁇ m.
  • the pore diameter refers to the maximum pore diameter measured by the bubble point method (JIS K3832: 1990).
  • the method for adjusting the mass fraction of the component having a molecular weight of 1000 or less of the polyethylene resin or resin composition that is the raw material of the porous hollow fiber membrane there is no limitation on the method for adjusting the mass fraction of the component having a molecular weight of 1000 or less of the polyethylene resin or resin composition that is the raw material of the porous hollow fiber membrane.
  • the component having a molecular weight of 1000 or less may have a mass fraction of 1.0% by mass or more.
  • a component having a molecular weight of 1000 or less can be obtained by blending an olefin wax with a polyethylene resin as a main raw material.
  • the resin composition having a mass fraction of 1.0% by mass or less can be obtained.
  • the olefinic wax is generally within a range of 0.1 to 10.0% by mass with respect to the total amount of the main raw material polyethylene resin and the olefinic wax (the content of the main raw material polyethylene resin is It may be blended with the polyethylene resin so that it falls within the range of 90.0 to 99.9% by mass.
  • the actual blending amount of the olefin-based wax can be determined according to the respective properties with the above as a guide.
  • the olefin wax preferably has a viscosity average molecular weight of 700 to 8000, more preferably in the range of 2000 to 6000.
  • the olefin wax having a viscosity average molecular weight of less than 700 has a molecular weight that is too low and may be eluted from the porous hollow fiber membrane.
  • an olefin wax having a viscosity average molecular weight of more than 10,000 loses its plasticizer effect due to its too high molecular weight and cannot be expected to promote the growth and uniformity of the lamellar laminate.
  • the olefin wax is a high density low molecular weight ethylene polymer having a density of 960 kg / m 3 or more, a low density low molecular weight ethylene polymer having a density of less than 940 kg / m 3 , a low molecular weight ethylene-propylene copolymer, And at least one selected from the group consisting of low molecular weight ethylene-butene copolymers.
  • the high density low molecular weight ethylene polymer means a polymer having an ethylene group as a basic skeleton having a density of 950 kg / m 3 or more and a viscosity average molecular weight of 10,000 or less.
  • the coalescence refers to a polymer having an ethylene group as a basic skeleton having a density of less than 950 kg / m 3 and a viscosity average molecular weight of 10,000 or less.
  • the low molecular weight ethylene-propylene copolymer means a copolymer having an ethylene-propylene group as a basic skeleton having a viscosity average molecular weight of 10,000 or less
  • the low molecular weight ethylene-butene copolymer means a viscosity average A copolymer having a molecular weight of 10,000 or less and having an ethylene-butene group as a basic skeleton.
  • the olefin wax is preferably a high density low molecular weight ethylene polymer having a density of 960 kg / m 3 or more, more preferably a density of 970 kg / m 3 in view of compatibility with the main raw material polyethylene resin. It is the above high-density low molecular weight ethylene polymer.
  • the MFR / D of the resin composition containing a polyolefin wax is preferably 3.0 to 10.0, more preferably 3.5 to 6.0, and still more preferably 3. 8 to 5.8.
  • the MFR / G of the polyethylene resin mixed with the polyolefin wax is preferably 150 to 300, more preferably 160 to 270, and still more preferably 170 to 200.
  • the porous hollow fiber membrane may contain any additive in addition to the polyethylene resin and the olefin wax.
  • additives include antioxidants, lubricants, ultraviolet absorbers, light stabilizers, and the like.
  • antioxidant include trade names “Irganox 1010”, “Irganox 1076”, and Irgafos 168 ”.
  • lubricant include calcium montanate, calcium stearate, magnesium stearate and the like.
  • the total content of such optional additives is preferably 5% by mass or less, more preferably 2% by mass or less, and further preferably 1% by mass or less of the porous hollow fiber membrane. .
  • the porous hollow fiber membrane of this embodiment contains a polyethylene resin that is a hydrophobic polymer. Hydrophobic polymers interact with blood, so when they are used for plasma separation membranes, etc., the surface of the porous hollow fiber membrane is covered with a hydrophilic layer containing a hydrophilic polymer. It is preferable to do.
  • the hydrophilic polymer include polyhydroxyethyl methacrylate, polyhydroxypropyl methacrylate, polyvinyl pyrrolidone, and an ethylene-vinyl alcohol copolymer. These may be used alone or in combination of two or more.
  • an ethylene-vinyl alcohol copolymer having good adhesion to a polyethylene resin and less peeling from the pore surface of the porous structure is preferable.
  • the ethylene-vinyl alcohol copolymer may be any type such as a random polymer, block polymer, or graft polymer, but the ethylene content of the copolymer is within the range of 20 to 70 mol%. Preferably, it is more preferably in the range of 25 to 50 mol% from the viewpoint of the balance between hydrophilicity and adhesiveness.
  • the adhesiveness of the ethylene-vinyl alcohol copolymer to the polyethylene resin is better, and it is possible to prevent the peeling of the pore surface of the porous structure from the hydrophilic layer. it can. Further, when the ethylene content is 70 mol% or less, the interaction between the hydrophilic layer containing the ethylene-vinyl alcohol copolymer and blood can be reduced.
  • the hydrophilic polymer may be ethylene-vinyl alcohol. It is preferable to use a copolymer.
  • the hydrophilic layer may be composed of only a hydrophilic polymer or may contain additives other than the hydrophilic polymer.
  • the content of the hydrophilic polymer is preferably 70% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more.
  • the degree of hydrophilicity of the porous hollow fiber membrane covered with the hydrophilic layer can be evaluated by the contact angle of water.
  • contact angle measurement methods There are two types of contact angle measurement methods, the static contact angle method and the dynamic contact angle method, but the dynamic contact angle method reflecting the morphology of the porous membrane surface is preferred.
  • the dynamic contact angle methods the well-helmi method is more preferable because it has a high degree of freedom in the shape of the sample.
  • the receding contact angle directly reflects the hydrophilicity of the surface of the substance in water, and is therefore an important index for judging the degree of hydrophilicity of the porous hollow fiber membrane.
  • the receding contact angle of water of the porous hollow fiber membrane covered with the hydrophilic layer is preferably 0 to 15 degrees, more preferably 0 to 10 degrees, and further preferably 0 to 5 degrees. When the receding contact angle of water exceeds 15 degrees, there is a risk of causing plasma protein adsorption, hemolysis, thrombus formation, etc. when used as a separation membrane for plasma separation.
  • the measurement of the receding contact angle with respect to the water of the porous hollow fiber membrane by a well Helmi method can be implemented as follows, for example.
  • Water for injection Japanese Pharmacopoeia manufactured by Fuso Pharmaceutical Co., Ltd.
  • a dynamic contact angle measuring device DCAT11 manufactured by DataPysics Instrument GmbH
  • the porous hollow fiber membrane is cut to about 2 cm and attached to the measuring device.
  • the motor speed at the time of measurement is 0.10 mm / second, the immersion depth is 10 mm, the forward and backward movements are one cycle, and five cycles are measured.
  • the average value of the values obtained by the five measurements is defined as the receding contact angle.
  • the method for producing a porous hollow fiber membrane according to the present embodiment includes a step of producing a porous hollow fiber membrane by a melt stretch opening method or the like, and further when the porous hollow fiber membrane is used as a separation membrane for plasma separation. It is preferable to include a step of forming a hydrophilic layer containing a hydrophilic polymer on the surface of the porous hollow fiber membrane by a coating method or the like.
  • the melt-stretch opening method the main raw material polyethylene resin and, if necessary, a resin composition containing an olefin wax are melt-spun into a hollow fiber shape, and the wound hollow fiber (original yarn before drawing) is made porous by drawing. To obtain a porous hollow fiber membrane.
  • the porous hollow fiber membrane is dipped in an organic solvent or the like (coating liquid) containing a hydrophilic polymer, and then taken out, and then the solvent is dried by heat to form a porous hollow fiber.
  • the surface of the membrane is coated with a hydrophilic polymer.
  • a main raw material polyethylene resin or a resin composition containing a main raw material polyethylene resin and an olefin wax is melt-kneaded by an extruder.
  • a molten polyethylene-based resin (or resin composition) is extruded into a hollow fiber into a spinning cylinder by a circular double nozzle and wound up with a high draft (for example, a draft ratio of 1000 to 8000). It winds up as the formed hollow fiber (original yarn before drawing).
  • the raw yarn before drawing is heat-treated in two stages in an oven.
  • the pre-stretch raw yarn is stretched (for example, a stretch ratio of 10 to 50%) at a low temperature (for example, 10 to 40 ° C.), and the lamellar laminate is cleaved to form micropores.
  • a low temperature for example, 10 to 40 ° C.
  • the pores are further expanded by thermal stretching (for example, at 80 to 130 ° C. and a stretching ratio of 200 to 500%).
  • the raw material of the porous hollow fiber membrane is a resin composition containing an olefinic wax
  • a polyethylene resin for example, 90.0 to 99.9% by mass
  • an olefinic wax for example, 0.1 to 10.0% by mass
  • a porous hollow fiber membrane is produced by a melt stretch opening method using a resin composition containing a polyethylene resin having a molecular weight of 1000 or less and 1.0 mass% or more, particularly an olefin wax polyethylene, an unstretched part It has been found that it is preferable to satisfy the following two requirements in order to produce a porous hollow fiber membrane with a low content.
  • the idle running time from the formation of the unstretched raw yarn to the winding (the residence time until the raw material is extruded from the spinning nozzle (specifically, a circular double nozzle) and wound as a hollow fiber) ) For 1 second or longer, more preferably 1.1 seconds or longer.
  • the temperature of the first stage is 10 to 15 ° C. lower than that of the second stage.
  • the heat treatment method, temperature and time are not limited.
  • the heat treatment method includes placing in a constant temperature room such as an oven.
  • the temperature and time are about 90 to 105 ° C. for 2 to 10 hours at the first stage.
  • the stage can be 100 to 120 ° C. for 1 to 2 hours.
  • a method for forming a hydrophilic layer containing a hydrophilic polymer on at least a part of the surface of the porous hollow fiber membrane is not particularly limited,
  • an ethylene-vinyl alcohol copolymer is used as the molecule, for example, a coating method disclosed in Japanese Patent Publication No. 4-27891 can be used. That is, the porous hollow fiber membrane is left to stand for a predetermined time in a solution in which an ethylene-vinyl alcohol copolymer is heated and dissolved in a water-miscible organic solvent aqueous solution having a predetermined concentration, and then the excess solution is removed.
  • porous hollow fiber membrane having a hydrophilic layer on the surface By drying with hot air at a predetermined temperature, a porous hollow fiber membrane having a hydrophilic layer on the surface can be obtained.
  • the obtained porous hollow fiber membrane having a hydrophilic layer has few unstretched parts, so there is no pseudo-leakage of blood, is excellent in homogeneity, and is a separation membrane suitable for plasma separation.
  • the porous hollow fiber membrane of the present embodiment has less elution of the hydrophilic polymer even when a hydrophilic layer containing the hydrophilic polymer is provided on the porous hollow fiber membrane.
  • a separation membrane having excellent protein adsorptivity and improved compatibility with blood can be obtained. The reason why the elution of the hydrophilic polymer is small is not clear, but it is assumed that the porous hollow fiber membrane of the present embodiment has a large specific surface area and a large contact area with the hydrophilic polymer.
  • the manufacturing method of the separation membrane of this embodiment includes the process of sterilizing a porous hollow fiber membrane.
  • Sterilization methods include ethylene oxide gas sterilization, high pressure steam sterilization, and radiation sterilization. Among these, radiation sterilization with an electron beam, gamma ray, or the like is preferable because the object to be processed can be processed in a packaged state.
  • the porous hollow fiber membrane is particularly preferably sterilized by irradiation with gamma rays having a high sterilization effect.
  • the irradiation dose of gamma rays is adjusted according to the material of the separation membrane. In the present embodiment, it is preferably in the range of 20 kGy to 40 kGy.
  • the MFR / D of the material constituting the porous hollow fiber membrane after sterilization with gamma rays is preferably 0.03 or more.
  • MFR / D is 0.03 or more, the performance as a separation membrane is not impaired.
  • the porous hollow fiber membrane having many unstretched parts is sterilized with gamma rays, it does not show melt viscosity and MFR / D cannot be measured. The cause is not clear, but since the unstretched part is not made porous, the energy density of the part becomes high, and the generation of radicals causes a crosslinking reaction between the molecular chains, resulting in the formation of a network structure that melts. It is assumed that the viscosity is lost.
  • the method for sterilizing the porous hollow fiber membrane with gamma rays is not limited, but an example of the procedure is given below.
  • a separation membrane bundle in which 2200 separation membranes having a length of 250 mm are bundled is inserted into a plasma separation container, a potting agent such as polyurethane resin is injected into both ends, both ends are sealed, a header is attached, and plasma is added
  • a separation module (hereinafter referred to as a module) is created.
  • (2) Fill the module with physiological saline, apply vibration, etc., and completely evacuate the internal air.
  • E (n / L) ⁇ 100 (pieces / m ⁇ %)
  • the filtrate flow ports at both ends of each module were closed, the module was removed from the holder, and the outer periphery of the inner separation membrane bundle was visually observed from the side of the module to confirm the presence of vermilion spots.
  • a vermilion spot was regarded as a simulated blood leak, and it was determined that there was no simulated blood leak when there were no vermilion spots in all 10 modules.
  • the separation membrane was inserted into a polyethylene tube having an inner diameter of 5 mm, and a silicon adhesive was injected around the separation membrane in the tube. After the silicone adhesive was cured, the cross section of the polyethylene tube was cleaved with a razor. The cross section of the separation membrane exposed on the end face of the tube was observed with a microscope, and the outer diameter (DO) and inner diameter (DI) as the equivalent circle diameter were determined using image analysis software (Image-pro plus manufactured by Media Cyberbertics). . DI was defined as the inner diameter of the separation membrane, and half of the difference between DO and DI was determined as the thickness of the separation membrane.
  • mf (1000) ratio a mass fraction of a component having a molecular weight of 1000 or less (hereinafter referred to as “mf (1000) ratio”) of a polyethylene resin (or a resin composition in which an olefin wax is blended with a polyethylene resin)
  • TCB 1,2,4-Trichlorobenzene
  • mf (10000) fraction The mass fraction of the polyethylene-based resin constituting the porous hollow fiber membrane, or the component having a molecular weight of 10,000 or less (hereinafter referred to as “mf (10000) fraction”) and the mass fraction having a molecular weight of 1,000,000 or more.
  • ⁇ Measuring device High-temperature GPC device (PL-GPC220 manufactured by Agilent Technologies) ⁇ Column: TSKgel GMHHR-H (20) 2 ⁇ Device temperature: 160 °C for all channels -Eluent: TCB (containing 0.05% dibutylhydroxytoluene) Sample injection volume: 500 ⁇ L ⁇ Detector: Suggested refractive index detector RI ⁇ Calibration curve: Calculation was carried out in the first order using a monodisperse polystyrene as a standard sample and a conversion factor (0.43). (6-7) The mass fraction for each molecular weight was calculated from the calibration curve, and the mf (10000) rate and mf million) rate were determined.
  • Example 1 High-density polyethylene (density 965 kg / m 3 , MFR / D: 5.1, MFR / G: 186, mf (1000) rate: 1.4 mass%) as a raw material, polymer extrusion using a hollow double nozzle Spinning was performed at an amount of 16.1 g / min, a hollow nitrogen amount of 22.5 mL / min, a spinning temperature of 150 ° C., a spinning speed of 200 m / min, a spinning draft ratio of 3400, and an idle running time of 1.2 seconds. Thread). Next, the raw yarn before drawing was further heated in an oven at 100 ° C. for 6 hours, and further heat treated at 115 ° C. for 1 hour.
  • this porous hollow fiber membrane When the inner wall of this porous hollow fiber membrane was confirmed by SEM (5000 times), it was composed of a plurality of microfibrils oriented in the yarn length direction and a knot portion composed of a lamellar laminate connected to both ends of the microfibril. It was confirmed that The unstretched incidence of the porous hollow fiber membrane was 0.07 (pieces / m ⁇ %). An ethylene-vinyl alcohol copolymer having an ethylene content of 38 mol% was dissolved by heating in a 75 vol% aqueous ethanol solution to give a 0.5 mass% solution. The porous hollow fiber membrane was immersed in the solution maintained at a temperature of 50 ° C. and left for 10 minutes.
  • the obtained separation membrane had an inner diameter of 320 ⁇ m and a film thickness of 45 ⁇ m.
  • the porous hollow fiber membrane obtained by removing the ethylene-vinyl alcohol copolymer from the separation membrane had an mf (10000) ratio of 19.0 mass% and an mf (1 million) ratio of 1.4 mass%.
  • the blood pseudoleakage confirmation test no vermilion spot was confirmed, and the blood pseudoleakage was determined to be “none”.
  • a plasma separation module was prepared using the separation membrane, and irradiated with gamma rays at a dose of 25 kGy. Thereafter, the separation membrane was taken out from the plasma separation module, and the separation membrane was immersed in dimethyl sulfoxide for 50 hours, then washed with a 50% by volume aqueous methanol solution, vacuum-dried for 5 hours, and MFR / D was measured. 03.
  • Example 2 High-density polyethylene (density 962 kg / m 3 , MFR / D: 5.2, MFR / G: 195, mf (1000) rate: 1.0 mass%) as a raw material, polymer extrusion using a hollow double nozzle Spinning was carried out at an amount of 16.0 g / min, a hollow nitrogen amount of 22.0 mL / min, a spinning temperature of 149 ° C., a spinning speed of 200 m / min, a spinning draft ratio of 3430, an idle running time of 1.2 seconds, and a hollow fiber (original before drawing) Thread). Next, the raw yarn before drawing was further heated in an oven at 100 ° C.
  • this porous hollow fiber membrane When the inner wall of this porous hollow fiber membrane was confirmed by SEM (5000 times), it was composed of a plurality of microfibrils oriented in the yarn length direction and a knot portion composed of a lamellar laminate connected to both ends of the microfibril. It was. The unstretched incidence was 0.07 (pieces / m ⁇ %). According to the procedure described in Example 1, an ethylene-vinyl alcohol copolymer was applied to obtain a separation membrane. The obtained separation membrane had an inner diameter of 315 ⁇ m and a film thickness of 44 ⁇ m.
  • the porous hollow fiber membrane obtained by removing the ethylene-vinyl alcohol copolymer from the separation membrane had an mf (10000) ratio of 18.0 mass% and an mf (1 million) ratio of 1.3 mass%.
  • mf (10000) ratio of 18.0 mass% and an mf (1 million) ratio of 1.3 mass% In the blood pseudoleakage confirmation test, no vermilion spot was confirmed, and the blood pseudoleakage was determined to be “none”. In the eluate test, elution of hydrophilic polymer was not observed. According to the procedure described in Example 1, the MFR / D was measured after irradiating the separation membrane with gamma rays and found to be 0.05.
  • Example 3 High-density polyethylene (density 967 kg / m 3 , MFR / D: 2.8, MFR / G: 114, mf (1000) ratio: 0.7% by mass) as a raw material, polymer extrusion using a hollow double nozzle Spinning was performed at an amount of 16.1 g / min, a hollow nitrogen amount of 22.5 mL / min, a spinning temperature of 155 ° C., a spinning speed of 200 m / min, a spinning draft ratio of 3400, and an idle running time of 1.2 seconds. Thread). Next, the raw yarn before drawing was further heated in an oven at 100 ° C. for 8 hours, and further heated at 115 ° C. for 1 hour.
  • cold drawing, hot drawing, and heat setting were continuously performed. Specifically, cold drawing at a cold drawing ratio of 30% is performed at room temperature, followed by two-stage hot drawing at 102 ° C. with a hot drawing ratio of 200% and 115 ° C. with a further 43%, followed by air heating at 127 ° C. By adjusting the speed between the rolls in the tank, a two-stage heat setting was performed at a heat setting rate of 27% for the first stage and 17% for the second stage to obtain a porous hollow fiber membrane.
  • the inner wall of the porous hollow fiber membrane at this time was confirmed by SEM (5000 times), a plurality of microfibrils oriented in the yarn length direction, and a knot portion composed of a lamellar laminate connected to both ends of the microfibrils It was confirmed that it was configured.
  • the unstretched incidence of the porous hollow fiber membrane was 0.29 (pieces / m ⁇ %).
  • the inner diameter of the separation membrane was 315 ⁇ m and the film thickness was 45 ⁇ m.
  • the porous hollow fiber membrane obtained by removing the ethylene-vinyl alcohol copolymer from the separation membrane had an mf (10000) rate of 17.5% by mass and an mf (million) rate of 1.4% by mass.
  • Example 1 The procedure described in Example 1 was followed except that high-density polyethylene (density 966 kg / m 3 , MFR / D: 5.1, MFR / G: 183, mf (1000) ratio: 0.8 mass%) was used as a raw material. A porous hollow fiber membrane and then a separation membrane were obtained. When the inner wall of this porous hollow fiber membrane was confirmed by SEM (5000 times), it was composed of a plurality of microfibrils oriented in the yarn length direction and a knot portion composed of a lamellar laminate connected to both ends of the microfibril. In addition, the unstretched incidence was 1.20 (pieces / m ⁇ %).
  • the inner diameter of the separation membrane was 320 ⁇ m and the film thickness was 46 ⁇ m.
  • the porous hollow fiber membrane obtained by removing the ethylene-vinyl alcohol copolymer from the separation membrane had an mf (10000) ratio of 17.3 mass% and an mf (1 million) ratio of 1.1 mass%.
  • mf (10000) ratio of 17.3 mass% a bundle having vermilion spots in the test module was confirmed, and the blood pseudoleakage was determined to be “present”. No elution was observed.
  • Example 1 After irradiating the separation membrane with gamma rays, measurement of MFR / D was attempted, but it could not be measured because it did not melt.
  • Example 2 The procedure described in Example 1 was followed except that high-density polyethylene (density 965 kg / m 3 , MFR / D: 5.0, MFR / G: 155, mf (1000) ratio: 0.8% by mass) was used as a raw material. A porous hollow fiber membrane and then a separation membrane were obtained. When the inner wall of this porous hollow fiber membrane was confirmed by SEM (5000 times), it was composed of a plurality of microfibrils oriented in the yarn length direction and a knot portion composed of a lamellar laminate connected to both ends of the microfibril. In addition, the unstretched incidence was 0.34 (pieces / m ⁇ %).
  • the inner diameter of the separation membrane was 320 ⁇ m and the film thickness was 46 ⁇ m.
  • the porous hollow fiber membrane obtained by removing the ethylene-vinyl alcohol copolymer from the separation membrane had an mf (10000) rate of 17.5% by mass and an mf (million) rate of 1.5% by mass.
  • this porous hollow fiber membrane When the inner wall of this porous hollow fiber membrane was confirmed by SEM (5000 times), it was composed of a plurality of microfibrils oriented in the yarn length direction and a knot portion composed of a lamellar laminate connected to both ends of the microfibril. It was. The unstretched occurrence rate was 2.75 (pieces / m ⁇ %). Thereafter, according to the procedure described in Example 1, a separation membrane was obtained. The inner diameter of the separation membrane was 320 ⁇ m and the film thickness was 43 ⁇ m. The porous hollow fiber membrane obtained by removing the ethylene-vinyl alcohol copolymer from the separation membrane had an mf (10000) rate of 16.9% by mass and an mf (1 million) rate of 2.4% by mass. In the blood pseudoleakage confirmation test, a bundle having vermilion spots in the test module was confirmed, and the blood pseudoleakage was determined to be “present”. Elution was observed.
  • this porous hollow fiber membrane When the inner wall of this porous hollow fiber membrane was confirmed by SEM (5000 times), it was composed of a plurality of microfibrils oriented in the yarn length direction and a knot portion composed of a lamellar laminate connected to both ends of the microfibril. It was. The unstretched incidence was 13.80 (pieces / m ⁇ %). Thereafter, according to the procedure described in Example 1, a separation membrane was obtained. The inner diameter of the separation membrane was 320 ⁇ m and the film thickness was 43 ⁇ m. The porous hollow fiber membrane obtained by removing the ethylene-vinyl alcohol copolymer from the separation membrane had an mf (10000) rate of 16.0% by mass and an mf (million) rate of 2.8% by mass.
  • the blood pseudoleakage confirmation test a bundle having vermilion spots in the test module was confirmed, and the blood pseudoleakage was determined to be “present”.
  • the dissolution test elution of hydrophilic substances was observed, and the dissolution was judged as “present”.
  • Example 5 The procedure described in Example 3 was followed except that high-density polyethylene (density 961 kg / m 3 , MFR / D: 2.9, MFR / G: 145, mf (1000) ratio: 1.0 mass%) was used as a raw material. A porous hollow fiber membrane and then a separation membrane were obtained. When the inner wall of this porous hollow fiber membrane was confirmed by SEM (5000 times), it was composed of a plurality of microfibrils oriented in the yarn length direction and a knot portion composed of a lamellar laminate connected to both ends of the microfibril. In addition, the unstretched incidence was 0.66 (pieces / m ⁇ %).
  • the inner diameter of the separation membrane was 316 ⁇ m and the film thickness was 45 ⁇ m.
  • the porous hollow fiber membrane obtained by removing the ethylene-vinyl alcohol copolymer from the separation membrane had an mf (10000) rate of 17.0% by mass and an mf (million) rate of 1.7% by mass.
  • mf (10000) rate of 17.0% by mass
  • mf (million) rate of 1.7% by mass.
  • Example 4 A resin containing 99.0% by mass of the high-density polyethylene used in Comparative Example 1 and 1.0% by mass of a high-density low molecular weight ethylene polymer (olefin wax) (density 970 kg / m 3 , viscosity average molecular weight 4000).
  • a composition (MFR / D: 5.1, MFR / G: 188, mf (1000) ratio: 1.1% by mass) was obtained.
  • a porous hollow fiber membrane was prepared according to the procedure described in Example 1, and a separation membrane was further obtained.
  • a knot portion comprising a plurality of microfibrils oriented in the yarn length direction and a lamellar laminate connected to both ends of the microfibrils.
  • the unstretched incidence was 0.08 (pieces / m ⁇ %).
  • the inner diameter of the separation membrane was 321 ⁇ m and the film thickness was 45 ⁇ m.
  • the porous hollow fiber membrane obtained by removing the ethylene-vinyl alcohol copolymer from the separation membrane had an mf (10000) ratio of 18.5 mass% and an mf (1 million) ratio of 1.1 mass%.
  • Example 5 A resin containing 95.0% by mass of the high-density polyethylene used in Comparative Example 1 and 5.0% by mass of a high-density low molecular weight ethylene polymer (olefin wax) (density 980 kg / m 3 , viscosity average molecular weight 2000).
  • a composition was obtained (MFR / D: 5.8, MFR / G: 239, mf (1000) ratio: 1.2% by mass).
  • a porous hollow fiber membrane was prepared according to the procedure described in Example 1, and a separation membrane was further obtained.
  • Example 6 Resin containing 98.0% by mass of the high-density polyethylene used in Comparative Example 1 and 2.0% by mass of a low-density low-molecular-weight ethylene polymer (olefin wax) (density 935 kg / m 3 , viscosity average molecular weight 2000).
  • a composition was obtained (MFR / D: 5.5, MFR / G: 263, mf (1000) ratio: 1.0 mass%).
  • a porous hollow fiber membrane and then a separation membrane were obtained according to the procedure described in Example 1, except that the second heat treatment temperature and heat treatment time were 117 ° C. and 2 hours, respectively.
  • this porous hollow fiber membrane When the inner wall of this porous hollow fiber membrane was confirmed by SEM (5000 times), it was composed of a plurality of microfibrils oriented in the yarn length direction and a knot portion composed of a lamellar laminate connected to both ends of the microfibril. In addition, the unstretched incidence was 0.16 (pieces / m ⁇ %). The inner diameter of the separation membrane was 322 ⁇ m, and the film thickness was 46 ⁇ m. The porous hollow fiber membrane obtained by removing the ethylene-vinyl alcohol copolymer from the separation membrane had an mf (10000) rate of 18.7% by mass and an mf (1 million) rate of 1.1% by mass. No simulated blood leak or eluate was observed.
  • Example 7 98.0% by mass of the high density polyethylene used in Comparative Example 1 and 2.0% by mass of a low density low molecular weight ethylene-propylene polymer (olefin wax) (density 940 kg / m 3 , viscosity average molecular weight 2000)
  • the obtained resin composition was obtained (MFR / D: 6.0, MFR / G: 290, mf (1000) rate: 1.1 mass%).
  • a porous hollow fiber membrane was prepared according to the procedure described in Example 1 except that the spinning temperature was 152 ° C., and a separation membrane was obtained.
  • Example 8 A resin containing 95.0% by mass of the high-density polyethylene used in Comparative Example 1 and 5.0% by mass of a high-density low molecular weight ethylene polymer (olefin wax) (density 970 kg / m 3 , viscosity average molecular weight 4000).
  • a composition was obtained (MFR / D: 5.7, MFR / G: 191 and mf (1000) ratio: 1.5 mass%).
  • a porous hollow fiber membrane and a separation membrane were obtained according to the procedure described in Example 1.
  • this porous hollow fiber membrane When the inner wall of this porous hollow fiber membrane was confirmed by SEM (5000 times), it was composed of a plurality of microfibrils oriented in the yarn length direction and a knot portion composed of a lamellar laminate connected to both ends of the microfibril. In addition, the unstretched occurrence rate was 0.17 (pieces / m ⁇ %). The inner diameter of the separation membrane was 318 ⁇ m, and the film thickness was 44 ⁇ m. The porous hollow fiber membrane obtained by removing the ethylene-vinyl alcohol copolymer from the separation membrane had an mf (10000) ratio of 20.2 mass% and an mf (1 million) ratio of 1.0 mass%. In the blood pseudoleakage confirmation test, no vermilion spot was confirmed, and the blood pseudoleakage was determined to be “none”. In the eluate test, elution of the hydrophilic polymer was determined to be “present”.
  • a porous hollow fiber membrane was prepared according to the procedure described in Example 1, and then a separation membrane was obtained.
  • the inner wall of the porous hollow fiber membrane obtained here was confirmed by SEM (5000 times), a plurality of microfibrils oriented in the yarn length direction, and a knot portion composed of a lamellar laminate connected to both ends of the microfibrils, Consisted of.
  • the unstretched incidence was 1.55 (pieces / m ⁇ %).
  • the inner diameter of the separation membrane was 322 ⁇ m, and the film thickness was 43 ⁇ m.
  • the porous hollow fiber membrane obtained by removing the ethylene-vinyl alcohol copolymer from the separation membrane had an mf (10000) rate of 17.4% by mass and an mf (million) rate of 1.5% by mass.
  • mf (10000) rate of 17.4% by mass had an mf (million) rate of 1.5% by mass.
  • mf (million) rate was determined to be “present”.
  • eluate test elution of the hydrophilic polymer was judged as “none”.
  • the separation membrane was irradiated with gamma rays, and then MFR / D measurement was attempted. However, the MFR / D could not be measured because it did not melt.
  • the polyethylene resin porous hollow fiber membrane of the present invention has industrial applicability in the medical field that it can be used in plasma exchange therapy.

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Abstract

La présente invention concerne une membrane de fibres creuses poreuse en résine de polyéthylène comportant une pluralité de microfibrilles qui comprennent une résine de polyéthylène et qui sont alignées dans la direction longitudinale des fibres, et des parties nodulaires comprenant un stratifié lamellaire relié aux deux extrémités des microfibrilles, la fraction de masse des composants ayant un poids moléculaire de 10 000 ou moins étant de 17,5 % en masse ou plus, et la fraction en masse des composants ayant un poids moléculaire de 1 000 000 ou plus étant inférieure à 1,5 % en masse.
PCT/JP2017/010112 2016-05-13 2017-03-14 Membrane de fibres creuses poreuse en résine de polyéthylène, membrane de séparation et procédé de fabrication desdites membranes WO2017195457A1 (fr)

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