Porous polymer membranes and related filters and methods

Abstract

Described are porous polymer membranes with two opposing surfaces and having a pore structure that varies through the thickness of the membrane; filter elements and filters that include porous polymer membranes of this type; methods of making the membranes, filter elements, and filters; and methods of using the polymer filtration membranes, filter elements, or filters.

Description

Technical Field

[0001] The following description relates to a porous polymer filtration membrane having two mutually opposite surfaces and a pore structure that varies throughout the thickness of the membrane; further, a filter component and a filter comprising this type of porous polymer filtration membrane; a method for producing a porous polymer filtration membrane, a filter component, and a filter; and a method for filtering a fluid such as a liquid chemical substance and removing unwanted substances from the fluid.

Background Art

[0002] The main use of filtration membranes is to remove unwanted substances from the flow of useful fluids. Many gaseous and liquid fluids in industry, including ambient air, drinking water, liquid industrial solvents and process fluids, industrial gases used in manufacturing or processing (e.g., semiconductor manufacturing), and liquids for medical or pharmaceutical applications, are treated using filters. Unwanted substances removed from the fluid include impurities and contaminants such as particles, microorganisms, dissolved chemical species, etc. Detailed examples of impurity removal applications of filtration membranes include the removal of particles or bacteria from therapeutic fluids in the pharmaceutical industry, the treatment of ultrapure aqueous and organic solvent solutions for use in microelectronics and semiconductor processing, and the use of filtration membranes in air and water purification processes.

[0003] To perform the filtration function, a filter product comprises a filtration membrane that serves to remove unwanted substances from the fluid. The filtration membrane can be in the form of a flat sheet, which may be wound (e.g., in a spiral) or pleated as necessary. Alternatively, the filtration membrane can be in the form of hollow fibers. The filtration membrane can be placed within a housing having an inlet and an outlet such that the fluid being filtered enters through the inlet and passes through the filtration membrane before passing through the outlet.

[0004] Filtration membranes can be constructed from porous polymer films with average pore sizes that can be selected based on the expected application of the filter, i.e., the type of filtration performed using the filter. Typical pore sizes range from microns to submicrons, e.g., approximately 0.001 microns to approximately 10 microns. Membranes with an average pore size of approximately 0.001 to approximately 0.05 microns may be classified as ultrafiltration membranes. Membranes with a pore size of 0.05 to 10 microns may be classified as microporous membranes.

[0005] Commercial filtration membranes should be of a type that can be efficiently manufactured and assembled into filter products. The membranes must be efficiently manufactured and possess mechanical properties such as strength and flexibility to withstand assembly into filter cartridges or filters. In addition to mechanical properties, the membranes should have chemical functionality and microstructure suitable for high-performance filtration.

[0006] Various techniques for forming porous filtration membranes are known. Exemplary techniques include, in particular, melt extrusion (e.g., melt casting) and immersion casting (phase inversion) techniques. Different techniques for forming porous materials can produce different porous membrane structures in terms of pore size and distribution formed within the membrane. That is, different techniques produce different pore sizes and membrane structures (sometimes called morphology, which refers to the uniformity, shape, and distribution of pores within the membrane).

[0007] Examples of membrane morphologies include uniform (isotropic) and asymmetric (anisotropic). Membranes with substantially uniformly sized pores distributed uniformly throughout are often called isotropic or "uniform." Anisotropic (also known as "asymmetrical") membranes can be thought of as having a morphology in which a pore size gradient exists throughout the membrane. For example, a membrane may have a porous structure in which the pore structure changes along the thickness of the membrane, with relatively large pores on one surface and relatively small pores on the other. The term "asymmetrical" is often used interchangeably with the term "anisotropic." Often, parts of the membrane with relatively small pores (compared to other parts of the membrane) are called "tight" regions. Parts of the membrane with larger pores are often called "open" regions.

[0008] Industries that use filters, including the semiconductor materials and microelectronic device manufacturing and processing industries, have a continuing interest in discovering improved filtration membranes and filters, including new filter products with improved performance, such as enhanced capture capabilities. New filters should be able to be manufactured in an efficient and cost-effective, for example, profitable, manner. [Overview of the project]

[0009] In the field of microelectronic device processing (e.g., microelectronics and semiconductor device manufacturing), steady improvements in processing materials and methods are necessary to maintain corresponding steady improvements in the performance (e.g., speed and reliability) of microelectronic devices. Opportunities to improve the manufacturing of microelectronic devices exist in all aspects of the manufacturing process, including methods and systems for filtering liquid materials used during manufacturing.

[0010] Two key aspects of commercial filtration membrane manufacturing are efficient and cost-effective production, and high performance in terms of capture capacity, which relates to the amount of particles the filtration membrane can remove from the fluid flow.

[0011] An effective technique for improving capture performance is to use multiple membranes in sequence, such as stacking the filtration surfaces of two membranes together and bringing them into contact, allowing the fluid to pass through both membranes continuously. This is sometimes called "layering" or "stacking" of filtration membranes to form a multilayer membrane. When layering techniques are implemented using asymmetric membranes, each having a "tight" region and an "open" region, the fluid passing through the two membranes must pass through both "tight" regions, which can improve the membrane's capture performance.

[0012] While layering techniques are feasible and sometimes effective, using two layered films doubles the material cost of the film. Therefore, it is interesting to replicate the structure of two films, i.e., two-layer laminated films, in a single, integrated film produced by a single film formation process; that is, to produce a single, integrated film with two tight layers, e.g., a "double-tight" film, using a single manufacturing process. Preferably, the two tight layers of the film are not prepared using separate processes and then combined. For example, the film is not produced by combining two separate films to form a multilayer film.

[0013] Accordingly, this specification relates to a membrane formed integrally in a single forming step to have two tight regions and at least one open region, a method for preparing the membrane, and a method for using the membrane as a filtration membrane and a filter product incorporating the membrane. Such a porous membrane can be prepared by a novel and inventive method of extruding a polymer solution through a die in the form of a polymer solution film, and subsequently exposing both sides of the film, opposite to each other, to conditions that cause the polymer in the film to solidify on both sides of the film, in particular conditions that produce tight morphology on both sides of the solidified film.

[0014] As an example of a useful method for preparing a described film having the described morphology, the film may be formed by extruding a liquid film of a liquid polymer solution containing a non-coagulated or partially coagulated polymer dissolved or suspended in a solvent, and simultaneously exposing two opposite surfaces of the film to conditions (e.g., temperature, non-solvent, humidity, evaporation) that induce coagulation of the dissolved polymer on both sides of the film, for substantially the same time and in the same manner, thereby causing the polymer to coagulate within the film. In one example, the technique for inducing coagulation is by a non-solvent-induced phase separation (NIPS) technique. In another example, polymer coagulation may be induced by thermal-induced phase separation (TIPS). In yet another example, polymer coagulation may be induced by exposing the extruded film to moisture. In yet another example, polymer coagulation may be induced by solvent evaporation from the extruded film.

[0015] In one embodiment, the extruded porous polymer sheet film comprises a first surface, a second surface, a thickness between the first and second surfaces, a first thickness region including the first surface and a portion of the film in the thickness direction, a second thickness region including the second surface and a portion of the film in the thickness direction, and a third thickness region extending in the thickness direction between the first and second thickness regions. The average pore diameter of both the first thickness region and the second thickness region is smaller than the average pore diameter of the third region.

[0016] In another embodiment, a method for producing an extruded porous polymer sheet film having first and second surfaces on opposite sides, a thickness between the opposite surfaces, and pores having non-uniform pore diameters comprises: forming a polymer-containing liquid containing a polymer in a solvent; passing the polymer-containing liquid through an extrusion die to form an extruded film of the polymer-containing liquid; and exposing both sides of the extruded film to conditions that induce polymer coagulation on both sides of the film. [Brief explanation of the drawing]

[0017] [Figure 1A] This is a cross-sectional photograph of the membrane as used herein. [Figure 1B] This is a cross-sectional photograph of the membrane as used herein. [Figure 2A-B] These are schematic diagrams illustrating exemplary methods and systems as described herein (they are schematic and not necessarily to a specific scale). [Figure 3A-B] These are schematic diagrams illustrating exemplary methods and systems as described herein (they are schematic and not necessarily to a specific scale). [Figure 4] This figure shows exemplary filtration membrane performance data as used herein. [Modes for carrying out the invention]

[0018] The following description relates to extruded porous polymer membranes that may be effective as filtration membranes, filter products comprising filtration membranes, and related methods for preparing and using porous membranes.

[0019] A porous polymer membrane has two opposite surfaces (or "faces") and a thickness between the two opposite surfaces. The pores of the porous membrane are arranged throughout the entire thickness of the membrane so that a fluid can flow from one surface of the membrane through its thickness to the opposite surface, while removing particles or contaminants from the fluid. Thus, the membrane is permeable to fluids such as liquids. This type of membrane is sometimes called an "open-pore" membrane in contrast to a "closed-pore" membrane. An open-pore membrane can take the form of a thin film or sheet of extruded porous polymer material having a relatively uniform thickness and an open-pore porous structure containing a polymer matrix that defines numerous open "cells" which are three-dimensional void structures or pores. The open cells are widely interconnected between adjacent cells so that a fluid such as a liquid can flow from one surface of the membrane to the other through its thickness, and may be called an opening, pore, channel, or passage.

[0020] The described porous membrane contains pores with different pore diameters, and the pore diameters within the membrane vary along the thickness of the membrane. As used herein, "pore diameter" refers to the pore diameter (e.g., average diameter) within a region (or "portion") of the membrane, such as a thickness region located between two different depths of the membrane, or a specific depth defined with respect to the thickness of the membrane. For example, the region of the membrane can be the portion of the membrane between the surface of the membrane and a specific depth, such as a depth of 10 microns below the surface. As another example, the region of the membrane can be a portion located between two different depths, such as the middle one-third of the thickness of the membrane.

[0021] The described porous membrane has a morphology that is non-uniform (anisotropic, heterogeneous) with respect to pore diameter across the entire thickness of the membrane. The non-uniform morphology may be referred to as a "variable" morphology having multiple (e.g., at least three) regions with different pore diameters at different positions along the thickness of the membrane. In the context herein, a membrane having a "variable pore structure" is a structure comprising pores of different sizes across the thickness of the membrane between two opposite surfaces of the membrane. The pore diameter may vary either stepwise or non-stepwise across the thickness (depth-based) of the membrane. (See, for example, FIGS. 2A, 2B, 3A, and 3B.)

[0022] The membranes described herein more particularly include two "tight" regions and at least one "open" region located between the two "tight" regions. These membranes are herein referred to as "double-tight" membranes, or membranes having a "double-tight" morphology. One region of the membrane is a region that may be referred to as a "tight region", which means a region having relatively smaller pores throughout the thickness of the membrane. The second region of the membrane is a second tight region that also has relatively smaller pores throughout the thickness of the membrane. Inside (or "middle") the membrane is an "open region" located between two opposed tight regions. The "open" region is a thickness portion having pores that are relatively larger than the pores in both of the two tight regions. Due to this configuration, i.e., having two tight regions and an open region inside the membrane between the two tight regions, the membranes described may be referred to as "double-tight" porous membranes having a "variable" pore size.

[0023] A porous membrane having two tight regions and an internal open region is considered "integral". More particularly, the overall thickness of the membrane and both opposed surfaces are formed and constructed together as a single, structurally continuous membrane by a single forming process, e.g., a single process including extrusion of a film and coagulation of the film's polymer (including co-extrusion using a multi-slot die).

[0024] In contrast to the integral porous membranes described, other known types of porous membranes may be non-integrated. These include membranes sometimes called multilayer or “composite” membranes, which are prepared by combining or arranging two separate membrane layers, each having a different morphology or chemical composition, on opposing surfaces and optionally adhering or bonding them together. Such composite membranes may comprise a multilayer structure formed by combining a first porous membrane layer formed in one formation step and having a first (e.g., larger pore diameter) morphology with a second porous membrane layer formed in a second formation step different from the step of forming the first porous layer. This type of multilayer or “composite” membrane structure, formed from multiple separate films prepared in multiple steps, is not considered an “integrated” membrane.

[0025] Other examples of films not considered integral according to this specification include porous films coated on one or both surfaces, i.e., films comprising a substrate film prepared during the film formation process and one or more coatings (e.g., one or more polymer coatings) applied to one or more surfaces of the substrate film in a subsequent coating process. An exemplary film may be a uniform (or non-uniform) substrate film having relatively uniform (or non-uniform) pore sizes throughout, with one or both surfaces coated with polymer after formation. The polymer coating may be the same as or different from the polymer of the substrate film. The polymer coating may reduce the pore size of one or two coated surfaces.

[0026] The films described herein may have any useful thickness in the range of 10 to 300 microns, for example, a thickness in the range of 25 or 40 microns to a maximum of 250 or 200 microns.

[0027] The membrane comprises two relatively parallel surfaces on opposite sides, extending in both the length and width directions, and a thickness extending in a third direction, located between the two opposite surfaces. The position midway between the two surfaces is considered an imaginary "centerline" that bisects the thickness of the membrane, i.e., an imaginary line extending in the length and width directions at equidistant from each of the two opposite surfaces.

[0028] A “thickness region” of a film is a portion of the film that extends in the dimensions of length and width over a certain portion of the film’s thickness. For the purposes of this specification and the claims, a film can be considered to comprise at least three thickness regions: a first tight region, one open region, and a second tight region. The open region is located between the two tight regions. One or both tight regions may include the surface of the film, but neither tight region is required to include the surface.

[0029] In certain embodiments, the film may comprise a first thickness region including a first surface of the film and extending to a depth below the first surface but not to the centerline of the film; a second thickness region including a second surface of the film and extending to a depth below the second surface but not to the centerline of the film; and a third thickness region between the first and second thickness regions, extending over the remaining portion of the film's thickness and optionally, and usually, including the centerline. Examples of useful depths below the first surface of the film that define the size (thickness) of the first thickness region relative to the total thickness of the film include depths equal to 2, 5, 10, 20, 25, 30, or 33% of the total thickness of the film. Similarly, examples of useful depths below the second surface of the film that define the size (thickness) of the second thickness region relative to the total thickness of the film include depths equal to 2, 5, 10, 20, 25, 30, or 33% of the total thickness of the film.

[0030] According to an exemplary membrane, double-tight morphology can be defined in terms of a relatively small average pore diameter in each of the two tight regions compared to a relatively large pore diameter in the open region. The average pore diameter of the tight region can be any average pore diameter in the tight portion of a useful filtration membrane, including, but not limited to, average pore diameters in the range of 1 nanometer to 10 microns, e.g., 1 nanometer to 5 microns, or 10 nanometers to 1 or 2 microns. The first and second tight regions may independently have the same or different average pore diameters, both of which fall within one of the defined ranges. The average pore diameter of the open region can be any average pore diameter in the open portion of a useful filtration membrane, including, but not limited to, average pore diameters in the range of 5 nanometers to 50 microns, such as 20 nanometers to 10 microns, or 50 nanometers to 1, 2, or 5 microns. Alternatively or additionally, the average pore size of the open region may also be at least 10, 20, 50, or 100%, or more, larger than the average pore size of one or both tight regions. That is, the average pore size of the open region may be at least 10, 20, 50, or 100%, larger than the average pore size of the average pore size in both tight regions.

[0031] When considering the size of thickness regions along the thickness of the film, the present invention does not require a specific size of each region or a relative size of the regions, except that the average pore diameter of the region is as described, the first thickness region has a depth position of a first minimum pore diameter on one side of the centerline, the second thickness region has a depth position of a second minimum pore diameter on the second side of the centerline, and the minimum pore diameter of the third region is greater than the first minimum pore diameter and greater than the second minimum pore diameter.

[0032] More specifically, double-tight morphology can be defined, alternatively or additionally, in terms of the presence of two distinct "minimum" pore diameters (measured minimum pore diameters), each independently located at a specific depth in the membrane and each on the opposite side of the membrane's centerline. The "minimum" pore diameter is the smallest pore diameter measured on one side of the centerline, at a single uniform depth below the surface of the membrane, measured over at least a portion of the membrane's region. According to these membranes described, the membrane has a first minimum pore diameter at a specific depth on one side of the centerline and a second minimum pore diameter at a specific depth on a second side of the centerline. The depth of the first minimum pore diameter from the first surface may be the same as or different from the depth of the second minimum pore diameter from the second surface. The first minimum pore diameter is the smallest pore diameter located at a specific depth between the centerline and the first surface. The second minimum pore diameter is the smallest pore diameter located at a specific depth between the centerline and the second surface. These two minimum pore diameters are the two smallest pore diameters in the membrane, and there are no other depths in the membrane where smaller average pore diameters exist.

[0033] According to certain exemplary embodiments, the minimum pore diameter (first minimum pore diameter or second minimum pore diameter) may be located on the surface (first surface or second surface) (where the depth of the minimum pore diameter location is 0), or near the surface, for example, within 2, 5, 10, or 20% of the film thickness from the surface.

[0034] The locations of the first minimum pore diameter and the second minimum pore diameter can independently be on the surface or at a depth from the surface. For example, the location of the first minimum pore diameter may be on the first surface (depth 0) and the location of the second minimum pore diameter may be on the second surface; the location of the first minimum pore diameter may be below the first surface and the location of the second minimum pore diameter may be below the second surface; the location of the first minimum pore diameter may be on the first surface and the location of the second minimum pore diameter may be below the second surface; or the location of the first minimum pore diameter may be below the first surface and the location of the second minimum pore diameter may be on the second surface.

[0035] The average pore diameter in a membrane region or at a specific depth can be measured by any useful technique, including manual or electronic visual verification of images created by a scanning electron microscope (SEM). Examples of these methods include using computer software programs to evaluate pore diameter in a membrane region or depth. In other examples, pore diameter in a membrane region or depth can be measured by visually inspecting hard copies of SEM micrographs.

[0036] An exemplary membrane can be described in terms of asymmetry, which is the relationship between the pore size in the open region and the pore size in the tight region. The asymmetry (D) of the described membrane can be defined as follows: D = (Average pore diameter of the third thickness region) / A A can be defined as one of the following: the average pore diameter of the first region; the average pore diameter of the second region; the first minimum pore diameter; or the second minimum pore diameter.

[0037] Useful and preferred films in this specification may have an asymmetry (D) of at least 5, for example, at least 10, 20, or 30, when calculated using more than or equal to the different possible pore sizes of group A.

[0038] Referring to Figure 1A, a cross-section of an exemplary porous membrane 10 is shown, having a surface 12, a second surface 14, and a thickness between these two surfaces. The center line 50 is located midway between surface 12 and surface 14. The first thickness region 20 is between surface 12 and the first depth D 1 It is located in the thickness region between the second surface 14 and the second depth D. 2The third thickness region 30 is located in the thickness region between the first thickness region 20 and the second thickness region 40. The average pore diameter in each of the first thickness region 20, the second thickness region 40, and the third thickness region 50 can be measured over the three-dimensional thickness of each region. According to this specification, the average pore diameter of the pores in the first thickness region is substantially (e.g., measurably) smaller than the average pore diameter of the pores in the third thickness region, and the average pore diameter of the pores in the second thickness region is substantially smaller than the average pore diameter of the pores in the third thickness region.

[0039] Figure 1A also shows the depth 22 of the first minimum pore diameter located at a depth on one side of the midpoint 50. As shown, the depth 22 of the first minimum pore diameter is depth 0, which means that the first minimum pore diameter is located on surface 12. Figure 1A also shows the depth 42 as the second minimum depth located on the second side of the midpoint 50, at a depth slightly below the second surface 14. The first and second minimum pore diameters are located at or below each of the depths on or below surface 12 and surface 14, respectively, and each depth is measured as the depth of the membrane where the pores continuing along the length and width of the membrane have the smallest average pore diameter for all pores on the same side of the midpoint 50, i.e., within the membrane 10 between surface 12 and midpoint 50 (depth 22), and within the membrane 10 between surface 14 and midpoint 50 (depth 42). Each minimum pore diameter is the smallest average pore diameter at any given depth on each side of the centerline, and there are no other depths on each side of the membrane relative to the centerline that have an average pore diameter smaller than the minimum pore diameter.

[0040] Referring to Figure 1B, a cross-section of the porous membrane 10 is shown, having a surface 12, a second surface 14, and a thickness between these two surfaces. The center line 50 is located midway between surface 12 and surface 14. The first thickness region 20 is between surface 12 and the first depth D 1 It is located in the thickness region between the second surface 14 and the second depth D. 2 It is located in the thickness region between the first thickness region 20 and the second thickness region 40, for example, depth D.1 and depth D 2 It is located between the two. The average pore diameter of the pores throughout each of the first thickness region 20, the second thickness region 40, and the third thickness region 50 can be measured over the three-dimensional thickness region. According to this specification, the average pore diameter of the pores in the first thickness region is substantially smaller than the average pore diameter of the pores in the third thickness region, and the average pore diameter of the pores in the second thickness region is substantially smaller than the average pore diameter of the pores in the third thickness region.

[0041] Figure 1B also shows the depth 22 of the first minimum pore diameter located at or near the surface depth of the membrane 10 on one side of the midpoint 50, and the depth 42 of the second minimum pore diameter located at or near the second surface depth of the membrane 10 on the second side of the midpoint 50. In the illustrated membrane, the locations of the first minimum pore diameter 22 and the second minimum pore diameter 42 are on or near the surface 12 and surface 14, respectively. Each of the two minimum pore diameters is the smallest average pore diameter on one side of the membrane relative to the centerline, and there are no other depths on each side of the membrane that have an average pore diameter smaller than the minimum pore diameter.

[0042] The porous films described can be prepared by a method for forming a polymer extruded film, which includes a novel and inventive method, the method of exposing both surfaces of the film to conditions that cause the polymer of the film to solidify, the conditions being the same and applied to both surfaces in the same manner. Since both surfaces of the extruded film are exposed to the same conditions that cause solidification, in the same manner and at the same time, the method described may be effective in forming a solidified film having two opposite surfaces having pores formed simultaneously by the same solidification step; the pores on each of the two opposite surfaces may be smaller than the pores in the interior region of the film to produce a “double-tight” film; the pores on the two opposite surfaces may have equivalent morphologies, since each surface undergoes solidification based on substantially the same or similar solidification-inducing conditions and timing. The resulting solidified film has two opposite (tight) surfaces or thickness regions, one on each side of a centerline, having similar, equivalent, or substantially identical morphologies, and an interior region having a different (open) morphology from the morphologies of the two surfaces. An exemplary membrane may have one surface or region having a morphology with relatively small pore diameters, a second (opposite) surface or region having a morphology with similarly relatively small pore diameters, and an inner portion between the two surfaces or regions having a morphology with relatively larger pore diameters compared to the first and second surfaces.

[0043] As an example of a useful method for preparing a described film having the described morphology, the film may be formed by extruding a liquid film of a liquid polymer solution containing a non-coagulated (optionally, a certain amount of coagulated or partially coagulated) polymer dissolved (or suspended) in a solvent, and then coagulating the polymer within the film by exposing two opposite surfaces of the film to conditions (e.g., temperature, non-solvent, humidity, solvent evaporation) that cause the polymer to coagulate on both surfaces in parallel or simultaneously. In one example, the technique for inducing coagulation is by a non-solvent-induced phase separation (NIPS) technique. In another example, polymer coagulation may be induced by thermal-induced phase separation (TIPS).

[0044] In conventional non-solvent-induced phase separation (NIPS), a polymer solution containing a polymer dissolved or suspended in a solvent is typically extruded and cast onto a support layer (e.g., a support polymer film) to form a cast film. The cast film has one surface that is in contact with and covered by the support layer, and another (opposite) surface that is exposed or open. The support layer and the extruded and cast film are then immersed in a solidification bath containing a “non-solvent,” i.e., a liquid in which the polymer is substantially insoluble. When the cast film is immersed in the non-solvent, solvent-to-non-solvent exchange occurs between the non-solvent bath and the solvent in the extruded film polymer solution at the exposed surface. This solvent exchange allows the non-solvent to be present with the polymer in the cast film, causing the polymer to precipitate from the cast polymer solution film onto the support layer. The polymer needs to be highly soluble in the solvent of the polymer solution and substantially insoluble in the “non-solvent” of the bath so that the polymer efficiently precipitates or solidifies upon contact with the non-solvent of the solidification bath (e.g., an aqueous liquid).

[0045] According to these techniques, the liquid non-solvent contacts only one surface of the cast polymer solution film, which is the exposed surface, but not the other surface of the film, which is in contact with the support layer. Because the non-solvent contacts only one surface of the cast film and solvent exchange occurs only through that one surface of the cast film, the solidified polymer film has a heterogeneous, for example, asymmetric morphology, with one surface of the film exhibiting a different morphology compared to the other surface of the film. Typically, after solidification, the film has an asymmetric morphology with a first morphology on one surface of the film, a substantially different second morphology on the second surface of the film, and an intermediate morphology between the two surfaces that varies throughout the entire thickness of the film, for example, with pore sizes that change stepwise over a range of pore sizes between the pore size on one surface and the pore size on the second surface. For example, one surface may have a relatively small average pore diameter, while the opposite surface has a relatively large average pore diameter, and the average pore diameter at all positions (depths) between the two surfaces may be between the two average pore diameters on the opposite surfaces. Optionally, one surface may be considered to exhibit a "tight" morphology, and the second surface may be considered to exhibit an "open" morphology.

[0046] Equivalent results can be achieved using conventional thermally induced phase separation (TIPS) techniques. Conventional TIPS techniques typically involve extruding a polymer-containing liquid, which usually contains a non-coagulated polymer (and optionally a partially coagulated polymer) in a solvent, through a slot die to form an extruded film. In conventional TIPS methods, one side of the extruded film is cooled to a low temperature, for example, by contacting it with a low-temperature "cooling roll," thereby coagulating the polymer in the extruded film.

[0047] This technique exposes one surface of the extruded film to a low temperature. The opposite surface is not directly or indirectly exposed to the low temperature, resulting in a difference in how the polymer solidifies on one surface of the extruded film compared to the other surface. Because only one side of the film is exposed to the low temperature, the solidified polymer film has a heterogeneous morphology, with one surface exhibiting a substantially different morphology compared to the other surface. Typically, after solidification, the film has an asymmetric morphology that includes a first morphology on one surface, a substantially different morphology on the second surface, and an intermediate morphology between the two surfaces. For example, the average pore size of one surface may be relatively small, the average pore size of the opposite surface may be relatively large, and the average pore size at all positions (depths) between the two surfaces may be between the two average pore sizes on the opposite surfaces. Optionally, one surface can be considered to exhibit a "tight" morphology, and the second surface can be considered to exhibit an "open" morphology.

[0048] The exemplary methods described herein differ from prior phase separation techniques used to form porous polymer films in that the exemplary methods described herein expose both surfaces of an extruded (including co-extruded) film to the same or equivalent conditions to induce solidification, to a relatively similar or equivalent degree. These conditions may include contact with a liquid "non-solvent" and may include low-temperature conditions, such as a low-temperature liquid bath. Compared to the extruded film methods described herein, the methods of the present invention do not require, and may preferably not include, the steps of casting the extruded film of the polymer solution onto a support layer (e.g., a polymer film or a release liner) or positioning only one side of the extruded film to contact a cooled surface such as a cooling roll (e.g., by the support layer). According to the methods of the present invention, both surfaces of the extruded film are exposed to the same conditions effective in inducing solidification for the same time, optionally to the same degree (e.g., depending on the identity of the polymer on each surface), for example, simultaneously. By exposing both surfaces of an extruded film to the same or equivalent solidification-inducing conditions, the conditions affect both sides of the film in a similar manner, causing a solidification effect on both sides of the film. During solidification, a film is formed with respect to the internal region of the film, consisting of two opposite surfaces or planes, each having a tight morphology, and optionally two opposite surfaces with equivalent or identical morphologies.

[0049] According to the examples and preferred embodiments for preparing the films described, a polymer-containing liquid (hereinafter referred to as "polymer solution" or "polymer-containing liquid") can be formed by combining a polymer with a solvent (for example, completely dissolving it in the solvent) to form a polymer-containing liquid containing a non-coagulated or partially coagulated polymer that can be extruded as a liquid into a sheet, and then coagulation can be induced on both sides of the sheet by using a immersion deposition method, such as the TIPS or NIPS method, or by another method such as exposure to moisture or solvent evaporation. A single polymer-containing liquid may be used, or multiple polymer-containing liquids may be used in the co-extruded film.

[0050] A common method may be carried out using one or more steps, including: forming or otherwise preparing one or more polymer-containing liquids containing polymers for preparing a porous polymer membrane, which are dissolved or suspended in a solvent; extruding (including co-extrusion) one or more polymer-containing liquids from a die to form an extruded (including co-extruded) sheet or film containing the polymer-containing liquids; solidifying (e.g., precipitating) the polymers in the polymer-containing liquids from the polymer-containing liquids to form a solidified porous polymer membrane ("porous polymer membrane"); and optionally drying or otherwise further processing the formed porous polymer membrane.

[0051] Examples of such methods may include the use of an extrusion die for extruding one or more polymer-containing liquids as a film. The extrusion die may be a single-slot die or a multi-slot die. A single-slot die can be used when forming a film using only a single polymer-containing liquid. A multi-slot die can be used when forming a film using two or more different polymer types or polymer-containing liquids. When a multi-slot die is used and two or more different polymers or polymer-containing liquids are used, the extruded film is considered a single extruded film when extruded, even if the polymer compositions are chemically or physically different; a co-extruded film is considered a single, integrated film. A co-extruded film from a multi-slot die is exposed to solidification-inducing conditions only on two mutually opposite surfaces, and the resulting solidified film is considered to be formed in a single extrusion process and is considered an integrated film.

[0052] Any effective extrusion conditions and processing parameters can be used, including a useful stretching rate of the extruded film, a useful flow rate of the polymer-containing liquid, the air gap distance between the die and the solidification bath (if present), the humidity of the air in the air gap region (if present), and any useful, optionally conventional types and sizes of dies. The flow rate of the polymer-containing liquid passing through the die and the stretching rate of the extruded film can be used to influence the thickness of the extruded film.

[0053] After extrusion, both sides of the film are exposed to conditions that solidify the polymer contained in the extruded film. For example, the extruded film can be solidified by contacting it with a solidification bath that contains a liquid at a lower temperature than the extruded film, or a "non-solvent," or both. An example of a solidification bath in the TIPS method is a liquid bath such as water that has a temperature that solidifies the (non-solidified) polymer dissolved from the polymer-containing liquid of the extruded film, for example, a liquid with a temperature below 30, 20, or 10°C. An example of a solidification bath in NIPS is a bath made of a non-solvent, for example, water, or a mixture of water and an organic liquid that can dissolve the polymer solution solvent.

[0054] According to certain more detailed examples in these types of film formation techniques, the extruded (with non-coagulated or partially coagulated polymers) film may be extruded directly into the coagulation bath, or it may be extruded out of the coagulation bath (e.g., vertically upward) and then immediately placed into the coagulation bath after extrusion. In the latter example, the film is exposed to air after being extruded from the die and before the extruded (non-coagulated) film comes into contact with the liquid of the coagulation bath. Exposing the extruded film to air before it enters the coagulation bath ("air gap") is optional. If an air gap is present, the time the extruded film is exposed to air before contact with the coagulation bath may be as desired, for example, less than 2 seconds, less than 1 second, or less than 0.5 seconds. In other exemplary methods, the extruded film is extruded directly into the coagulation bath without contact with air before contact with the coagulation bath.

[0055] The type of polymer in the polymer solution and the resulting porous polymer film may be any type of polymer known or to become known for use in forming porous films by NIPS or TIPS techniques. In particular, for the NIPS method, examples of currently known or preferred polymers include, among others, polysulfones such as polyamides, polyimides, polyamide-polyimides, polyethersulfones, or polyphenylsulfones, and fluoropolymers such as polyvinylidene fluoride. In particular, for the TIPS method, examples of currently known or preferred polymers include, among others, polyolefins such as polyethylene and polypropylene, and fluorinated polymers such as perfluoroalkoxys (PFAs). Methods using single-slot dies require only a single polymer and a single polymer solution, although polymer mixtures can also be used. Methods using multi-slot dies, such as two-slot or three-slot dies, allow different polymer types, or polymer solutions of the same polymer but with different compositions, to flow through different slots. For example, a first type of polymer and a first polymer solution can be used in the slots forming the film surface, and one or more different polymers (or polymer solutions) can be used in one or more slots forming the interior regions of the film.

[0056] Referring here to Figures 2A, 2B, 3A, and 3B, some exemplary extrusion systems that are effective in preparing the exemplary polymer films described are shown. Figures 2A and 3A are front views of the exemplary system, and Figures 2B and 3B are side views of the exemplary system.

[0057] Referring to Figures 2A and 2B, the system 100 comprises an extrusion die 120, which may be, for example, a sheet extrusion die of a type conventionally called a coat hanger manifold die. The die 120 is a single-slot extrusion die with a slot 122 at the bottom of the die. The polymer solution 130 passes through the manifold of the die 120, then through the slot 122, and the extruded polymer solution then forms an extruded film 140a, which moves vertically downward under the die 120 without support. A liquid solidification bath 150 having an upper surface or "bathline" 152 is located below the die 120.

[0058] A source (not shown) of the polymer solution 130 is supplied at a constant and regular rate by a pump or other flow device so that it flows continuously through the die 120. After exiting the slot 122 downwards, the extruded film 140a enters and is immersed in the liquid in the solidification bath 150. The extruded film 140a exits the die slot 122 as a thin, continuous film of the polymer solution 130 having unsolidified polymer present in the polymer solution. To solidify the dissolved polymer in the polymer solution 130 of the film 140a, the film 140a with unsolidified polymer is then brought into contact with the liquid in the solidification bath 150.

[0059] The liquid in the coagulation bath 150 starts from the bath line 152 and comes into contact with the two opposite surfaces of the film 140a, causing the dissolved polymer on both surfaces of the film 140a to coagulate. The polymer on the film 140a precipitates (e.g., coagulates) from the solution to form a porous polymer film membrane 140b containing the polymer in its coagulated form. Because the liquid in the coagulation bath 150 comes into contact with the two opposite surfaces of the film 140a simultaneously, both surfaces are equally affected by the coagulation of the polymer by the liquid, resulting in the production of a film 140b having two opposite surfaces with equivalent or identical morphologies.

[0060] Optionally, as shown in Figures 2A and 2B, the film 140a made from the non-coagulated polymer solution 130 passes through a space ("air gap") after exiting the die slot 122 and before coming into contact with the liquid in the coagulation bath 150. Upon entering the coagulation bath 150, the liquid in the coagulation bath 150 causes phase separation in the polymer solution 130, forming a filter film 140b. Alternatively, according to other exemplary systems and methods, such as those shown in Figures 3A and 3B, there is no air gap between the die slot 122 and the liquid in the coagulation bath 150, and the phase separation (coagulation) of the polymer in the film 140a occurs immediately in the coagulation bath 150 as soon as the polymer solution 130 exits the die slot 122, forming the film 140b.

[0061] It should be noted that these figures show extruded films formed from a single polymer solution using a single-slot die. In other methods and systems, two or more different polymer solutions (optionally one or more different types of polymers) can be flowed through different slots of a multi-slot extrusion die.

[0062] As one or more optional subsequent steps, the film 140b may be further processed or modified using a washing tank, a heating step, a drying step, or a winding section. For example, after the phase separation (coagulation) step in the coagulation bath 150, the film 140b may be guided through a washing tank to extract any residual solvent. The washed (still wet) film 140b may then be collected on a roll, optionally before or after a post-processing drying step.

[0063] As shown in Figures 2A, 2B, 3A, and 3B, an extruded film undergoes a reduction in width, thickness, or both immediately after exiting the die. This phenomenon is sometimes called "necking," meaning that after the film exits and separates from the die, it "necks down," resulting in a decrease in width, thickness, or both. Alternatively, this phenomenon is sometimes called the "dogbone" effect. Due to this necking effect, the thickness of the extruded film, measured across the entire width and at the edges, may also show reduced uniformity—the film thickness may become less uniform, i.e., it may exhibit increased variability throughout the width and at the edges. Specific locations of reduced uniformity may occur at both ends (ends) of the film, with the thickness increasing (like a dogbone) at each end. A further potential advantage of this system and method is the desired high uniformity in film thickness across the entire width of the film, including the ends, i.e., the reduction of the dogbone effect.

[0064] The filtration membrane described may be useful for producing a filtered liquid by passing a liquid through the filtration membrane to remove one or more impurities from the liquid. The filtered liquid contains one or more impurities or particulate matter at reduced levels compared to the levels of impurities or particles present in the liquid before the liquid passed through the filtration membrane.

[0065] The polymer membranes described may offer a useful, desirable, or advantageous combination of physical properties, including performance (filtration performance as measured by "capture performance"), pore size or bubble point (related to pore size), flow rate, and mechanical properties (flexibility and durability, or reduced fragility).

[0066] The level of effectiveness of a filtration membrane in removing unwanted substances (i.e., "impurities") from a liquid can be measured in one way as "capture performance." Capture performance, in relation to the effectiveness of a filtration membrane (e.g., the filtration membrane described), generally refers to the total amount of impurities removed from a liquid (actual or during performance testing) relative to the total amount of impurities present in the liquid when the filtration membrane is passed through the impurity-containing liquid. Therefore, the "capture performance" value of a filtration membrane is a percentage, and a filter with a high capture performance value (high percentage) is relatively effective at removing particles from a liquid, while a filter with a low capture performance value (low percentage) is relatively ineffective at removing particles from a liquid.

[0067] Particle capture performance can be measured by measuring the number of test particles removed from the fluid flow by a membrane placed in the middle of the fluid flow. In one method, particle capture performance can be measured by passing a sufficient amount of an aqueous feed solution of 0.1% Triton X-100 containing 8 ppm polystyrene particles (e.g., G25 polystyrene round particles with a nominal diameter of 5-15 nanometers) through a 47 mm diameter membrane test piece at a constant flow rate of 7 ml / min to achieve a monolayer coverage of 1%, and collecting the permeate. The concentration of polystyrene particles in the permeate can be calculated from the absorbance of the permeate. Then, particle capture performance is calculated using the following formula. TIFF0007851241000001.tif15170

[0068] As used herein, “nominal diameter” refers to the diameter of a particle determined by photon correlation spectroscopy (PCS), laser diffraction, or optical microscopy. Typically, the calculated diameter, or nominal diameter, is expressed as the diameter of a sphere having the same projected area as the projection image of the particle. PCS, laser diffraction, and optical microscopy techniques are well known in the art (see, for example, Jillavenkatesa, A., et al.; “Particle Size Characterization;” NIST Recommended Practice Guide; National Institute of Standards and Technology Special Publication 960-1; January 2001).

[0069] In preferred embodiments of the described membranes, the membranes may exhibit capture performance exceeding 90% at monolayer coverages of 0.5%, 1.0%, 1.5%, and 2.0%, and may exceed 95%, 96%, or 97% at monolayer coverages of 0.5%, 1.0%, 1.5%, and 2.0%. This level of capture performance means that these embodiments of the membranes of the present invention exhibit a higher level of capture performance compared to many commercially available filtration membranes, such as equivalent flat sheet and hollow fiber filtration membranes fabricated by UPE. These exemplary membranes also exhibit useful, good, or very good flow rates (short flow times) and mechanical properties that allow the membranes to be prepared and assembled into filter cartridges or filter products.

[0070] Bubble points are a known property in porous materials, including the composite filtration membranes described herein. Bubble points may correspond to pore size, and pore size may correspond to filtration performance. Smaller pore sizes may be associated with higher bubble points and, in some cases, with higher filtration performance (higher capture performance). However, typically, higher bubble points are also associated with relatively greater resistance to flow through the porous material and lower flux. According to certain exemplary dual-tight membranes described herein, bubble points may correspond if measured in either direction of flow through the membrane. If the higher of two bubble points is not more than 20% larger than the lower one, for example, if the higher of two bubble points is not more than 10, 5, 2, or 1% larger than the lower one, then the bubble points measured in one direction are considered to correspond to the bubble points measured in the opposite direction. Bubble points corresponding in this way may indicate that the film has a high degree of symmetry with respect to the membrane's centerline.

[0071] One method for determining the bubble point of a porous material involves wetting a sample of the porous material by immersion in a liquid with a known surface tension, and applying gas pressure to one side of the sample. The gas pressure is increased in steps. The minimum pressure at which the gas flows through the sample is called the bubble point. Examples of useful bubble points for the described porous filtration membranes, measured at temperatures of 20–30°C (usually 25°C) using Novec HFE 7200, IPA, or water, compressed air, or compressed N2 gas, may range from 2 to 400 psi, e.g., 135–185 psi.

[0072] The filtration membranes described herein, or filters or filter components containing the filtration membranes described herein, may be useful in methods for filtering and purifying liquid chemicals, or for removing unwanted substances from liquid chemicals, particularly in methods for producing highly pure liquid chemicals useful in industrial processes requiring the input of very high-purity chemicals. Generally, the liquid chemicals may be any of the various useful commercially available substances and may be liquid chemicals useful or used for any application, any industrial or commercial use. Specific embodiments of the filters described herein can be used to purify liquid chemicals used or useful in semiconductor or microelectronics manufacturing applications, for example, to filter liquid solvents used in semiconductor photolithography or cleaning methods or processes for processing semiconductor wafers or microelectronic devices, or other processing liquids.

[0073] Some of the specific, non-limiting examples of solvents (including washing solutions) that can be filtered using the filtration membranes described include n-butyl acetate (nBA), isopropyl alcohol (IPA), 2-ethoxyethyl acetate (2EEA), xylene, cyclohexanone, ethyl lactate, methyl isobutylcarbinol (MIBC), methyl isobutyl ketone (MIBK), isoamyl acetate, undecane, propylene glycol methyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), or mixtures thereof, such as mixtures of PGME and PGMEA; or combinations thereof, such as concentrated or diluted ammonium hydroxide, hydrogen peroxide, hydrochloric acid, HF, sulfuric acid, another peroxide solution, or combinations thereof, such as combinations of ammonium hydroxide and hydrogen peroxide, or combinations of hydrochloric acid and hydrogen peroxide.

[0074] The membrane can be placed within a larger filter structure, such as a filter or filter cartridge used in a filtration system. The filtration system, for example, places the composite filtration membrane as part of a filter or filter cartridge in the flow path of a liquid chemical, allowing at least a portion of the flow of the liquid chemical to pass through the filter layer of the composite filtration membrane, so that a certain amount of impurities or contaminants are removed from the liquid chemical by the filter layer. The structure of the filter or filter cartridge may include one or more various additional materials and structures that support the composite filtration membrane within the filter, so that the fluid flows from the filter inlet through the membrane (including the filter layer) and through the filter outlet, thereby passing through the composite filtration membrane as it passes through the filter. [Examples]

[0075] Referring to Figure 4, Figure 4 shows a comparison of three filtration membranes made of polyethersulfone, prepared in different ways, and having different structures or morphologies.

[0076] One of the films is a "single-layer PES film." This film was fabricated using conventional phase separation methods such as NIPS. The single-layer PES film has asymmetric properties, with one side having a tight surface and the other side having an open surface.

[0077] One of the films is a "double-layer PES film." This film is a multilayer film made by stacking two single-layer PES films together, and the two films are used in a continuous manner.

[0078] One of the films is a "double-tight layer PES film" prepared according to this specification.

[0079] As shown in Figure 4, the double-tight layer PES film of the present invention exhibits significantly improved capture performance compared to other films made of the same material but with different morphologies or structures.

[0080] In the first embodiment, the integrally extruded porous polymer sheet film comprises a first surface, a second surface, a thickness between the first surface and the second surface, a first thickness region including the first surface and a portion of the film in the thickness direction, a second thickness region including the second surface and a portion of the film in the thickness direction, and a third thickness region extending in the thickness direction between the first thickness region and the second thickness region, wherein both the average pore diameter of the first thickness region and the average pore diameter of the second thickness region are smaller than the average pore diameter of the third region.

[0081] A second embodiment according to the first embodiment, wherein the film has a center line between a first surface and a second surface, the first thickness region includes a depth position having a minimum pore diameter on the first side of the center line, and the second thickness region includes a depth position having a minimum pore diameter on the second side of the center line.

[0082] A third embodiment according to the second embodiment, wherein the first minimum pore diameter is in the range of 1 nanometer to 10 microns, and the second minimum pore diameter is in the range of 1 nanometer to 10 microns.

[0083] A fourth embodiment according to the second or third embodiment, wherein the first minimum pore diameter is located between the first surface and a depth of one-third of the thickness from the first surface, the second minimum pore diameter is located between the second surface and a depth of one-third of the thickness from the second surface, and the average pore diameter of the third thickness region is measured at the central one-third of the thickness.

[0084] It has at least 5 degrees of asymmetry, and its symmetry (D) is D = (Average pore diameter in the third thickness region) / A [In the formula, A is one of the following: the average pore diameter of the first region; the average pore diameter of the second region; the minimum pore diameter of the first region; or the minimum pore diameter of the second region.] A fifth aspect which is defined as any one of the first to fourth aspects.

[0085] A sixth embodiment according to any one of the first to fifth embodiments, wherein the film comprises a polymer selected from polyethersulfone and polyamideimide.

[0086] A seventh embodiment, having a thickness in the range of 40 to 300 microns, according to any one of the first to sixth embodiments.

[0087] An eighth embodiment according to any one of the first to seventh embodiments, having at least 90% capture performance when measured based on a 1% monolayer using G25 polystyrene round particles with a nominal diameter of 5 to 15 nanometers.

[0088] A ninth embodiment according to any one of the first to eighth embodiments, which is prepared by a non-solvent-induced phase separation step, wherein a first thickness region, a second thickness region, and a third thickness region are formed using the same phase separation step.

[0089] A tenth embodiment according to any one of the first to ninth embodiments, essentially comprising an extruded porous polymer sheet film having first and second surfaces, a thickness between the surfaces, a first thickness region, a second thickness region, and a third thickness region.

[0090] An eleventh embodiment according to any one of the first to tenth embodiments, comprising an extruded porous polymer sheet film having first and second surfaces, a thickness between the surfaces, a first thickness region, a second thickness region, and a third thickness region.

[0091] In the twelfth embodiment, the filter comprises a film according to any one of the first to eleventh embodiments.

[0092] A thirteenth embodiment comprising a membrane in a pleated configuration housed within a housing.

[0093] In the fourteenth embodiment, a method for filtering a fluid includes passing the fluid through a filter according to the eleventh embodiment.

[0094] A 15th embodiment according to the 14th embodiment, wherein the fluid is a semiconductor photolithography solvent, a cleaning solution, or an etching solution.

[0095] A 16th embodiment according to the 15th embodiment, wherein the fluid is selected from propylene glycol methyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), cyclohexanone, and n-butyl acetate.

[0096] A 17th aspect according to the 15th aspect, wherein the fluid comprises a dilute or concentrated solution containing ammonium hydroxide, hydrogen peroxide, hydrochloric acid, HF, sulfuric acid, peroxide solution, or a combination thereof.

[0097] In the 18th embodiment, a method for producing an extruded porous polymer sheet film having first and second surfaces on opposite sides, a thickness between the opposite surfaces, and pores having non-uniform pore diameters includes forming a polymer-containing liquid containing a polymer in a solvent, passing the polymer-containing liquid through an extrusion die to form an extruded film of the polymer-containing liquid, and exposing both sides of the extruded film to conditions that induce polymer coagulation on both sides of the film.

[0098] A 19th aspect according to the 18th aspect, further comprising causing solidification on both sides of the extruded film by a thermally induced phase separation technique.

[0099] A 20th aspect according to the 18th aspect, further comprising causing coagulation on both sides of the extruded film by a non-solvent-induced phase separation technique.

[0100] A 21st aspect according to the 18th aspect, further comprising causing solidification on both sides of the extruded film by exposing both sides of the extruded film to moisture.

[0101] A 22nd aspect according to the 18th aspect, further comprising causing solidification on both sides of the extruded film by evaporating a liquid on both sides of the extruded film.

[0102] A 23rd embodiment according to the 18th embodiment, comprising bringing a first surface and a second surface of an extruded film into contact with a solidification bath to solidify the polymer dissolved in a polymer solution, thereby forming an extruded porous polymer film containing the solidified polymer of the polymer solution.

[0103] A 24th embodiment according to any one of the 18th to 23rd embodiments, wherein the film comprises a first surface, a second surface, a thickness between the first surface and the second surface, a first thickness region including the first surface and a portion of the film in the thickness direction, a second thickness region including the second surface and a portion of the film in the thickness direction, and a third thickness region extending in the thickness direction between the first thickness region and the second thickness region, wherein both the average pore diameter of the first thickness region and the average pore diameter of the second thickness region are smaller than the average pore diameter of the third region.

[0104] A 25th embodiment according to the 23rd or 24th embodiment, wherein the extruded film exits the die through the die opening and the die opening is immersed in a solidifying solution.

Claims

1. An integrated porous polymer sheet membrane for filtering a liquid material, The first surface, the second surface, and the thickness between the first surface and the second surface, A first thickness region that includes the first surface and extends to a depth below the first surface, but does not extend to the centerline of the film, A second thickness region including the second surface and extending to a depth below the second surface, but not extending to the centerline of the film, and It comprises a third thickness region extending in the thickness direction between a first thickness region and a second thickness region, When the average pore diameter of both the first thickness region and the second thickness region is smaller than the average pore diameter of the third thickness region, and when measured using polystyrene round particles with a diameter of 5 to 15 nanometers, the film exhibits at least 90% capture performance. The film has an asymmetry of at least 5, and the asymmetry (D) is D = (Average pore diameter of the third thickness region) / A [In the formula, A is one of the following: the average pore diameter of the first region; the average pore diameter of the second region; the first minimum pore diameter; or the second minimum pore diameter.] Defined as, The capture performance is measured by passing a sufficient amount of 0.1% Triton X-100 aqueous feed solution containing 8 ppm polystyrene round particles through a 47 mm diameter membrane test piece at a constant flow rate of 7 ml / min, achieving a monolayer coverage of 1%, and collecting the permeate. film.

2. The film has a center line between the first surface and the second surface. The first thickness region has a minimum pore diameter at a position between the first surface and the center line. The film according to claim 1, wherein the second thickness region has a minimum pore diameter at a position between the second surface and the center line.

3. A method for producing an integrated porous polymer sheet membrane for filtering a liquid material, Forming a polymer-containing liquid that includes a polymer in a solvent, The process involves passing a polymer-containing liquid through an extrusion die to form an extruded film of the polymer-containing liquid, and This includes exposing both sides of the extruded film to conditions that induce polymer coagulation on both sides of the film, An integrated porous polymer sheet film, The first surface, the second surface, and the thickness between the first surface and the second surface, A first thickness region that includes the first surface and extends to a depth below the first surface, but does not extend to the centerline of the film, A second thickness region including the second surface and extending to a depth below the second surface, but not extending to the centerline of the film, and It comprises a third thickness region extending in the thickness direction between a first thickness region and a second thickness region, When the average pore diameter of both the first thickness region and the second thickness region is smaller than the average pore diameter of the third thickness region, and when measured using polystyrene round particles with a diameter of 5 to 15 nanometers, the film exhibits at least 90% capture performance. The film has an asymmetry of at least 5, and the asymmetry (D) is D = (Average pore diameter of the third thickness region) / A [In the formula, A is one of the following: the average pore diameter of the first region; the average pore diameter of the second region; the first minimum pore diameter; or the second minimum pore diameter.] Defined as, The capture performance is measured by passing a sufficient amount of 0.1% Triton X-100 aqueous feed solution containing 8 ppm polystyrene round particles through a 47 mm diameter membrane test piece at a constant flow rate of 7 ml / min, achieving a monolayer coverage of 1%, and collecting the permeate. method.

4. The method according to claim 3, further comprising inducing solidification on both sides of the extruded film by thermally induced phase separation technology.

5. The method according to claim 3, further comprising inducing coagulation on both sides of the extruded film by a non-solvent-induced phase separation technique.

6. The method according to claim 3, further comprising causing solidification on both sides of the extruded film by evaporating a liquid on both sides of the extruded film.

7. The method according to claim 3, further comprising bringing the first surface and the second surface into contact with a solidification bath to induce solidification on both sides of the extruded film.

8. The extruded film exits the extrusion die from the die opening. The method according to any one of claims 3 to 7, wherein the die opening is immersed in a solidifying solution.

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