TW201137000A - Biaxially oriented porous membranes, composites, and methods of manufacture and use - Google Patents

Abstract

At least a selected microporous membrane is made by a dry-stretch process and has substantially round shaped pores and a ratio of machine direction tensile strength to transverse direction tensile strength in the range of 0.5 to 6.0. The method of making the foregoing microporous membrane may include the steps of: extruding a polymer into a nonporous precursor, and biaxially stretching the nonporous precursor, the biaxial stretching including a machine direction stretching and a transverse direction stretching, the transverse direction including a simultaneous controlled machine direction relax. At least selected embodiments of the invention may be directed to biaxially oriented porous membranes, composites including biaxially oriented porous membranes, biaxially oriented microporous membranes, biaxially oriented macroporous membranes, battery separators, filtration media, humidity control media, flat sheet membranes, liquid retention media, and the like, related methods, methods of manufacture, methods of use, and the like.

Description

201137000 VI. Description of the invention: [Technical field of invention] Cross-reference to related application This application claims the benefit of US Provisional Patent Application No. 61/313,152 in the application filed on March 12, 2010. And priority. FIELD OF THE INVENTION The present invention relates to biaxially oriented porous membranes, composites comprising biaxially oriented porous membranes, biaxially oriented microporous membranes, biaxially oriented macroporous membranes, battery separators, percolating media, humidity control media, flat membranes Liquid retention media and the like, related methods, methods of manufacture, methods of use, and the like.

BACKGROUND OF THE INVENTION Microporous polymer membranes are known which can be made by a variety of methods and the method of making the film can have a material impact on the physical properties of the film. See, for example, Kesting, Robert E. 'Synthetic Polymeric Membranes, A Structural Perspective' (Second Edition, John Wiley &; Sons), New York, NY, (1985)). Three different methods known for making microporous polymer films include: dry stretching methods (also known as the CELGARD method), wet methods, and particle stretch methods. The dry stretching method (Silga method) refers to a method of stretching a nonporous, semicrystalline, extruded polymer precursor (MD stretching) from the machine direction for the pore forming system. See, for example, Kestin, supra, 201137000, pp. 29-297, which is incorporated herein by reference. This dry stretching method is different from the wet method and the particle stretching method. In general, in a wet process (also known as a phase inversion method, an extraction method (extmetiGn) or a method), the polymer is compounded with I oil (sometimes referred to as a plasticizer). The mixture is extruded to "when the processing oil is removed" into holes (these films can be stretched before or after the oil is removed). See, for example, Kestin, supra, page 237, 286, which is incorporated herein by reference. Generally speaking, in the particle stretching method, the polymer raw material is mixed with the particulate matter to squeeze the mixture, and during the stretching, when the interface between the polymer and the particulate matter is broken due to the tensile force, a hole is formed. . See, for example, U.S. Patent No. 6, 〇 57, 061 and 6, 〇 8, 5, 7, which is incorporated herein by reference. Moreover, the films produced by these various forming methods are generally physically different, and the method of making each film typically distinguishes the films from each other. For example, a dry draw process film may have slit-shaped holes due to stretching the precursor in the machine direction (md) (see, for example, Section 1.3). The fishing process film tends to have an oil or plasticizer and stretches the precursor in the machine direction (MD) and in the transverse sling or direction of detection (TD) (see, for example, Figure 4). The pores and lace-like appearance of the skull. Alternatively, the particle stretching process has elliptical holes such as particulate matter, and the machine direction stretching (MD^t stretching) tends to form the holes (see, for example, Fig. 5). In addition, each film can be distinguished from others by its manufacturing method. Although films made by the dry stretching process have achieved excellent commercial success (such as a variety of Sergey 8 sold by Sylvain LLC in Charlotte, North Carolina, 201137000 (Charlotte). Dry stretched porous membranes, including flat membranes, battery separators, hollow fibers, and the like, there is a need to modify, modify or enhance at least their selected physical properties so that they can be used in a wide range of applications. Have a good performance for a particular purpose or a similar purpose. The use of air filters to remove or reduce airborne contaminants such as dust, dust mites, mold, bacteria, dog hair dander, odors and gases is generally known. Conventionally, an air cleaner comprises a filter medium formed from a batt, a mat or a sheet of porous material which is folded and placed in a rectangular frame or support or folded into a wavy oval or cylinder so that Provides a large filtration area in a relatively small volume. While at least some air filters have achieved commercial success, there are still improvements to filter media or filters so that they can be used in a wide range of filtration or separation applications, for better performance for a particular purpose, or the like. demand. The use of porous materials to selectively pass gases and block liquids is known. For example, LIQUI-CEL® Hollow Fiber Membrane Contactors (Membrana-Milbrana-based City of Sylvester LLC in Charlotte, North Carolina) have been used. Charlotte) sells) degassing or defoaming liquids. More specifically, the Riquis® membrane contactor is widely used in the global microelectronics, pharmaceutical, power, food, beverage, industrial, photographic, ink and analytical markets to degas liquids. The use of porous materials for the treatment of percolation or separation is known. For example, by Buppertal, Wuppertal, Germany (Membrana 201137000)

GmbH) or a variety of flat membranes sold or sold by Sylvain LLC and Daramic LLC (both in Charlotte, North Ten Carolina) have been used in filtration or separation processes. More specifically, these flat films have been used to separate solid particles from liquids, gases and liquids, particles and gases, and the like. Although some of the porous materials dedicated to filtration or separation processes have achieved commercial success, improvements have been made to porous materials so that they can be used in a wide range of applications, for better performance for special purposes, or the like. Have requests. The use of porous materials to selectively pass moisture (moisture vapor) and [5 and to block liquid water, liquid desiccants or other aqueous solutions is known. In this liquid filling system, the temperature and humidity can be controlled by a salt solution (forming a dehumidifying agent) that absorbs or emits water vapor. The use of porous materials to selectively pass water vapor (heat and moisture) and barrier gases (discharge and introduction of gases) can be known to be linked to energy recovery ventilation (ERV), where heat and moisture are present in the ventilation system. Exchange between compensation and exhaust air. The use of porous materials to selectively pass pure or fresh water and resistive salts or brine is also known to be linked to reverse osmosis desalting, wherein porous materials such as reverse osmosis buffers (RO filters) allow pure water (fresh water) to This passes but curbs the salt. As the brine is under high pressure, fresh water is forced through the porous material and forms a fresh water stream. The use of porous materials to selectively pass water vapor or moisture (moisture vapor) and barrier liquid brines is also known to be desalted in connection with vapors, wherein the porous material 201137000 material (such as a high charge density film) can block brine but pass salt-free Water vapor to separate brine from fresh water. As the brine is at a high temperature, fresh water vapor is evolved from the brine which can drift through the porous material and condense to form a fresh water stream. The use of porous materials to selectively pass gases or moisture (moisture vapor) and barrier liquids (such as water) is known to be linked to fuel cells, such as hydrogen fuel cells with proton exchange membranes (PEM), which must be kept moist. . Waste water in the form of moist steam can pass through the porous material and can be collected in or discharged from the wastewater containment compartment. Although some of these porous materials for selectively passing gases or moisture (moisture vapor) and blocking liquid water or brine may have gained commercial success (such as RO films sold by Dow Chemical, or by WL) The expanded polytetrafluoroethylene (ePTFE) film sold by Gore BHA and its bismuth) are still suitable for improving porous materials so that they can be used in a wide range of applications, and can be better for special purposes or There are needs for similar purposes. SUMMARY OF THE INVENTION Summary of the Invention According to at least selected porous materials, films, layers, films, laminates, coextrudates or composite embodiments of the present invention, certain modified regions may include pore shapes other than slits, circles Shaped holes, increased lateral tensile strength, balance of MD and TD physical properties, high performance associated with, for example, moisture transfer and head pressure, reduced Gurley, high porosity with balanced physical properties, and pore structure ( Consistency of pore size and pore size distribution, improved durability, composite of these films with other porous materials, 201137000; composites or laminates of such films, films or layers with porous nonwovens; coated films, Coextruded film, laminated film; film with desired moisture transport (or moisture vapor transport), head performance and physical strength properties; no practical loss of desired film characteristics in more physical and harsh environments Combination of film moisture transport performance and macroscopic physical properties, hydrophobicity, high permeability, chemical and mechanical stability With high tensile strength, combinations thereof, and / or similar properties. Although some films made by the dry stretching process have achieved excellent commercial success, they have been modified, modified or improved to at least their selected physical properties so that they can be used in a wide range of applications for special purposes. There is a need for better performance and/or similar purposes. According to at least selected specific examples of the dry drawing process film of the present invention, certain modified regions may include a hole shape other than a slit, a circular hole, an increase in the transverse direction tensile strength, a balance between MD and TD physical properties, and a hole. Consistency of structure (including pore size and pore size distribution), high performance associated with, for example, moisture transfer (or moisture vapor transport) and head pressure, reduced Gore, high porosity with balanced physical properties, improved durability, a composite of the film with other porous materials, a composite or laminate of the film and porous nonwoven, a coated film, a coextruded film, a laminated film; having desired moisture transport, head properties and physical strength properties The film; useful in more physical and harsh environments without loss of desired film characteristics, combination of film moisture transport properties and macrophysical properties, combinations thereof, and/or the like. The porous membrane of the present invention may preferably be a porous membrane, film, layer or composite of a dry stretching process, according to at least selected preferred preferred embodiments, 201137000 八八水!1生同透性,化学和Mechanical stability, high tensile strength, degree and combination. Some of the properties seem to make it ideal for the following applications: 4 membranes or membranes each of which (10) air filtration) may include selective passage of moisture vapor (or its body) and 卩*Mt liquid water (or other liquid): 1. HVAC: a. Liquid Dehumidification (LD) Air Conditioning (Temperature and Humidity Control): In a film-based LD system, temperature and humidity can be controlled by a salt solution that absorbs or releases moisture vapor through the porous membrane. In this system, heat is the driving force (non-pressure, as in most air conditioning systems). To allow the n to be 'requires a film that is hydrophobic and easily allows moisture vapor to pass (to prevent liquid). b. Water-based air conditioning (temperature and humidity control): The evaporative cooling system or cooling water system operates on a slightly different principle than the LD system, but it will use the same basic properties of the film. C_Energy Recovery Ventilation (ERV): The simplest HVAC application, using a far film as a key component in the exchange of heat and moisture between the compensation and exhaust air. 2. Desalination: Vapor desalination uses the same film properties as HVAC. Because the membrane blocks liquid brine but allows water vapor to pass through, a system for separating brine and fresh water by membrane can be constructed. As the brine is at a higher temperature, fresh water vapor is evolved from the brine, which drifts through the membrane and condenses to form a fresh water stream. 3. Fuel cells: In fuel cells, the proton exchange membrane (PEM) must be kept moist. This can be achieved with the use of a film-based wet 201137000 run unit. 4_Liquid and/or air filtration: In these specific examples, the porous membrane acts as a simple filter. When liquid, vapor, gas or air passes through the thin material, particles that are too large to pass through the pores are blocked at the surface of the film. Particularly in the case of liquid and air filtration, the unique pore structure of at least selected embodiments of the present invention can provide specific examples, materials or films having certain specific benefits, such as durability, high efficiency, narrow pore size. Distribution and consistent flow rate benefits. According to the at least selected porous material or porous film of the present invention, at least the selected porous single layer polypropylene (single layer pp) film (10) has good MD and TD physical properties, and is also a high performance film ( Such as by moisture transfer and head performance measurement). This selected single layer pp film can also have high porosity (> 60%), but still maintains balanced physical properties (when compared to more conventional films). Similarly, this single layer of choice? 1> The film or film can be produced by laminating or laminating one or both of the porous polypropylene (PP) nonwoven material (woven pp). The resulting composite, film or product (single layer pp/non-woven PP) or (non-woven PP/single layer PP/non-woven PP) preferably retains excellent moisture transport and altered head performance. Likewise, the resulting composite product (single layer PP/non-woven PP) or (non-woven PP/single layer PP/non-woven PP) can have properties far exceeding the physical strength of the comparative film. Therefore, this newly produced composite product (single layer PP/non-woven PP) can have the advantage of being added, which is useful in a more physical and harsh environment without Loss of the desired film characteristics. The selected single-layer Pp film and composite 201137000 product (single layer PP; single layer Pp/non-woven PP; or non-woven pp/single layer pp/non-woven pp) have their moisture transport properties and their macroscopic properties. The combination of physical properties is unique in people. For example, 'previous films may have porosity but insufficient head pressure or performance, other films are too fragile, other films are strong but lack other properties or the like, although at least selected specific examples of the invention may have, for example, The required porosity, moisture transport 'head pressure, strong production and similar properties. According to at least selected porous material or porous film embodiments of the present invention, at least the selected porous multilayer polypropylene (multilayer PP) film has excellent balance of physical properties of MD and TD' while also being a high performance film (eg, by moisture) Transfer and head performance measurement). This selected multilayer PP film can also have a high porosity (>6 〇 /.), but still maintain balanced physical properties (when compared to more conventional films). Similarly, the selected multilayer PP film or film can be produced by laminating or laminating one or both of the porous polypropylene (PP) nonwoven material (non-woven PP). The resulting composite, film or product (multilayer pp/non-woven PP) or (non-woven PP/multilayer PP/non-woven PP) preferably retains excellent moisture transport and altered head performance. Likewise, the resulting composite product (multilayer PP/non-woven PP) or (non-woven PP/multilayer PP/non-woven PP) can have properties far exceeding the physical strength of the comparative film. Therefore, this newly produced composite product (multilayer PP/non-woven PP) or (non-woven PP/multilayer PP/non-woven PP) can have the advantage of being added, which is useful in a more physical and harsh environment without loss of height. The desired film characteristics. The combination of these selected multilayer PP films and composite products (multilayer PP; multi-layer PP/non-woven PP; or non-woven PP/multi-layer PP/non-woven PP) in combination with their film moisture transport properties and their macroscopic physical properties On the exclusive 201137000 special. For example, previous remedies may have porosity but a sufficient head pressure or performance, others (10) are too fragile, other films are strong but lack other properties or the like. However, at least selected specific examples of the invention may have Desirable porosity, moisture transfer, head pressure, strength and similar properties. According to at least selected porous material or porous film embodiments of the present invention, at least the selected porous single layer polyethylene (single layer PE) film has excellent balance of MD and TD physical properties, and is also - high performance (four) (eg By moisture transfer and head performance measurement) <5 This selected single layer 1> film may also have a high porosity (> 6 G%), but still maintain a balanced physical f (when compared to more conventional films). Similarly, the selected monolayer film or film may be on its or both sides with a porous polyethylene (PE) nonwoven (non-woven pE) or porous polypropylene (PP) nonwoven material (not woven) PP) manufactured by merging or laminating. The resulting composite, film or product (single layer PE/non-woven PE) or (non-woven pE/single layer PE/non-woven PE) preferably retains excellent moisture transport and altered good head performance. Similarly, the resulting composite product (single layer pE/non-woven pE) or (non-woven PE/single layer PE/non-woven PE) can have far more physical properties than the comparative (four) film. Therefore, this new generation The composite product (single layer pE/non-woven pE) or (non-woven PE/single layer PE/non-woven PE) can have the advantage of being added, which is useful in a more physical and severe environment without loss. Film characteristics. The selected single-layer PE film and composite products (single layer pE; single layer pE/non-woven PE; or non-woven PE/single layer PE/non-woven PE) have their moisture transport properties and their macroscopic physics. The combination of properties is unique. For example, previous films may have porosity but insufficient head pressure or performance, other films are too fragile, other films are strong but lack other properties or the like, although at least selected specific examples of the invention may be There are, for example, desirable porosity, moisture transfer, head pressure, strength, and the like. According to at least selected porous material or porous film embodiments of the present invention, at least the selected porous multilayer polyethylene (multilayer PE) film has excellent balance of MD and TD physical properties, and is also a high performance film (eg, by Moisture transfer and head performance measurement). The selected multilayer 1 > film can also have a high porosity (> 60%) but still maintains a balanced physical property (when compared to more conventional films). Similarly, the selected multilayer PE film or film may be coated on one or both sides with a porous polyethylene (PE) nonwoven material (non-woven PE) or a porous polypropylene (PP) nonwoven material (non-woven PP). Made by combining or layering. The resulting composite, film or product (multilayer PE/non-woven PE) or (non-woven PE/multilayer PE/non-woven PE) preferably retains excellent moisture transport and altered head performance. Likewise, the resulting composite product (multilayer PE/non-woven PE) or (non-woven PE/multilayer PE/non-woven PE) can have physical strength properties far exceeding that of the comparative film. Therefore, this newly produced composite product (multilayer PE/non-woven PE) or (non-woven PE/multilayer PE/non-woven PE) can have the advantage of being added, which is useful in a more physical and harsh environment without loss of height. The desired film characteristics. The combination of these selected multilayer PE films and composite products (multilayer PE; multi-layer PE/non-woven PE; or non-woven PE/multi-layer PE/non-woven PE) in combination with its moisture transport properties and its macroscopic physical properties Unique on the ground. For example, 'previous films may have porosity but insufficient head pressure or performance, other films are too fragile, other films are strong but lack other properties or the like, although at least selected specific examples of the invention may have, for example The desired pores 13 201137000 degrees, moisture transfer, head pressure, strength and similar properties. At least selected porous single layer polymeric film (e.g., a single layer (which may have one or more layers) of a polyolefin (PO) film, such as polypropylene (pp), in accordance with at least selected porous material or porous film embodiments of the present invention. And/or polyethylene (PE) (including PE, PP or PE+PP blends) single-layer film) has excellent balance of md and TD physical properties, and is also a high performance film (eg by moisture transport ( Or moisture vapor transmission) and head performance measurement). The selected monolayer p〇 film may also have a germanium porosity (> 60°/.) but still maintain a balanced physical property (when compared to more conventional films). Similarly, the selected single-layer PO film or film may be on one or both sides with a porous nonwoven material (such as a non-woven polymer material 'for example, a PO non-woven material (such as porous polyethylene (PE) not woven) The material (non-woven PE) and/or porous polypropylene (PP) nonwoven material (non-woven pp) (including PE, PP or PE+PP blend))) are produced by lamination or lamination. The resulting composite, film or product (single layer PO/non-woven PO) or (non-woven PO/single layer PO/non-woven PO) preferably retains excellent moisture transport (or moisture vapor transport) and good modification Head performance. Likewise, the resulting composite product (single layer PO/non-woven PO) or (non-woven p0/monolayer P〇/non-woven PO) can have properties far exceeding the physical strength of the comparative film. Therefore, 'this newly produced composite product (single layer p〇/non-woven p〇) or (non-woven P〇/single layer P〇/non-woven P〇) can have the advantage of being added, which is more physically and severely It is useful in the environment without loss of highly desirable film characteristics. The selected single-layer p◦ film and composite products (single layer P0; single layer PO/non-woven PO; or non-woven PO/single layer PO/non-woven PO) have good moisture transport properties and their macroscopic properties. The combination of physical properties is unique in combination. For example, a prior film may have a porosity but insufficient head pressure or property 201137000, other films are too fragile, other films are strong but lack other properties or the like, although at least selected specific examples of the invention may have For example, desired porosity, moisture transport, moisture vapor transport, head pressure, strength, and the like. At least selected porous multilayer polymeric films (eg, multilayer (two or more layers) polyolefin (PO) films, such as polypropylene (PP), and at least selected porous material or porous film embodiments in accordance with the present invention. / or polyethylene (PE) (including PE, PP or PE + PP blend) multilayer film) has excellent MD and TD physical properties balance, but also a high performance film (such as by moisture transport (or moisture vapor) Transfer) and head performance measurement). The selected multilayer PO film can also have a high porosity (> 60%), but still maintain balanced physical properties (when compared to more conventional films). Similarly, the selected multilayer PO film or film may be on one or both sides with a porous PO nonwoven material (such as a porous polyethylene (PE) nonwoven material (non-woven PE) and/or a porous polypropylene (PP). ) Non-woven materials (non-woven PP) are manufactured by combining or laminating. The resulting composite, film or product (multilayer PO/non-woven PO) or (non-woven PO/multilayer PO/non-woven PO) preferably retains excellent moisture transport and altered good head performance. Similarly, the composite product (multilayer PO/non-woven PO) or (non-woven P/multilayer P〇/non-woven PO) produced by this can have physical strength properties far exceeding that of the comparative film. Therefore, this newly produced composite product (multilayer PO/non-woven PO) or (non-woven PO/multilayer PO/non-woven PO) can have the advantage of being added, which is useful in a more physical and harsh environment without loss of height. The desired film characteristics. These selected multi-layer PO films and composite products (multilayer PO; multi-layer p〇/non-woven PO; or non-woven PO/multi-layer PO/non-woven PO) in their film moisture transport properties and their macroscopic materials 15 201137000 The combination of properties is unique. For example, previous films may have porosity but insufficient head pressure or performance, other films are too brittle, other films are strong but lack other properties or similar events, but at least selected examples The invention may have, for example, the desired porosity, moisture transport, head pressure, strength, and the like. According to at least one selected porous material or porous film embodiment of the present invention, the hole (opening) has the following hole depth ratio (according to the hole opening in the machine direction (MD) (length) and the transverse machine direction (TD) ( The physical size of the width, by measuring one or more of the SEMs, for example, on the surface (upper or front (A side)) of the selected film or composite (eg, 'single, second or triple film') Holes (several holes are preferred to confirm the average)): Typical: MD/TD depth ratio is better in the range 0.75 to 1.50: MD/TD depth ratio is best in the range 0.75 to 1.25: MD/TD depth The ratio is in the range of 0.85 to 1.25. According to at least the selected porous material or porous film embodiment of the present invention, if the MD/TD hole depth ratio is 1.0, the three-dimensional or 3D hole ball diameter factor or ratio (MD/TD/ND) range may be :1. 〇 to 8_〇 or larger; may preferably be 1.0 to 2_5; and most preferably 1.0 to 2·〇 or less (according to the opening of the hole in the machine direction (MD) (length), lateral Physical dimension in machine direction (TD) (width) and thickness direction or cross section (ND) (thickness); for example, one of SEMs measured on the upper or front surface (A side) or the lower or back surface (B side) Or more than 16 201137000 holes MD and TD (several holes are preferred to confirm the average), and measure one of the SEMs in section, depth or height (C side) (length or width section or both) Or ND of multiple holes (several holes are preferred to confirm the average) (when it is difficult to measure the ND, MD, and TD dimensions of the same hole, the ND size may be a hole different from the MD and TD sizes)). According to at least selected porous material or porous film embodiments of the present invention, the holes (openings) have the following hole depth ratios (in the machine direction (MD) (length) and transverse machine direction (TD) (width) of the hole opening Based on the physical dimensions, based on the measurement of the holes in the SEMs above or in front of the selected single and triple film (A side): machine direction MD (length) and lateral direction TD (width) Typical values for the depth ratio range: The MD/TD depth ratio is in the range of 0.75 to 1.50. According to at least selected porous material or porous membrane embodiments of the present invention, the holes (openings) have the following three-dimensional or 3D hole sphericity factor or ratio (with hole opening in machine direction (MD) (length), transverse machine Based on the physical dimensions of the direction (TD) (width) and the thickness direction or section (ND) (thickness); for example, measuring the selected film, layer or composite (eg 'selected single and triple film One or more holes in the SEMs of the top or front surface (A side), the lower or back surface (B side), and the section, depth or height (C side) (length or width section or both) Several holes are preferred to confirm the average) (When it is difficult to measure the ND, MD and TD dimensions of the same hole, the ND size can be a hole different from the MD and TD dimensions): For example: 17 201137000 Typical: MD/TD The depth ratio is in the range of 0.75 to 1.50. The MD/ND size ratio is in the range of 0.50 to 7.50. The TD/ND size ratio is preferably in the range of 0.50 to 5.00: The MD/TD depth ratio is in the range of 0.75 to 1.25. The TD/ND size ratio in the range of 1.0 to 2.5 is in the range 1. Optimum within 0 to 2.5: The MD/TD depth ratio is in the range of 0.85 to 1.25. The MD/ND size ratio is in the range of 1.0 to 2.0. The TD/ND size ratio is in the range of 1.0 to 2.0. At least the selected porous according to the present invention. In the material or porous film embodiment, the holes (openings) have the following hole sphericity factors or ratios (in terms of machine direction (MD) (length), transverse machine direction (TD) (width), and thickness direction according to the opening of the holes) Or physical dimensions in section (ND) (thickness) to measure the length and cross section (C side) of the SEMs of the holes above or in front of the selected single and triple film (A side): Machine Typical values for the ball diameter factor or ratio range of direction MD (length), lateral direction TD (width), and thickness direction ND (vertical height): MD/TD depth ratio in the range of 0.75 to 1.50 MD/ND size ratio in the range The TD/ND size ratio in the range of 0.50 to 7.50 is in the range of 0.50 to 5.00. According to at least selected specific examples of the present invention, the microporous film and its substantially circular pores are produced by the dry stretching method 18 201137000, and Machine direction tensile strength The ratio of the tensile strength in the direction is in the range of 0.5 to 6.0, preferably 0.5 to 5.0. The method of producing the aforementioned microporous film comprises the steps of extruding a polymer into a nonporous precursor, and biaxial stretching. The non-porous precursor comprising machine direction stretching and transverse direction stretching, the transverse direction stretching comprising synchronously controlled machine direction relaxation. According to at least selected specific examples of the invention, by The modified dry stretching process produces a porous membrane having substantially circular pores, a ratio of machine direction tensile strength to transverse tensile strength in the range of 0.5 to 6.0, and a low gloss (as with prior dry) Stretched film comparisons) have larger and more consistent average flow pore sizes (as compared to previous dry stretched films), or lower Gorey and larger and more consistent average flow pore sizes. While some films made by conventional dry stretching methods have achieved excellent commercial success, at least selected physical properties are provided that are modified, modified or improved in accordance with at least selected specific examples of the present invention. , so that they can be used in a wide range of applications, can be better for special purposes and / or the like. While at least some air cleaners have achieved commercial success, in accordance with at least selected specific examples of the present invention, there are provided improved, modified or enhanced filter media so that they can be used in a wide range of filtration or separation applications. It can have a good performance for a special purpose and / or its like. While at least some of the flat porous materials used in the filtration or separation process have achieved commercial success, in accordance with at least selected specific examples of the present invention, there are provided improved, modified or enhanced porous materials so that they can be used at 19 2011 37000 Wide range of applications, good performance for special purposes and / or similar purposes. Although some of the porous materials used to selectively pass gas or moisture (moisture vapor) and block liquid water or brine have achieved commercial success (such as RO film sold by Dow Chemical, ePTFE sold by W丄 Gower BHA) Films and others, according to at least selected specific examples of the invention, there are provided improved, modified or enhanced porous materials so that they can be used in a wide range of applications, have better performance for special purposes and / or its similar purpose. According to at least selected embodiments of the present invention, the air cleaner 包括 comprises at least one sheet of a folded porous membrane (such as a microporous membrane). BRIEF DESCRIPTION OF THE DRAWINGS In order to clarify the various aspects or specific examples of the present invention, the present invention is shown in the drawings as a typical form; however, it is understood that the invention is not limited to such specific examples, precise arrangements or tool. Figure 1 is a photograph of a single layer of siggaide® (SEM surface photomicrograph), which is a conventional dry stretch type polypropylene battery separator. Fig. 2 is a photograph of a dry stretch type film (single layer film) of the prior art. Fig. 3 is a photograph of a dry stretch type film (multilayer film, several layers laminated and then stretched) of the prior art. Figure 4 is a photograph of a single layer of siggaide® (SEM surface photomicrograph), which is a wet process type polyethylene battery separator. Fig. 5A is a photograph of a particle-stretched film (SEM surface photomicrograph). Figure 5B is a photograph of a particle-stretched film (SEM cross-section photomicrograph). 20 201137000 Fig. 6 is a photograph (Sem surface photomicrograph) of a film (single layer film, biaxial orientation method) according to a specific example of the present invention. Fig. 7 is a photograph (saEM surface micrograph) of a film (multilayer film, a plurality of layers and then a stretched 'biaxial orientation method) according to another embodiment of the present invention. Fig. 8 is a photograph (s running surface photomicrograph) of a film (multilayer film' multi-layer co-extrusion and then stretching, biaxial orientation method) according to still another specific example of the present invention. Fig. 9 is a schematic representation of a typical TD stretching method according to at least one specific example of the method for producing a biaxially oriented film of the present invention. ^ Figure 10 is a photograph of a conventional Sirga 825 〇〇 film (PP monolayer, dry stretching method) at 20,000X magnification (SEM surface micrograph). Figure 11 is a photograph of the film of Figure 10 at 5 〇〇〇χ magnification (SEM surface photomicrograph). Figure 12 is a photograph of the film of Figures 10 and 11 at 2〇, 〇〇〇χ magnification (SEM cross-section photomicrograph). 13 and 14 are respective photographs of a film sample ΡΡ (ΡΡ single layer, collapsed bubble, biaxial orientation method) according to another film embodiment of the present invention (sem surface Α at 20,000 Χ and 5,000 Χ magnification) (upper) photomicrograph). Figures 15 and 16 are separate photographs of film sample B of Figures 13 and 14 (SEM surface B (bottom) photomicrograph at 20,000X and 5,000X magnification). Figures 17 and 18 are photographs of film samples B of Figures 13 through 16 (SEM cross-section micrographs at 20,000X and 5,000X magnification). Figures 19, 20 and 21 are still another film or composite 21 according to the present invention. Specific examples of the 2011 37000 material (PP single layer [sample B] / non-woven pp, laminated [heat + pressure D film sample C respective photos) (SEM surface Α (top) photomicrograph at 20,000X, 5,000X and 1, 〇〇〇χ magnification). Figures 22, 23 and 24 are separate photos of film sample C of sheets 19 to 21 ( SEM surface B (bottom) photomicrographs at 20,000 Χ, 5, ΟΟΟΧΑ1〇〇〇χ magnification. Figures 25 and 26 are individual photographs of film samples C of Figures 19 to 24 (at 20,000X and 5) SEM cross-section photomicrograph at 0〇〇χ magnification.) Figure 2-7 is a photograph of a film sample C (inverted) with a non-woven pp layer on the top (SEM cross section at 615X magnification) Photomicrograph). Figure 27A is a photograph of a portion of a single layer pp layer of film sample C of Figure 27 (SEM cross-section photomicrograph at 3,420X magnification) (note the rectangle in Figure 27). 28 and 29 are the respective phases of the film sample A (single layer PP, non-collapsed bubble, biaxial orientation method) according to still another specific film example of the present invention. Sheets (SEM surface A (upper) photomicrographs at 20,000X and 5,000X magnification). Figures 30 and 31 are separate photographs of film sample A of sheets 28 and 29 (at 20,000X and 5,000X magnifications) SEM surface B (bottom) photomicrograph). Figures 32, 33 and 34 are film or composite sample G according to another embodiment of the invention (PP monolayer, non-collapsed bubble, biaxial orientation method [ Sample A]/non-woven PP, laminated [hot + pressure]) separate photographs (micrographs of SEM surface Α (top) at 20,000 Χ, 5,000 Χ and 1, 〇〇〇Χ magnification). Figures 36 and 37 are separate photographs of Film Sample G from Figures 32 to 34. 22 201137000 (2SENt Surface B (bottom) photomicrograph at 20,000 Χ, 5,000 乂 and 1,000乂). Figures 38 and 39 Each photo of the film sample G of Figures 32 to 37 (SEM cross-section photomicrograph at 20,000X and 3,420X magnification). Figure 40 shows that the 3rd to 3rd figure has a non-woven p P at the top. Photograph of layer film G (inverted) of the layer (SEM cross-section micrograph at 615X magnification). Figure 40A is a phase of a portion of the single layer PP layer of film sample G of Figure 40. Sheet (SEM cross-section micrograph at 3,420X magnification) (note the rectangle in Figure 4). Figures 41 and 42 are film samples E (PP monolayer) according to still another film example of the present invention. Individual photographs of 'collapsed bubbles, biaxial orientation method' (SEM surface A (upper) photomicrograph at 20,000X and 5,000X magnification). Figures 43 and 44 are separate photographs of Film Sample E of Figures 41 and 42 (SEM surface B (bottom) photomicrograph at 20,000X and 5,000X magnification). Figures 45 and 46 are separate photographs of film sample E of Figures 41 to 44 (SEM cross-section micrographs at 20,000X and 5,000X magnification). 4th and 7th are respective photographs of film sample F (single layer PP 'non-collapsed bubble, biaxial orientation method) according to another film embodiment of the present invention (at 20,000X and 5,000X magnification) SEM Surface A (upper) photomicrograph) 〇 49 and 50 are separate photographs of film sample F of Figures 47 and 48 (SEM surface B (bottom) photomicrograph at 20,000X and 5,000X magnification) ). Figures 51 and 52 are still further photographs of another film embodiment of the present invention 23 film 3 of 201137000 (co-extruded PP/PE/PP three layers, collapsed bubbles, biaxial orientation method) (Sem surface A (upper) photomicrograph at 20,000X and 5,000X magnification). Figures 53 and 54 are separate photographs of Film Sample D of Figures 51 and 52 (SEM surface B (bottom) photomicrograph at 20,000X and 5, 〇〇〇χ magnification). C. Embodiment 3 DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT According to at least selected specific examples of the present invention, a microporous film is obtained by a preferably modified dry stretching method (biaxial orientation method) having substantially The ratio of the circular hole and machine direction tensile strength to the transverse direction tensile strength is in the range of 0.5 to 6.0, preferably 0.5 to 5.0, most preferably 〇5 to 4 Torr. A porous membrane, such as a microporous membrane, is a thin, flexible, polymeric sheet, foil or film having a plurality of pores therethrough. These films may be single or multi-layer, single or multi-layer, composite, laminate or the like and may be used in a wide variety of applications including, but not limited to, mass transfer films, pressure regulators, over-ruthenium films, Medical devices, separators for electrochemical storage devices, films used in fuel cells, and/or the like. At least selected specific examples of films of the present invention are made by modified versions of the dry drawing process (also known as the Syracuse method). The present dry stretching method refers to a method of producing a self-stretching, non-porous, and soil-forming material for a hole-forming system. See, Kestin' R., Synthetic Polymer Films, Social Perspectives (Second Edition, John Willy and Songs, New York, NY' (1985), pp. 29, 297), for reference The manner is incorporated herein. The dry stretching method can be distinguished from the clear method and the particle stretching method as discussed above. 24 201137000 The at least selected film embodiment of the present invention may differ from the prior dry stretch film in at least two respects: 1} substantially circular holes; and 2) machine direction tensile strength versus transverse direction tensile strength The ratio is in the range of 〇5 to 6.0, preferably 〇·5 to 5.0, and most preferably 〇5 to 4 〇. The at least selected film embodiment of the present invention may differ from the prior dry stretch film in at least five respects: 丨) substantially circular holes; 2) the ratio of machine direction tensile strength to transverse direction tensile strength at Range 〇5 to 6.0; 3) average flow pore size in the range 〇〇25 to 〇15〇μm; sentence height gas or water permeability, and JIS Gore is in the range 〇5 to 2 〇〇 seconds; and 5) The head pressure is above 14 psi. In view of the shape of the holes, the holes are preferably characterized by having a substantially circular shape. See, for example, Figures 6-8, 13-16, 19, 20, 22, 23, 28-31, 5 36 41-44, 47-50, and 51-54. This hole shape is in contrast to the previously known slit-shaped holes of the dry stretch film. See Figure U and Kay: Ting's as mentioned above. Further, the shape of the hole of the film may be characterized by a ratio of depth to length (MD) to width (TD) of the hole. In one embodiment of the present film, the depth ratio ranges from 0.75 to 1.25. This is in accordance with the county ratio of the previous dry stretch film (which is greater than 5 mm). See Table I below. Considering the ratio of the machine direction (MD) tensile strength to the transverse direction (10) tensile strength', in a specific example, the ratio is preferably 0.5 to 5_0 between 〇 5 and 6. This ratio is in contrast to the corresponding ratio of the prior art film, which is greater than that. See table j below. U.S. Patent No. M. 2,593 relates to the production of a 25 201137000 i L film by a dry stretching process which results in a film having a transverse direction resistance to machine direction tensile strength ratio of 0.12 to 1.2. Wherein the TD/MD pull ratio is obtained by at least a pull ratio of "Ha" (when the precursor is extruded). At least selected specific examples of the film may further have the following average The same size is in the range of 〇〇3 to 〇3〇μm. The porosity is in the range of 八8〇/° and/or the transverse tensile strength is greater than 250kg/平方”. The typical value of the value h and It is not intended to be limiting, and therefore should only be considered as typical of at least the specific examples selected for the 4 film. At least selected specific examples of the film may further have the following features: a pore size in the range of 〇 3 〇 to 1 〇 micrometer; and an average depth ratio in the range of about 1_0 to M0. The foregoing values are typical values and are not intended to be limiting, and therefore should be considered as typical of at least selected specific examples of the film. At least selected possible preferred embodiments of the film may further have the following features: an average water hole (called a apore) size in the range of 〇〇5 to 〇5 〇 microns; a porosity in the range of 40-90%; / or transverse tensile strength greater than 250 kg / cm ^ 2 . The foregoing values are typical values and are not intended to be limiting, and therefore should be considered only as typical of at least selected possible preferred embodiments of the film. Preferred polymers for use in the film may be characterized as a thermoplastic polymer. These polymers may further have characteristics such as semi-crystalline polymers. In one embodiment, the semi-crystalline polymer can be a polymer having a crystallinity in the range of 20% to 80%. These polymers may be selected from the group consisting of polyolefins, fluorocarbons, polyamines, polyesters, 26 201137000 polyacetals (or polyacetals), polysulfides, Polyvinyl alcohols, copolymers thereof, and combinations thereof. The polyolefins may preferably and include polyethylenes (LDPE, LLDPE, HDPE, UHMWPE), polypropylene, polybutene, polydecene, copolymers thereof, and blends thereof. The fluorocarbons may include polytetrafluoroethylene (PTFE), polygas trifluoroethylene (PCTFE), fluorinated ethylene propylene (FEP), ethylene chlorodifluoroethylene (ECTFE), ethylene tetrafluoroethylene (ETFE), poly Vinylidene fluoride (PVDF), polyvinyl fluoride (pvF), perfluoroalkoxy (pFA) resins, copolymers thereof, and blends thereof. Polyamines can include, but are not limited to, polyamidamine 6, polyamido 6/6, nylon 10/10, polydecylamine (ppA), copolymers thereof, and blends thereof. The polyesters may include polyester terephthalate (pET), polybutylene terephthalate (PBT), poly(p-capric acid 1,4_cyclohexylene dimethylene methyl ester (pCT), and liquid crystal polymer (LCP). ). Polysulfides include, but are not limited to, polyphenylene sulfide, copolymers thereof, and blends thereof. Polyvinyl alcohols include, but are not limited to, ethylene vinyl alcohol, copolymers thereof, and blends thereof. At least some specific examples of the film may include other ingredients as are well known. For example, 'those ingredients may include: fillers (inert particulate materials typically used to reduce film cost, but otherwise have no significant effect on the manufacture of the film), antistatic agents, anti-caking agents, antioxidants, lubricants ( Making it easy to manufacture), colorants and/or the like. A variety of materials can be added to the polymer to modify or enhance film properties. Such materials include, but are not limited to, (丨) polyene or polyolefin oligomers having a melting temperature below 13 〇〇c; (2) mineral fillers including, but not limited to: calcium carbonate, Zinc oxide, diatomaceous earth, talc, kaolin, synthetic cerium oxide, mica 'clay' boron nitride, cerium oxide, titanium dioxide, barium sulfate, 27 201137000 aluminum hydroxide, magnesium hydroxide, and/or the like And blends thereof; (3) elastomers, including but not limited to: ethylene-propylene (EPR), ethylene-propylene-diene (EPDM), styrene-butadiene (SBR), styrene Pentadiene (SIR), ethylene norbornene (ENB), epoxy resins and polyamino phthalates, and blends thereof; (4) wetting agents, including but not limited to ethoxylates Alcohols, primary polymeric carboxylic acids, glycols (for example, polypropylene glycol and polyethylene glycols), functionalized polyolefins, etc.; (5) lubricants, for example, polyoxyxides, fluoropolymers , Kemamide®, oleic acid amide, stearylamine, erucamide, calcium stearate or other metal stearates; (6) flame retardant For example, brominated flame retardants, ammonium phosphate, ammonium hydroxide, alumina trihydrate and phosphate esters; (7) crosslinking or coupling agents; (8) polymer processing aids such as (but not limited to) A plasticizer or processing oil (eg, less than 10% by weight processing oil); and (9) any type of nucleating agent, including a beta nucleating agent for polypropylene. (However, at least the preferred film of the present invention specifically excludes any beta nucleated polypropylene (ΒΝΡΡ), as disclosed in U.S. Patent No. 6,368,742, incorporated herein by reference. A nucleating agent is a substance that causes β crystal formation in polypropylene). The film may be a single layer or a multilayer film. In view of the multilayer film, the biaxially oriented film may be a layer of the multilayer film, or the film may be the entire layer of the multilayer film. If the film is less than all of the layers of the multilayer film, the multilayer film can be formed by coating, lamination or bonding. If the film is the entire layer of the multilayer film, the multilayer film can be produced by a lamination or extrusion method such as co-extrusion. Further, the multilayer film can be made of the same material or a different material layer. 28 201137000 The film is preferably produced by a modified dry stretching process wherein the precursor film is biaxially stretched (i.e., stretched not only in the machine direction but also in the transverse machine direction). This method will be discussed in more detail below. Generally, the method used to make the aforementioned film comprises a step of extruding a non-porous (single or multi-layer) precursor and then biaxially stretching the non-porous precursor. The non-porous precursor can be selectively annealed prior to stretching. In a specific example, the biaxial stretching includes machine direction stretching and transverse direction stretching and machine direction slack for synchronous control. The machine direction stretching and the transverse direction stretching can be synchronized or successive. In one embodiment, the machine direction stretching followed by the transverse direction stretching is accompanied by a synchronous machine direction slack. This method is discussed in more detail below. Extrusion is generally known (commonly referred to as conventional dry stretching methods). The extruder can have a slot die (for a planar precursor) or a ring die (for a parison or bubble precursor). In the latter case, an expansion type bad technique can be used (for example, when the precursor is extruded, the bl〇w叩 ratio (BUR) is less than 丨.5). However, the birefringence of the non-porous precursor is not necessarily as high as in the conventional dry stretching method. For example, in having a refining fluidity index (MFI) <i. A polypropylene resin having a porosity of /... a dry film stretching method in which the birefringence of the precursor will be > 0.0130', and along with the method, the pp The birefringence of the precursor can be as low as 〇·0100 1 In another embodiment, the poly-binder has a > 35% porosity; the birefringence of the «'(4) drive will be >qg liu; With this method, the birefringence of the 忒PE can be as low as the imitation. In one embodiment, annealing (selectivity) may be performed at a temperature of iron (the Tm of which is the melting temperature of the polymer in 29 201137000); and in another embodiment, at a temperature of KTm_5 〇 °C to Tm-15 °C. Certain materials (e.g., those having high crystallinity after extrusion, such as polybutene) may not require annealing. Additional optional steps can be performed such as, but not limited to, heat setting, extraction, removal, winding, slitting, and/or the like. The machine direction stretching can be carried out by cold stretching or hot stretching or both, and in a single step or in multiple steps. In a specific example, <Tm-50 °C for cold stretching; and in another embodiment, <Tm-80 ° C. In a specific example, <Tm_1〇〇c is subjected to hot stretching. In one embodiment, the total machine direction stretch can be in the range of 50-500%; and in another embodiment, in the range 1〇〇3〇〇%. The precursor can be shrunk in the transverse direction (conventional) during stretching in the machine direction. Lateral direction stretching includes machine direction slack for synchronous control. This means that when the precursor is stretched in the transverse direction (TD stretching), the synchronization allows the crucible to shrink (i.e., relax) in the machine direction in a controlled manner (MD relaxation). The transverse direction stretching can be carried out in a cold step, a thermal step, or a combination of the two. In one embodiment, the total transverse direction stretch can range from 100 to 1200 °/. Within; and in another specific example, within the range 2〇〇 9〇〇%. In one embodiment, the controlled machine direction slack can range from 5 to 80%; and in another embodiment, within the range of 15 65%. In one embodiment, the transverse stretching can be performed in multiple steps. The precursor may or may not be allowed to contract in the machine direction during stretching in the transverse direction. In a specific example of multi-step transverse direction stretching, the first transverse side 30 201137000 step may comprise transverse stretching and controlled machine direction slack, followed by simultaneous k-direction and machine direction stretching, followed by lateral direction slack and no Stretch or loosen in the machine direction. «Hai-e-loading can be selectively heat-set (as is well known) after stretching in the machine direction and in the transverse direction. Specific examples of the film and method of the present invention are further clarified in the following non-limiting examples. Unless otherwise described, the test values (thickness, porosity, tensile strength, and depth ratio) reported in this article are measured as follows. · Thickness ASTM D374' Uses Invic Microcaps (Emvec〇 Microgage) 210-A micrometer; porosity - ASTM D-2873; tensile strength - ASTM D-882, using Instron model 4201; and depth ratio measurement, obtained from sem micrographs. The following examples were made by conventional dry stretching techniques, except as mentioned. Example 1. The polypropylene (pp) resin was extruded using a 2 · 5 inch extruder. The squeezer has a temperature of 221 C. The polymer smelt is fed to a circular mold. The mold temperature was set at 220 ° C and the polymer melt was cooled by blowing air. The extruded precursor has a thickness of 27 microns and a birefringence of 0 0120. Then, the extruded film was annealed at 150 ° C for 2 minutes. Then, the annealed film was cold drawn at room temperature to 2%, and then at 14 Torr. The underarm heat is stretched to 228% and slack to 32%. The film stretched in the machine direction (MD) had a thickness of 16.4 microns and a porosity of 25%. Then, at 14 〇. Lateral direction of the underarm (D):)) 31 201137000 The MD stretched film was stretched by 300% and the yjD was relaxed by 50%. The finished film has a thickness of 14 to 1 micron and a porosity of 37%. The finished film had a TD tensile strength of 550 kg/cm 2 . See Figure 6. Example 2. The polypropylene (PP) resin was extruded using a 2.5 inch extruder. The extruder has a smelting temperature of 220 °C. The polymer melt is fed to a circular mold. The mold temperature was set at 200 ° C and the polymer smelt was cooled by blowing air. The extruded precursor has a thickness of 9. 5 microns and a birefringence of 〇16〇. The HDPE resin was extruded using a 2.5 inch extruder. The extruder melt temperature was 210 °C. The polymer melt is fed to a circular mold. The mold temperature was set at 2051 and the polymer melt was cooled by air. The extruded precursor has a thickness of 9.5 microns and a birefringence 〇·〇330. A two-layer pp layer and a PE layer are laminated together to form a PP/PE/PP three-layer film. The stacking roll temperature was 15 (rc. Then, the laminated three-layer film was annealed at 125 ° C for 2 minutes. Then, the annealed film was cold drawn at room temperature to 20%, and then heated at 113 ° C. Stretched to 160% and relaxed to 35%. The MD stretched film had a thickness of 25.4 microns and a porosity of 39%. Then, at 115. (: TD stretched the MD stretched film 400% and MD relaxed 30%. The finished film had a thickness of 19.4 microns and a porosity of 63%. The finished film had a TD tensile strength of 350 kg/cm 2 . See Figure 7. Example 3. Extrusion using a co-extrusion die Pp resin and 11 〇! > £ resin to form a PP/PE/PP three-layer film. PP extruder melt temperature is 243 ° C and PE extruder melt temperature is 214 t. Then, the polymer melt Feed to the co-extrusion die (which was set at 198 t). The polymer melt was cooled by blowing air. The extruded film had a thickness of 35.6 microns. Then, at 125. (: 32 201137000, annealed and extruded Precursor for 2 minutes. Then, the annealed film was cold drawn at room temperature to 45% and hot drawn to 247° at 113 X: /. Relaxed to 42 〇 /. MD stretched film has a thickness of 2 丨 5 microns and a porosity of 29 〇 / 〇. Then, the MD stretched film 450% and 50 TD stretched at 115 t The %MD is relaxed. The finished film has a thickness of 16 3 μm and a porosity of 59%. The finished film iTD has a tensile strength of 57 〇 kg/cm 2 . Example 4. Co-extruded PP resin and HDPE resin, and use MD stretching was carried out in the same manner as in Example 3. Then, the MD-stretched film was stretched by 800% and 65% MD in TD at 115 ° C. The completed film had a thickness of 17 - 2 μm and a porosity of 49 %. The finished film has a TE) tensile strength of 730 kg/cm 2 . See Figure 8. Example 5. Extrusion of pp resin and PB resin using a co-extrusion die. pp extruder melt temperature is 230 ° C And the PB extruder melt was 206 ° C. Then, the polymer melt was fed to a co-extrusion die (which was set at 21 ° C). Then the 'polymer melt was cooled by blowing air. The extruded film had a thickness of 36.0 microns. Then, the extruded precursor was annealed at 1 〇 5 ° C for 2 minutes. Then, cold The annealed film was stretched to 20%, then thermally stretched to 155% at 10 ° C, and then relaxed to 35%. Then, the MD stretched film 140 was stretched at 110 ° C in TD. % is relaxed with 20% MD. The finished film has a thickness of 14.8 μm and a porosity of 42%. The finished film has a TD tensile strength of 286 kg/cm 2 . Example 6. Extrusion of PP using a co-extrusion die Resin and PE resin to form a PP/PE/PP three-layer film. The extrusion temperature of the extruder of PP was 245 ° C and the melting temperature of the extruder of PE was 230 ° C. The polymer melt was then fed to coextrusion 33 201137000 compression die (which was set at 225 °C). The polymer melt is cooled by blowing air. The extruded film had a thickness of 27 microns and a birefringence of 0.0120. The extruded precursor was then annealed at 115 C for 2 minutes. The annealed film was then cold drawn at room temperature to 22% and at 120. (: hot stretch to 254% and relaxation to 25 ° / (total machine direction stretch = 25 %). The MD stretched film has a thickness of 15 microns and a porosity of 16%. Then, at 130T: TD stretching of the MD stretched film by 260% and 50% MD relaxation, followed by simultaneous MD and TD stretching in each direction at 130 ° C for 50% and 216%, and finally at temperature 13 (TC The film was quickly held in MD (100%) and allowed to relax 57.6 ° in TD. The finished film had a thickness of 7.6 μm and a porosity of 52%. The finished film had a Td tensile strength of 513 kg/square. C. Example 7. A co-extrusion die was used to extrude polypropylene and polyethylene resin to form a PP/PE/PP three-layer film. The extruder of pp had a melting temperature of 222»c and a melt of PE extruder. The temperature was 225 C. The polymer melt was then fed to a co-extrusion die set at 215 ° C. The polymer melt was cooled by blowing air. The extruded film had a thickness of 4 〇. Micron and birefringence of 0.0110. The extruded precursor was then annealed at 1 〇 5 ° C for 2 minutes. Then, the annealed film was cold drawn at room temperature to 36%. It was hot stretched to 264% and relaxed to 29% at 1〇9 (total machine direction stretch = 271%). The MD stretched film had a thickness of 23.8 microns and a porosity of 29.6%. Then, at 110 C The TD-stretched MD-stretched film was relaxed by 1034% and 75% MD. The finished film had a thickness of 16.8 μm and a porosity of 46%. The finished film had a TD tensile strength of 1〇37 kg/cm 2 . In the following Table I, the results of the foregoing examples were summarized and compared with the dry stretched films commercially available from the two commercially available 34 201137000: ComA) Sergeka @2400 (single layer of polypropylene film), see Figure 2 And Com B) Sergeant® 2300 (three layers of polypropylene/polyethylene/polypropylene), see Figure 3.

Table I TD Tensile Thickness (μm) Porosity TD Tensile Strength (kg/cm 2 ) MD Tensile Strength (kg/cm 2 ) MD/TD Tensile Ratio MD/TD Depth Ratio Com AN/A 25.4 37% 160 1700 10.6 6.10 Com BN/A 25.1 40% 146 1925 13.2 5.50 Example 1 300% 14.1 37% 550 1013 1.8 0.90 Example 2 400% 19.4 63% 350 627 1.8 0.71 Example 3 450% 16.3 59% 570 754 1.3 __ Implementation Example 4 800% 17.2 49% 730 646 0.9 0.83 Example 5 140% 14.8 42% 286 1080 3.8 - Example 6 418% 7.6 52% 513 1437 2.8 - Example 7 1034% 16.8 46% 1037 618 0.6 - According to the invention At least selected specific examples of the film: • For a single layer PP air filter film, a preferred JIS Glory ^2.5 to ~25. • For single layer PP HEPA/ULPA films, the preferred JIS GRAY is $0.5 to ~5 ° • a preferred round hole structure and a highly uniform hole structure throughout the film. In accordance with at least selected possible preferred embodiments of the present invention, preferred films have or are: The dry process is prepared without the addition of an oil/solvent. High porosity: 40-90%. 35 201137000 Hydrophobicity 0 Head pressure > 14 (four) / square inch, water intrusive pressure > 8_ square inch. Unique pore structure, such as by capillary flow perforation/water hole test surface: the average flow pore size is measured by a flow of at least about G.04 micron tube flow. 'Uniform circular or non-slit pattern The hole structure has a narrow range of apertures. The water hole size is at least about 微米 7 microns. Gas/air/moisture permeability: JIS Gore 1〇 to 1〇〇; high flow rate, as indicated by capillary flow perforation; WVTRd, gram/square metric-day. Balanced MD/TD intensity: TD intensity (> 300 kg/cm 2 ). Low TD shrinkage: TD shrinkage is 52% at 90 °C. Preferred PP polymer: MFI = 0.1 to 10.0, crystallinity of the polymer > 45%. Preferred PE polymers: ΜΠ = 0.01 to 5.0, crystallinity > 50%. MFI was tested by the ASTM D-1238 method. The following are the results of eight films (A-G and ruthenium), composites or laminates and comparative samples c〇m C of the specific examples selected according to the present invention: 36 201137000

Table II General Properties Sample ID Unit ComC Λ Β CD Β FG Μ Sample Description PP Single Layer Comparative Example ΡΡ Single Layer ΡΡ/ΡΡ Adhesive Two-layer ΡΡ and Non-woven Layer ΡΡ/ΡΕ/ΡΡ Co-extruded = ΡΡ/ΡΡ Bonded-layer ΡΡ Single layer ΡΡ and non-woven layer ΡΡ/ΡΕ/ΡΡ Co-extruded two-layer AVG thickness micro 25 18 20 79 21 24 14 77 22 Porosity % 55 73 65 • 76 80 81 - 60 Puncture strength gram 335 226 374 553 256 285 135 358 346 MD Tensile force per square centimeter 1055 754 938 - 500 533 507 - 862 TD pull force kg / cm ^ 2 135 493 711 - 450 491 461 * 473 MD shrinkage at 90 ° C 5.0 6.1 5.0 1.21 13.8 6.0 6.5 2.29 5.5 TD shrinkage at 90 °C 0.0 0.4 ~~αο 0.46 1.8 -0.0 ^0.0 0.19 1.5 AVGJIS Gore seconds / 100cc 200 32 60 85 35 26 14 45 65 Average flow aperture micron 0.0365 0.0543 0.0501 0.0468 0.0256 0.0610 0.0737 0.0542 0.250 Average flow rate 1 Standard deviation of pore size 0.0261 0.0183 0.0187 0.0181 0.0119 0.0190 0.0221 0.0183 0.110 Bubble point diameter micron 0.1141 0.0948 0.0892 0.0736 0.0504 0 .1078 0.1039 0.0808 0.049 Head pressure / square inch 155 149 159 277 364 222 153 206 377 Water intrusion pressure crush / square inch >80 >80 >80 >80 >80 >80 >80 ° &gt 80 > 80 WVTR g/m2 • day < 6000 293 (8) 178000 8560 29800 > 30000 > 30000 23000 16500 The WVTR test is based on ASTM F2298-03 using a moisture gradient method. The test method for water vapor diffusion and air flow resistance of fabric materials uses a dynamic moisture permeable trough. Test conditions: the upper tank humidity is 95%, the lower tank humidity is 5%, and the moisture difference rate is 9〇%. Zhou Wen. The thickness is measured according to ASTM-D374 using an Invic Microcapsule 210A micrometer. JIS Gore is a gas permeability test that is measured using a Oken permeability tester. Gore is defined as the time, in seconds, required for cc air to pass through a square inch film at a fixed pressure of 4.8 inches of water. Porosity is measured by the ASTM D2873 method. The puncture strength was measured using an Instron model 4442 according to ASTM D3763. The measurement across the width of the film and the average puncture energy (puncture strength) are defined as the force required to puncture the test sample. The tensile properties were tested using the ASTM-882 standard using the Instron Model 4201. The shrinkage was measured using a modified ASTM-2732-96 procedure at 90 °C for 60 minutes. The average flow pore size, bubble point aperture is measured by capillary flow analysis according to ASTM F3I6-86. The head pressure is measured according to ASTM D3393-91. Water intrusion is tested per ASTMF 316-93 (wetting fluid: water, 68.8 dynes/cm. gas: air). 37 201137000 Although less preferred, a filled, microporous ultrahigh molecular weight polyethylene film can be used as a precursor in the stretching process of the present invention. Similarly, for additional durability, the film of the present invention may be laminated to the nonwoven substrate on one or both sides, or it may be coated with a surfactant to render it hydrophilic. According to at least selected specific examples, the present invention can be directed to: 0 simultaneous stretching and relaxation to biaxially stretch a blown film to produce a high degree of permeability to air, moisture vapor, and other gases, but high A useful product in the application of degree of hydrophobicity. Such applications may include film-based humidity and temperature control systems such as liquid dehumidification HVAC systems; membrane desalination; discharge; fuel cell moisture control; liquid filtration; and the like. According to at least selected specific examples, the invention is directed to films having the following properties:

Table III Measurement unit performance thickness micron 10-100 JIS Gore seconds (per 100 ml) 1-100 MD tensile strength kg force / square centimeter 500-1500 TD tensile strength kg force / square centimeter 350-800 porosity percentage 60 -90% average flow pore size micron 0.04-0.07 bubble point diameter micron 0.09-0.11 water hole size micron 0.04-0.12 head pressure pounds per square inch 149-222 intrusion pressure pounds per square inch > 80 pressure drop psid (at 5_3 cm / (seconds) <3.90 percentage of particle efficiency (at 2.5 cm/sec) >99.99% melting point °C >165 38 201137000 According to a possible preferred embodiment of the invention, the film is hydrophobic and highly permeable Permeability, chemical and mechanical stability, high tensile strength film. These properties seem to make it an ideal film for the following applications, each of which (in addition to air filtration) can include selective passage of moisture vapor and blocking liquid water··

1. HVAC 2. Liquid Dehumidification (LD) Air Conditioner 3. Water-based Air Conditioning 4. Energy Recovery Ventilation (ERV) 5. Desalting 6. RO Desalting 7. Vapor Desalting 8. Fuel Cell 9. Liquid and / Or air filtration, particularly in the case of liquid and air filtration, the unique pore structure may have certain specific benefits. Preferred laminate products may have a combination of desired film moisture transport properties in combination with desired macrophysical properties, according to at least selected specific examples. 0. According to at least selected specific examples, preferred monolayer PP products may be It has excellent balance of physical properties of MD and TD, and is also a high performance film, such as moisture transport (moisture vapor transport) and head performance measurement. The film may also have a non-characteristically high porosity (> 60%), but still maintain balanced physical properties (when compared to more conventional films). Similarly, the thin 39 201137000 film can be combined with a laminated pp non-woven fabric. The resulting laminate product still retains excellent moisture vapor transmission and altered good head performance. Likewise, the resulting product can have properties that far exceed the physical strength of the comparative film. Thus, the product can have the added advantage of being used in more physically harsh environments without the loss of highly desirable film characteristics. In accordance with at least selected embodiments of the present invention, the film can have a unique pore structure and distribution or properties that appear to make it an ideal film for: High efficiency air filtration, HEPA/ULPA applications, near zero Dust removal applications (clean rooms, vacuum bags, masks, surgical suites, dust bags, ink cartridges), Filtration applications: 〇High efficiency HVAC filter media o HEPA/ULPA media 〇Filter film composite liquid filtration, Protective clothing, functional clothing/performance sports wear, medical fabrics, and the like. According to at least selected porous material, film, layer, film, laminate, co-extrusion or composite embodiment of the present invention, certain modified regions may include void shapes other than slits, circular holes, and increased lateral direction resistance. Tension 40 201137000 degrees, balanced MD and TD physical properties, high performance associated with, for example, moisture transfer (or moisture vapor transport) and head pressure, reduced Gore, high porosity with balanced physical properties, pore structure (including Consistency of pore size and pore size distribution, improved durability, composite of such films with other porous materials; composites or laminates of such films, films or layers with porous nonwovens; coated films, coextrusion Pressed film, laminated film; film with desired moisture transport, head performance and physical strength properties; no loss of useful film characteristics in a more physical and harsh environment, film moisture transfer (or moisture vapor) The combination of performance and macroscopic physical properties is 'hydrophobic, highly transparent, chemically and mechanically stable, with Tensile strength, combinations thereof, and / or similar properties. Although some of the thin chess made by the dry stretching method have achieved excellent commercial success, there is a need to improve, modify or improve at least the physical properties selected so that they can be used in a wide range of applications, The purpose is to have a good performance and / or its similar purpose. At least selected specific examples of the dry draw process film according to the present invention 'Some modified regions may include hole shapes other than slits, circular holes, increased transverse direction tensile strength, balanced MD and TD physical properties, holes Consistency of structure (including pore size and pore size distribution), high performance related to, for example, moisture transfer (moisture vapor transport) and head pressure, reduction of Gore, high porosity with balanced physical properties, improved durability, this a composite of a film and other porous materials, a composite or laminate of such films and porous nonwovens, a coated film, a coextruded film, a laminated film; having a desired moisture transport (or moisture vapor transport) Film with water head performance and physical strength properties; useful in the combination of the 201137000 _, its harsh environment without loss of the desired thin 臈 characteristics, film transfer (water vapor transmission) performance and giant physics The nature of the knot 4 combination, and / or its similar properties. The porous membrane of the present invention may preferably be a dry stretching process porous film, film, layer or composite having at least a selected, preferably preferred embodiment, which is hydrophobic, highly permeable, chemically and mechanically stable. Sex, 焉 tensile strength and its combination. These properties appear to make it an ideal film or film for the following applications. Each of them (other than air filtration) may include selective passage of moisture vapor (or other gas) and blocking of liquid water (or other liquids):

5. HVAC a. Liquid Dehumidification (LD) Air Conditioning (Temperature and Humidity Control): In a film-based LD system, temperature and humidity can be controlled by a salt solution that absorbs or releases water vapor through the porous membrane. Heat is the driving force in the system (non-pressure, as in most air conditioning systems). In order for the system to work, a hydrophobic film that is easily passed through water vapor (to block the liquid) is required. b. Water-based air conditioning (temperature and humidity control): The evaporative cooling system or cooling water system operates on a slightly different principle than the LD system' but it will use the same basic properties of the film. c•Energy Recovery Ventilation (ERV): The simplest hvac application uses this membrane as a key component in compensating for heat and exchange between the exhaust and exhaust air. 6. 5® · Friendly, Wind. Thermal oxygen desalination applications use the same film properties as HVAC. Because the 5 liter film blocks the liquid brine but passes through the water vapor, it can be constructed 42 201137000 A system for separating brine and fresh water by membrane. As the brine is at a higher temperature, fresh water vapor is evolved from the brine, which drifts through the membrane and condenses to form a fresh water stream. 7. Fuel cell: In a fuel cell, the proton exchange membrane (pEM) must be kept moist. This can be achieved with the use of a film-based humidification unit. 8. Liquid and/or air filtration: In these specific examples, the porous membrane acts as a simple filter. When liquid, vapor, gas or air passes through the film, particles that are too large to pass through the pores are blocked at the surface of the film. Particularly in the case of liquid and air filtration, the unique pore structure of at least selected embodiments of the present invention may have certain specific benefits such as durability, high efficiency, narrow pore size distribution, and consistent flow rate benefits. . According to at least the selected porous material or porous film embodiment of the present invention, at least the selected porous single-layer polypropylene (single-layer PP) film has excellent balance of MD and TD physical properties, and is also a high-performance film (such as By moisture transfer and head performance measurement). The single layer pp film selected may also have germanium porosity (> 60%), but still maintain balanced physical properties (when compared to more conventional films). Similarly, the selected single layer pp film or film can be produced by laminating or laminating a porous polypropylene (PP) nonwoven material (not pp) on one or both sides. The resulting composite 'film or product (single layer pp/non-woven PP) or (non-woven PP/single layer PP/non-woven PP) preferably retains excellent moisture transport and altered head performance. Similarly, the resulting composite 43 201137000 product (single layer PP/non-woven PP) or (non-woven PP/single layer PP/non-woven pp) can have properties far exceeding the physical strength of the comparative film. Therefore, this newly produced composite product (single layer PP/non-woven PP) or (non-woven PP/single layer pp/non-woven pp) can have the advantage of being added, which is useful in a more physical and harsh environment without Loss of the desired film characteristics. These are the single-layer pp films and composite products (single layer PP; single layer PP/non-woven PP; or non-woven pp/single layer pp/non-woven PP) in their film moisture transport properties and their macroscopic physics. The combination of properties is unique. For example, previous films may have real porosity but insufficient head pressure or performance, other films are too brittle, other films are strong but lack other properties, or the like. At the same time, at least selected specific embodiments of the invention may have, for example, desired porosity, moisture transport, head pressure, strength, and the like. At least selected porous multi-layer polypropylene (multilayer PP) films having at least selected porous multi-layer polypropylene (multilayer PP) films according to the present invention have excellent balance of MD and TD physical properties, and are also a high performance film (eg, by Moisture transfer and head performance measurement). The multilayer PP film selected may also have a high porosity (> 60%) but still maintain a balanced physical property (when compared to more conventional films). Similarly, the multilayer pp film or film selected as such can be produced by laminating or laminating one or both of the porous polypropylene (PP) nonwoven material (non-woven PP). The resulting composite, film or product (multilayer PP/non-woven PP) or (non-woven PP/multilayer PP/non-woven PP) preferably retains excellent moisture transport and altered head performance. Likewise, the resulting composite product (multilayer PP/non-woven PP) or (non-woven PP/multilayer PP/non-woven PP) can have properties far exceeding the physical strength of the comparative film. Therefore, this newly produced composite 44 201137000 product (multilayer pp/nonwoven pp) or (nonwoven pp/multilayer pp/nonwoven pp) can have the advantage of being added, which is useful in a more physical and harsh environment without Loss of the desired film characteristics. The selected multilayer PP film and composite products (multilayer PP; multi-layer PP/non-woven PP; or non-woven PP/multilayer PP/non-woven PP) combine their moisture transport properties with their macroscopic physical properties. Unique in combination. For example, previous films may have real porosity but insufficient head pressure or performance, other films are too brittle, other films are strong but lack other properties, or the like. At the same time, at least selected specific examples of the invention may have, for example, desired porosity, moisture transport, head pressure, strength, and the like. According to at least selected porous material or porous film embodiments of the present invention, at least the selected porous single layer polyethylene (single layer PE) film has excellent balance of MD and TD physical properties, and is also a high performance film (eg, By moisture transfer and head performance measurement). This selected single layer of P E film can also have high porosity (> 60%) but still maintain balanced physical properties (when compared to more conventional films). Similarly, the selected single-layer PE film or film may be coated on one or both sides with a porous polyethylene (PE) nonwoven material (non-woven PE) or a porous polypropylene (PP) nonwoven material (non-woven PP). ) Manufactured by merging or laminating. The resulting composite, film or product (single layer PE/non-woven PE) or (non-woven PE/single layer PE/non-woven PE) preferably retains excellent moisture transport and altered head performance. Likewise, the resulting composite product (single layer PE/non-woven pe) or (non-woven PE/single layer PE/non-woven PE) can have physical strength properties far exceeding that of the comparative film. Therefore, this newly produced composite product (single layer pE/non-woven PE) or (non-woven PE/single-layer PE/non-woven PE) can have the advantage of being added, which is useful in the more physical 45 201137000 harsh environment. There is no loss of the highly desirable _ characteristics. The choice of single-layer PE film and composite product (single-layer pE; single-layer pE/non-woven PE; or non-woven PE/single-layer pE/non-woven pE) in its film moisture transport performance and its macroscopic physics Combination of properties (4). For example, a cut film may have a water repellency of (four) degrees, other films that are too fragile, other films that are strong but lack other properties, or the like. At the same time, the specific examples of the at least the transition of the present invention may have, for example, the desired porosity 'moisture transfer, head pressure, strength and the like. According to at least the selected porous material or porous film embodiment of the present invention, at least the selected porous multilayer polyethylene (multilayer pE) film has excellent balance of MD and TD physical properties, and is also a high-quality film. The multilayer pE film selected by this means of moisture transport and head performance measurement can also have high porosity (> 60%), but still maintain balanced physical properties (when compared to more conventional films). Similarly, the selected multilayer PE film or film may be coated on one or both sides with a porous polyethylene (PE) nonwoven material (non-woven pE) or a porous polypropylene (PP) nonwoven material (non-woven PP). Made by combining or layering. The resulting composite, film or product (multilayer PE/non-woven pe) or (non-woven/multi-layer PE/non-woven PE) preferably retains excellent moisture transport and altered head performance. Likewise, the resulting composite product (multilayer PE/non-woven PE) or (non-woven PE/multilayer PE/non-woven PE) can have physical strength properties far exceeding that of the comparative film. Therefore, this newly produced composite product (multilayer PE/non-woven PE) or (non-woven PE/multilayer PE/non-woven PE) can have the advantage of being added, which is useful in a more physical and harsh environment without loss of height. The desired film characteristics. These selected multilayer PE films and composite products (multilayer PE; multilayer PE/ 46 201137000 non-woven PE; or non-woven PE/multilayer PE/non-woven PE) combine their moisture transport properties with their macroscopic physical properties. The combination is unique. For example, previous films may have real porosity but insufficient head pressure or performance, other films are too brittle, other films are strong but lack other properties, or the like. However, at least selected specific examples of the invention may have, for example, desirable porosity, moisture transport, head pressure, strength, and the like. At least selected porous single-layer polymer film (for example, a single layer (which may have one or more layers) of a polyolefin (PO) film, such as polypropylene (pp), according to at least selected porous material or porous film of the present invention. And / or polyethylene (PE) (including PE, pp or pE + pp blend) single-layer film) has excellent balance of md and TD physical properties, and is also a high-performance film (such as by moisture transport ( Or moisture vapor transmission) and head performance measurement). The selected monolayer p〇 film can also have a high porosity (> 60%), but still maintain a balanced physical location (when compared to more conventional films). Likewise, the selected single layer PO film or film may be on one or both sides with a porous nonwoven material (such as a non-woven polymeric material, such as a p〇 non-woven material (such as porous polyethylene (PE)). The woven material (non-woven PE) and/or the porous polypropylene (pp) nonwoven material (non-woven pp) (including PE, PP or PE+PP blend)) are produced by lamination or lamination. The resulting composite, film or product (single layer PO/non-woven PO) or (non-woven p/monolayer p〇/non-woven PO) preferably retains excellent moisture transport (or moisture vapor transport) and Change the performance of the head. Likewise, the resulting composite product (single layer PO/non-woven PO) or (non-woven PO/single layer PO/non-woven PO) can have properties far exceeding the physical strength of the comparative film. Therefore, this newly produced composite product (single layer PO/non-woven PO) or (non-woven PO/single layer PO/non-woven PO) can have the added excellent 47 201137000 points 'in a more physical and harsh environment Useful without loss of highly desirable film characteristics. These selected single-layer PO films and composite products (single layer PO; single layer p〇/non-woven PO; or non-woven PO/monolayer p〇/non-woven p〇) have their moisture transport properties in the film The combination of giant physical properties is unique in combination. For example, 'previous films may have porosity but insufficient head pressure or performance, other films are too fragile, other films are strong but lack other properties, or the like, although at least selected specific examples of the invention may have Desirable porosity, moisture transport, moisture vapor transport, head pressure, strength and similar properties. At least selected porous multilayer polymer films (eg, multilayer (two or more layers) polyolefin (PO) films, such as polypropylene (PP), and at least selected porous materials or porous films according to the present invention. / or polyethylene (PE) (including PE, PP or PE + PP blend) multilayer film) has excellent MD and TD physical properties balance, but also a high performance film (such as by moisture transport (or moisture vapor) Transfer) and head performance measurement). This selected multilayer PO film can also have high porosity (> 60%), but still maintain balanced physical properties (when compared to more conventional films). Similarly, the selected multilayer PO film or film may be on one or both sides with a porous PO nonwoven material (such as a porous polyethylene (PE) nonwoven material (non-woven PE) and/or a porous polypropylene (PP). ) Non-woven materials (non-woven PP) are manufactured by combining or laminating. The resulting composite, film or product (multilayer PO/non-woven PO) or (non-woven PO/multilayer PO/non-woven PO) preferably retains excellent moisture transport and altered good head performance. Likewise, the resulting composite product (multilayer PO/non-woven PO) or (non-woven PO/multilayer Pd/non-woven PO) can have physical strength properties far exceeding that of the comparative film. Thus, 48 201137000 This newly produced composite product (multilayer PO/non-woven PO) or (non-woven PO/multi-layer PO/non-woven PO) can have the added advantage that it is useful in more physical and harsh environments without Loss of the desired film characteristics. The combination of these selected multilayer PO films and composite products (multilayer PO; multilayer PO/non-woven PO; or non-woven PO/multilayer PO/non-woven PO) in combination with its moisture transport properties and its macroscopic physical properties Unique on the ground. For example, previous films may have porosity but insufficient head pressure or performance, other films are too fragile, other films are strong but lack other properties, or the like, although at least selected specific examples of the invention may have Desirable porosity, moisture transfer, head pressure, strength and similar properties. According to at least selected porous material or porous film embodiments of the present invention, the holes (openings) have the following hole depth ratios (according to the hole opening in the machine direction (MD) (length) and the transverse machine direction (TD) (width) Physical dimensions, by measuring, for example, one or more holes in the SEMs above or on the front surface (A side) of the selected film or composite (eg, a single layer, two or three layers of film) Several holes are preferred to confirm the average)): Typical: MD/TD depth ratio is better in the range of 0.75 to 1.50: MD/TD depth ratio is best in the range of 0.75 to 1.25: MD/TD depth ratio is in the range 0_85 to 1.25. According to at least the selected porous material or porous film embodiment of the present invention, if the MD/TD hole depth ratio is 1.0, the three-dimensional or 3D hole diameter 49 201137000 rate factor or ratio such as 0/but 0 claw 0) may be 1. 〇 to 8.0 or more; may preferably be 1.0 to 2.5; and most preferably 1.0 to 2.0 or less (according to the opening of the hole in the machine direction (MD) (length), transverse machine direction ( TD) (width) and physical dimensions in the thickness direction or section (ND) (thickness); for example, measuring one or more of the SEMs on the upper or front surface (edge) or the lower or back surface (edge) MD and TD of the hole (several holes are preferred to confirm the average), and one or more holes in the SEMs of the section, depth or height (C side) (length or width section or both) are measured ND (several holes are preferred to confirm the average) (when the same hole is difficult to measure ND, MD, and TD dimensions, the ND size can be a hole different from the MD and TD dimensions)). According to at least selected porous material or porous membrane embodiments of the present invention, the three-dimensional or 3D MD/TD/ND pore sphericity factor or ratio may range from 0.25 to 8_0 or more; it may preferably be from 5050 to 4.0. And most preferably it is preferably 1.0 to 2.0 or less. Specific examples of at least selected porous materials or porous membranes according to the present invention 'The holes (openings) have the following hole depth ratios (according to the hole opening in the machine direction (MD) (length) and the transverse machine direction (TD) (width) The physical dimensions in the measurement are based on the holes in the SEMs above or in the front (eight sides) of the selected single and triple film: in this machine direction MD (length) and transverse direction TD (width) Typical values for the range of depth ratios: The MD/TD depth ratio is in the range of 0.75 to 1.50. Specific examples of at least selected porous materials or porous membranes according to the present invention 'The holes (ports) have the following three-dimensional or 3D hole sphericity factor or 50 201137000 ratio (according to the hole opening in the machine direction (MD) (length), Transverse machine direction (TD) (width) and physical dimensions in thickness direction or cross section (ND) (thickness); for example 'measured in selected films, layers or composites (eg selected single and triple film) One or more holes in the SEMs of the top or front surface (A side), the lower or back surface side) and the section, depth or height (C side) (length or width section or both) (with a few holes) Preferably, to confirm the average) (when the same hole is difficult to measure ND, MD and TD dimensions, the ND size can be a hole different from the TD size)): For example: Typical: MD/TD depth ratio in the range of 0.75 to 1.50 The inner MD/ND size ratio is in the range 〇.5〇 to 7.50. The TD/ND size ratio is preferably in the range 〇.50 to 500. The MD/TD depth ratio is in the range of 0.75 to 1.25. ^0~0 size ratio In the range 1. 〇 to 2.5 丁 0 0 heart 0 size ratio in the range 1. 〇 to 2.5 Preferred: MD / TD ratio of depth within the range of 0.85 to 1.25 MD / ND ratio in size to within the range 1.〇 2.〇 TD / ND ratio of size to within the range 1.〇 2.〇. According to at least selected porous material or porous membrane embodiments of the present invention, the holes (openings) have the following pore sphericity factors or ratios (according to the opening of the hole in the machine direction (MD) (length), transverse machine direction (TD) ) (width) 51 201137000 and the physical dimension in the thickness direction or section (ND) (thickness) to measure above or before (A side), length and section (c side) of the selected single and triple film ) Based on the holes in the SEMs: The range of the ball diameter factor or ratio of the machine direction MD (length) and the lateral direction TD (width), and the typical value of the thickness direction ND (vertical height): MD/TD The depth ratio is in the range of 0.75 to 1.5 MD. The MD/ND size ratio is in the range 〇5 to 7.50 within the range 〇5 to 5.00. According to at least selected specific examples of the present invention, the microporous film is produced by a dry stretching process and has substantially circular pores, and the ratio of machine direction tensile strength to transverse tensile strength is in the range 〇5 It is preferably from 0.5 to 5.0 within 60%. The method of making the aforementioned microporous film comprises the steps of: extruding a polymer into a non-porous precursor, and biaxially stretching the non-porous precursor. The biaxial stretching comprises machine direction stretching and lateral direction. Stretching, the transverse direction stretching includes simultaneous machine direction slack control. According to at least selected specific examples of the present invention, the porous film is produced by a modified dry stretching process and has a substantially circular hole 'machine direction tensile strength to transverse direction tensile strength ratio in the range 〇. 5 to 6.0 'with low Gore (as compared to previous dry stretch film), with larger and more consistent average flow pore size (as compared to previous dry stretch film) 'or low Gorey and Both large and more consistent average flow pore sizes. While the film produced by the conventional dry stretching process has achieved excellent commercial success, in accordance with at least selected specific examples of the present invention, there is provided at least selected physical properties that have been modified, modified or enhanced so that it 52 201137000 We can use it in a wide range of applications, with good performance for special purposes and/or similar purposes. While at least some air cleaners have achieved commercial success, in accordance with at least selected specific examples of the present invention, there are provided improved, modified or enhanced filter media so that they can be used in a wide range of filtration or separation applications. It can have a good performance for a special purpose and / or its like. While some of these flat porous materials for filtration or separation processes have achieved commercial success, in accordance with at least selected specific examples of the present invention, there are provided improved, modified or enhanced porous materials so that they can be used over a wide range In the scope of application, it can be better for special purposes and/or its like. Although commercial materials have been commercially available for the selective passage of gases or moisture (moisture vapor) and porous liquids that block liquid water or brine (such as RO membranes sold by Dow Chemical, ePTFE membranes sold by W. Galle BHA and Further, according to at least selected specific examples of the invention, there are provided improved, modified or enhanced porous materials so that they can be used in a wide range of applications, have better performance for special purposes and/or It has a similar purpose. According to at least selected specific examples of the invention, the air cleaner comprises at least one porous membrane, such as a microporous membrane. In accordance with at least selected embodiments of the present invention, the microporous film is produced by a dry stretching process and has substantially circular voids, and the ratio of machine direction tensile strength to transverse tensile strength is in the range of 0.5 to 5.0. Inside. The method of making the aforementioned microporous film comprises the steps of: extruding a polymer into a non-porous precursor, and biaxially stretching the non-porous precursor, the biaxial stretching 53 201137000 including machine direction stretching and Stretching in the transverse direction, which includes machine direction slack for synchronous control. According to at least selected specific examples of the present invention, the porous film is produced by a t-modified dry stretching process and has substantially circular pores, and the ratio of the machine direction tensile strength to the transverse tensile strength is in the range @( ) 5 to 6 inches 'and have a low GRAY (as compared to the previous dry stretch film), with a higher and even average flow pore size (as compared to the previous dry stretch film) 'or low brother Both the larger and the more average flow pore size. The air eliminator according to the present invention may comprise at least a sheet-fingered microporous membrane, a plurality of microporous membranes' and its further comprising an end plate, a spacer or the like. As used herein, the air-passing device is used in the air I monthly air purifier. The present invention describes the invention in terms of an air cleaner filament; however, the present invention is limited to this, and it may equally include an air conditioner. As such, the film can be folded to provide a large area in a relatively small volume. In the alternative the film may have a sinusoidal pattern to provide a large transition area in a relatively small volume. Furthermore, the film may have any configuration; for example, it may have a configuration selected from the group consisting of a pointed cylindrical configuration, a folded flat configuration, and a spiral configuration. In the implementation of the manufacturing method, the construction of a small plate microporous film, 2 'the _ (four) into "or folding folding, so increase the shirt ^ P now" can be wound into a folded film The cylindrical shape and the end plate are sealed, so the air filter _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ In a particular embodiment, which may be quite suitable as a battery separator, at least selected, the possible preferred film is preferably made from one or more polyolefins, and may further be characterized by one or more of the following parameters: thickness , porosity, average pore size, puncture strength, jis mine number and shutdown temperature. The film thickness can be less than 6.0 mils (150 microns). In another specific embodiment, the thickness can range from 10 microns to 150 microns. In still another specific embodiment, the thickness can range from 10 microns to 50 microns. The porosity of the film can be from 40 to 90 ° /. between. In one embodiment, the porosity ranges from 60-90%. In still another embodiment, the porosity ranges from 65 to 800/. . The average pore size of the film can be between 〇·〇4-〇·2〇 micron. In a specific example, the average pore size ranges from 0.04 to 0.120 microns. In still another embodiment, the average pore size ranges from 0·07·0·12 microns. The puncture strength can be greater than or equal to 3 〇〇 gram-force/mil. The puncture strength was recorded using Midtech Stevens LFRA texture analysis and a needle with a diameter of 1.65 mm and a radius of 5 mm, recording data at a rate of 2 mm/sec and a maximum of 6 mm. , measured by an average of 10 measurements across the width of the final product. JIS Gore number (standardized to one mil thick) can be less than 1 sec / 1 〇〇 ec / ear thickness. In a specific example, the Gurley number ranges from 12 to 80 seconds / 100 cc / mil. According to some embodiments, the essential point (IV) of the film may be greater than or equal to: 〇 升/克. In another embodiment, IV can be greater than or equal to 5 55 55 201137000 liters / gram. In another embodiment, IV may preferably be greater than or equal to 3 〇 deciliter per gram. The IV of the film does not constitute a weighted average of the pre-extruded resin of the film because the polymer suffers from chain breakage and molecular weight during extrusion. As used herein, intrinsic viscosity refers to a measure of the ability of a polymer to increase the viscosity of a solution in solution. The intrinsic viscosity value is defined as the limit of the specific viscosity/concentration ratio at zero concentration. Therefore, it becomes necessary to find the viscosity at different concentrations and then extrapolate to zero concentration. Viscosity values vary with concentration depending on the molecular formula and solvent. In general, the intrinsic viscosity of a linear macromolecular substance is related to the weight average molecular weight or degree of polymerization. About linear macromolecules When the relationship between viscosity and molecular weight has been established, viscosity measurement provides a quick measure of molecular weight. The IV system was measured by the following: First, 0.02 g of the film was dissolved in 100 ml of decalin at 150 ° C for one hour 'then' and its intrinsic viscosity was measured at 135 ° C via an Ubbelohd viscometer. This is in accordance with ASTM D4020 (reporting RSV values herein). The shutdown temperature can be below 260 ° C (260 ° C). In one embodiment, the shutdown temperature can be below 190 °C. In still another embodiment, the shutdown temperature can be less than 140 °C. In still another embodiment, the shutdown temperature can be below 130 °C. In still another embodiment, the shutdown temperature can be below 120. . . The tantalum film of the present invention can be made from a single polymer, or a blend of polymers, or a layer of the same or different polymers, or a different layer of material that is bonded, laminated or coextruded together. The possible preferred polymers are polyolefins such as polypropylene (PP) and/or polyethylene (PE). For example, the film can be made from one or more layers of PP and/or PE. In a particular embodiment, the film is a porous pp 56 201137000 film or sheet. In another particular embodiment, the film is a porous PE film or sheet. In still another particular embodiment, the film is a three layer film made from two outer PP layers and one intermediate or central PE layer. In another particular embodiment, the film is a two-layer film made of a two-layer PP layer, a two-layer PE layer, or a layer of PP bonded to a layer of PE, laminated or co-extruded together. In still another particular embodiment, the film is a composite of a porous PP film or sheet and a porous material such as a non-woven glass or PP material. In yet another particular embodiment, the film is a porous film or sheet made from a blend of polyolefins having different molecular weights. The gas filtering medium comprises a microporous membrane, according to at least selected specific examples. As used herein, a gas filtering medium refers to a filtering medium used to remove particulate matter from a gas (e.g., air). The gas filter medium of the present invention may comprise ultra high molecular weight polyethylene and inorganic materials. The gas filter medium may further comprise processing oil (i.e., oil remaining in the medium after withdrawal). The gas filter media can further comprise thermoplastic polyolefins, conventional additives such as stabilizers and antioxidants, and analogs thereof as are well known in the art. The gas filter media can be used as a filter media for any end use application. For example, the gas filter medium can be used as a filter medium for end use applications selected from the group consisting of: removal of particulate matter from gases, air filtration applications, high temperature applications, inter-filter bag applications, Filtration of particulate matter in food and medicine, filtration of particulate matter in combustion methods, filtration of particulate matter in metals, and filtration of particulate matter in cement. Removal of particulate matter from gases includes industrial (such as HVAC, 57 201137000 HEPA and ULPA clean rooms), vacuum cleaning, respirator, cement, metal, food, pharmaceuticals, processed fluids, and combustion processes. The gas filter, the media can be used independently as a filter media; or in another case' can be joined to (e.g., laminated or bonded to) a support material (e.g., 'nonwoven or fabric). Typical lamination or bonding techniques include such conventional methods as, but not limited to, adhesives, welding (heating/ultrasonic), and the like. Further, the gas filter medium may be flat or formed in a folded or shaped shape. Larger batteries require separators that have greater dimensional stability (or high temperature melt integrity) because battery breakage can be more pronounced if a short circuit occurs because a larger amount of lithium material is included in the larger battery. Thus, according to at least some specific examples, the battery separator is from a nonwoven sheet material having high temperature melt integrity, a microporous film having low temperature shutdown characteristics, and selectively bonding the nonwoven sheet to the microporous film. And adapted to be made by an expanding adhesive when contacted by an electrolyte. The still temperature melt integrity separator may comprise a microporous film and a non-woven sheet with or without an adhesive or polymer bonded therebetween. Non-woven panels can refer to a plurality of fibers that are bound together by a variety of methods, such as thermal fusion, resin, solvent bonding, or mechanical interlocking of fibers, sometimes occurring simultaneously with extrusion. The collar plate area is a fibrous structure obtained by a method such as a dry type, a calendar or a gas ML-forming method, a spunbond method or a blister blowing method, and a hydroentanglement method. The fibers can be oriented in a direction or randomly. At the same time, no fabric typically does not include paper, and for this application, paper is included. The edge fibers can be made from thermoplastic polymers, cellulose, and/or pottery. Thermoplastics 58 201137000 Polymers include, but are not limited to, polystyrenes, polystyrenes, polyacrylics, polycondensation, polyamines, polycarbons, and gems. Imines, polyimines, polyketones, polyphenylene ethers, polyphenylene sulfides, polyliths. Cellulose includes, but is not limited to, cellulose (e.g., cotton or other naturally occurring sources), regenerated cellulose (e.g., sputum), and cellulose acetate (e.g., acetate cellulose and triacetate cellulose). Ceramics include all types of glass and oxidized, cerium oxide and zirconia compounds (e.g., aluminum silicate). Additionally, the non-woven or non-woven fibers can be coated or surface treated to improve the functionality of the non-woven fabric. For example, the coating or surface treatment can improve the adhesion of the non-woven fabric or its fibers, improve the high temperature melt integrity of the non-woven fabric, and/or improve the wetting ability of the non-woven fabric. Regarding the improvement of the high temperature melt integrity, the non-woven fabric and/or its fibers may be coated or surface treated with a ceramic material. Such ceramic materials include, but are not limited to, alumina, ceria and zirconia compounds, and combinations thereof. According to at least selected specific examples, the adhesion of the microporous membrane to the nonwoven web should maintain a desired high release rate, wherein the ionic species of the electrolyte between the anode and the cathode will have a free mobility. The mobility of ionic species is typically measured as the resistance (ER) or MacMullen number (the ratio of the resistance of the electrolyte-saturated porous medium to the resistance of an equal volume of electrolyte [see: US Patent No. 4,464,238, which is incorporated by reference. The way is incorporated into this article]). In addition, there may be a need to adhere the sheet to the film using a material that does not reduce the rate of ion mobility (or increase resistance) through the separator. 5Had adhesive may be selected from, but not limited to, polyvinylidene fluoride 59 201137000 (PVDF); polyamino phthalate; polyethylene oxide (PEG); polyacrylonitrile (PAN); Ester (PMA); poly(methyl methacrylate) (PMMA); polyacrylamide; polyvinyl acetate; polyvinylpyrrolidone; polytetraethylene glycol diacrylate; any of the foregoing copolymers and combinations thereof. One criterion for comonomer selection is the ability of the comonomer to modify the surface energy of the homopolymer. The surface energy affects at least: the solubility of the copolymer, thus affecting the application of the copolymer to the film; the adhesion of the copolymer to the film, thus affecting the cell manufacturing and subsequent performance; and the ability of the coating to wet, thus affecting the liquid electrolyte Absorbed into the separator. Suitable co-monomers include, but are not limited to, hexafluoropropylene, octafluoro-1-butene, octafluoroisobutylene, and tetrafluoroethylene. The comonomer component preferably ranges from 3 to 20% by weight and most preferably from 7 to 15%. Preferably, the adhesive or swellable polymer is a copolymer of polyvinylidene fluoride. More preferably, the PVDF copolymer is a copolymer of polyvinylidene fluoride and hexafluoropropylene (PVDF: HFP), and most preferably the PVDF: HFP ratio is 91:9. The PVDF copolymer is available from the love of Philadelphia in the United States and Elf Atochem; in Brussels, Solvay SA; and Ibaraki in Ibaraki Kureha Chemical Industries, LTD. is commercially available. The preferred PVDF: HFP copolymer is from KYNAR 2800 from Atoin Chemicals. The wetting agent may be selected from materials that are compatible (ie, miscible or non-separable) with the swellable polymer (such as wetting agents including sulfones, sulfates, and nitrogen), A trace amount (for example, 10-20% of the swellable polymer) will not have a detrimental effect in battery chemistry, and it is a fluid at room temperature or 60 201137000 with Tg (glass transition temperature) <50 ° C. The wetting agent can be selected from, but is not limited to, phthalate-based esters, cyclic carbonates, polymeric carbonates, and mixtures thereof. The phthalate-based ester is selected from, but is not limited to, dibutyl phthalate (DBP). The cyclic carbonate is selected from the group consisting of ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), and mixtures thereof. The polymerized carbonate is selected from the group consisting of, but not limited to, polyvinyl carbonate and linear propylene carbonate. At least selected embodiments of the present invention can provide a microporous battery separator having two bonded portions. Each portion may be composed of a coextruded or non-coextruded layer and may be made of the same or different materials. In order to achieve greater puncture strength, some specific examples may bond the two portions together, which are screened to have the desired total separator thickness when combined. Preferably, the selected specific example can be made by a collapsed bubble technique; that is, a blown film technique in which a single smelting polymer (or blend of polymers) is extruded through an annular die from a mold. The bubble emitted therein has a first portion and a second portion (each portion roughly representing half of the circumference of the bubble), and then the bubble collapses onto itself and before the micropore is formed (preferably by annealing and stretching) Bonding. When bubbles are released from the mold, they are oriented substantially in the machine direction. Thus, when the bubble collapses onto itself and is bonded, the first portion and the second portion can be oriented in substantially the same direction (with an angular deviation of less than 15 在 between the oriented portions). In the same step, collapse and adhesion are carried out by allowing the molten (or nearly molten) polymer of the bubbles to join together. By collapsing the bubble onto itself and bonding it, an increased puncture strength is obtained at a thickness comparable to the other baffles. The first portion and the second portion 61 201137000 (which provides a precursor for micropore formation methods (eg, annealing and stretching operations) when bonded) may be made of the following materials, such as polyolefins, preferably polyethylene. Or polypropylene, copolymers thereof and mixtures thereof, and most preferably polyethylene and polypropylene. A three-layer, shutdown battery separator can be referred to as a porous membrane for use in an electrochemical cell (e.g., a battery, particularly a secondary (or rechargeable) battery, such as a lithium battery). The three-layer separator may have a polypropylene-polyethylene-polypropylene structure. The separator can have a thickness of less than 3 mils (about 75 microns). The separator preferably has a thickness in the range of from 0.5 mils (about 12 microns) to 1.5 mils (about 38 microns). The separator is preferably about 1 mil (about 25 microns) thick. Preferably, the separator is permeable (as measured by JIS Gorey) for less than 300 seconds. Preferably, the separator has a puncture strength of at least 300 grams. The separator has a porosity in the range of 40% to 70°/. The inside is better. One of the methods for producing the three-layer, shutdown battery separator generally comprises the steps of: extruding a non-porous polypropylene precursor; extruding a non-porous polyethylene precursor; forming a non-porous three-layer precursor, wherein the polymerization An ethylene precursor is sandwiched between the polypropylene precursors; the three-layer precursor is bonded; the three-layer precursor is annealed; and the bonded and annealed non-porous three-layer precursor is stretched to form the porous battery separator . In at least one embodiment, the film can be a microporous sheet made from a blend of at least two ultrahigh molecular weight polyolefins having different molecular weights. In one embodiment, these ultrahigh molecular weight polyolefins may be ultra high molecular weight polyethylene (UHMWPE). In another embodiment, the film is a blend of a first ultrahigh molecular weight polyethylene having a first molecular weight and a second ultrahigh molecular weight polyethylene having a second molecular weight of 62 201137000, the first molecular weight and the The second molecular weights are all greater than 1 million and are different from each other. In another embodiment, the film is a first ultrahigh molecular weight polyethylene having a first molecular weight and a second ultrahigh molecular weight polyethylene having a second molecular weight (the first molecular weight and the second molecular weight are both greater than 1 million) And different from each other) with a blend of a third polyolefin having a third molecular weight (the third molecular weight is less than 1 million). In still another embodiment, the film can have an IV greater than or equal to 6.3 deciliters per gram. In another embodiment, the film can have an IV greater than or equal to 7.7 deciliters per gram. In at least selected specific examples, the present invention relates to biaxially oriented porous membranes, composites comprising biaxially oriented porous membranes, biaxially oriented microporous membranes, biaxially oriented macroporous membranes, battery separators, filter media, Humidity control media, flat membranes, liquid retention media and the like, related methods, methods of manufacture, methods of use, and the like. According to at least selected specific examples, the laminate material or fabric can be incorporated into a composite film made in accordance with the present invention that is wind and liquid resistant, moisture vapor permeable, and air permeable. The laminate fabric may also comprise one or more layers of textile substrate or face cloth material which are laminated to the film by any suitable means. The face cloth can be made from any suitable material that satisfies the performance and other criteria established for the application provided. "Moisture Vapor Penetration" is used to describe an article that permits water vapor to pass through the article, such as a laminated fabric or composite film. The term "anti-liquid permeable" is used to describe an article that is not "wet" or "wet" by a challenge liquid, such as water, and that prevents liquid from passing through the film under relatively low pressure ambient conditions. The term "resistance 63 201137000 broadcasts air permeability is described throughout an object 〇 5, under the pressure difference of water, the object prevents air permeability greater than about three (3) per square sigh (: TM ability. Illustratively, the inflamed crepe, outer jacket or its crepe or the resulting product incorporated into the laminated fabric may permit moisture vapor to penetrate through the garment. The waterjet hot air may be generated from the user's sweat, and the garment or finished The product permits better penetration of moisture vapor at the user's foot rate, so that (4) thieves (4) and comfort under typical conditions. The laminated fabric is also resistant to liquid and wind penetration, while air Permeable according to at least selected embodiments of the present invention, the air cleaner cartridge comprises at least one folded microporous membrane. At least the selected microporous membrane is produced by a dry stretching process and has substantial The upper circular system and the ratio of the tensile strength of the machine to the transverse tensile strength are in the range of 0.5 to 6. The method of manufacturing the aforementioned microporous film may include the following steps: extruding the polymer into a non-porous shape. I. performance drive, and double shaft pull Before the secret (4), the double recording includes stretching in the direction of the filament and stretching in the transverse direction. The transverse direction comprises synchronously controlled machine direction relaxation. At least selected specific examples of the invention may be directed to a biaxially oriented porous membrane, a composite comprising a biaxially oriented porous membrane, a bisecretic microporous membrane, a biaxially oriented macroporous membrane, a battery separator, a material, a humidity control medium, a flat membrane, a liquid retention medium and the like, related methods, Manufacturing method, method of use, and the like. According to at least selected specific examples of the invention, there is provided at least one of the following: a film comprising: 64 201137000 at least one layer of porous polymerization produced by a dry stretching process The film comprises the steps of: extruding a polymer into at least a single layer of non-porous precursor, and biaxially stretching the non-porous precursor, the biaxial stretching comprising machine direction stretching and transverse direction Stretching, the transverse direction stretching comprises synchronously controlled machine direction relaxation; and having substantially circular holes, porosity of about 40% to 90%; machine direction tensile strength pair The ratio of the direction tensile strength is in the range of about 0.5 to 5.0, the Gurley is less than about 100, the average flow pore size is at least about 0.04 microns, the water pore size is at least about 0.07 microns, and the head pressure is greater than about 140 psi. Wherein the machine direction stretching of the biaxial stretching comprises the steps of stretching in the transverse direction and stretching in the synchronous machine direction, and wherein the biaxial stretching further comprises the step of relaxing in the transverse direction. The film, wherein the nonporous precursor The biaxial stretching further includes an additional machine direction stretching step. The above film, wherein the dry stretching method further comprises the following steps: machine direction stretching to form a porous intermediate before the biaxial stretching. The biaxial stretching of the non-porous precursor includes machine direction stretching, additional transverse direction stretching and simultaneous machine direction stretching, and lateral direction relaxation. The above film, wherein the dry stretching method comprises the steps of: machine direction stretching followed by biaxial stretching of the transverse direction stretching and synchronously controlled machine direction relaxation, second transverse direction stretching and simultaneous machine direction stretching, Then the lateral direction is relaxed. 65 201137000 The film, the porous polymer film further having a thickness of at least about 8 microns, a transverse tensile strength of at least about 300 kilograms per square centimeter, a standard deviation of the average flow pore size of less than about 0.025, and a water intrusion pressure of at least about 8 inches. / square inch and WVTR at least about 8,000 grams / square meter - day. The above film ' the porous polymer film further has a transverse direction shrinkage of less than about 1.0% at 90 °C. The above film ' the porous polymer film further has a transverse direction shrinkage of less than about 1.5% at 105 °C. In the above film, the porous polymer film further has a transverse direction shrinkage of less than about 3.0 Å/Torr at 120 °C. In the above film, the porous polymer film further has a machine direction shrinkage of less than about 10% at 90 °C. In the above film, the porous polymer film further has a machine direction shrinkage of less than about 20% at 105 °C. In the above film, the porous polymer film further has a machine direction shrinkage of less than about 30% at 120 °C. In the above film, the porous polymer film further has a thickness in the range of about 8 μm to 80 μm. The above film, wherein the non-porous precursor is one of a blown film and a slit film. The above film, wherein the non-porous precursor is a single layer precursor formed by at least one of a single layer extrusion and a multi-layer extrusion. The upper film·the film wherein the non-porous precursor is a multilayer precursor formed by at least one of co-extrusion and lamination. The above/specific film, wherein the porous polymer film comprises one of polypropylene, polyethylene, 66 201137000, a blend thereof, and a combination thereof. The above film, wherein the porous polymer film uses a polyolefin resin having a melt flow index (MFI) of about 0.01 to 1.0% and a polymer crystallinity of at least about 45%. The above film, wherein the precursor is one of a single layer precursor and a multilayer precursor. The above film, wherein the film further comprises at least one non-woven, woven or braided layer bonded to at least one side of the porous polymer film. The above film, wherein the film is composed of a plurality of layers of the porous polymer film. The above film, wherein the porous polymer film is composed of at least two layers. The above film, wherein the film has substantially circular pores, a porosity of about 40% to 90%, a ratio of machine direction tensile strength to transverse direction tensile strength in a range of about 0.5 to 5.0, and a Gurley of less than about 100, an average The flow aperture is at least about 0.04 microns, the water hole size is at least about 0.07 microns, and the head pressure is greater than about 140 psi. The above film, wherein the polymer is a semi-crystalline polymer. The above film, wherein the polymer is selected from the group consisting of polyolefins, fluorocarbons, polyamines, polyesters, polyacetals (or polyoxymethylenes), polysulfides, Polyphenylene sulfide, polyvinyl alcohols, copolymers thereof, blends thereof, and combinations thereof. In the above film, the porous polymer film further has a porosity of about 65% to 90%, and the ratio of the machine direction tensile strength to the transverse direction tensile strength is in the range of about 1.0 to 5_0, the Gurley is less than about 20, and the average flow pore diameter is at least about 0.05 microns, water hole size at least about 0.08 microns and head pressure greater than about 145 pounds / 67 201137000 square inches. The above film, wherein the substantially circular hole has a depth ratio in a range of about 0.75 to 1.25 and a ball diameter factor in a range of at least about 0.25 to 8.0. At least one of a filtration membrane, a humidity control membrane, a gas and/or liquid separation membrane, a membrane selectively permeable to moisture and liquid water, and a multilayer film structure comprising the above membrane. The above film, wherein the biaxial stretching step of the dry stretching method comprises simultaneous biaxial stretching of a plurality of layer separated, stacked nonporous precursor layers, wherein the layers are not bonded together during the stretching process. The above film, wherein the biaxial stretching step of the dry stretching method comprises simultaneous biaxial stretching of at least three layers of the separated, stacked nonporous precursor layer. The above film, wherein the biaxial stretching step of the dry stretching method comprises simultaneous biaxial stretching of at least eight layers of the separated, stacked nonporous precursor layer. The above film, wherein the biaxial stretching step of the dry stretching method comprises simultaneous biaxial stretching of at least sixteen layers of the separated, stacked nonporous precursor layer. The above film, wherein the biaxial stretching step of the dry stretching method comprises synchronously biaxially stretching a plurality of layers of a bonded, stacked nonporous precursor layer, wherein all of the layers are bonded together during the stretching process. The above film, wherein the biaxial stretching step of the dry stretching method comprises simultaneous biaxial stretching of a plurality of layers, a stacked nonporous precursor layer, and a plurality of layers of a bonded, stacked nonporous precursor layer , wherein some of the layers are bonded together during the stretching process. The above film, wherein the pressing step is a dry extrusion method using 68 201137000 an extruder having at least one of a slit die and an annular die. A battery separator comprising: at least one porous polymer film produced by a dry stretching process, the method comprising the steps of: extruding a polymer into at least one single layer nonporous precursor, and biaxial Stretching the non-porous precursor, the biaxial stretching comprising machine direction stretching and transverse direction stretching, the transverse direction stretching comprising synchronously controlled machine direction relaxation; and having substantially circular holes, having a porosity of about 40 From % to 70%, the ratio of machine direction tensile strength to transverse direction tensile strength is in the range of about 0.5 to 5.0, Gore is less than about 300, average flow pore size is at least about 0.01 microns, and water pore size is at least about 0.04 microns. The battery separator, wherein the at least one porous polymer film further has a thickness of at least about 8 microns, a transverse tensile strength of at least about 300 kilograms per square centimeter, and a standard deviation of the average flow pore size of less than about 0.025. The above battery separator, wherein the at least one porous polymer film further has a transverse direction shrinkage of less than about 2% at 90 °C. The above battery wherein the at least one layer of the porous polymer film further has a machine direction shrinkage of less than about 6% at 90 °C. The above battery separator, wherein the non-porous precursor is formed by at least one of a single layer extrusion and a multilayer extrusion. The above battery separator, wherein the non-porous precursor is a multilayer precursor formed by at least one of co-extrusion and lamination. The above battery separator, wherein the separator is composed of a plurality of layers of the porous polymer film 69 201137000. The above battery separator, wherein the polymer is selected from the group consisting of: a polyhydrocarbon, a carbon a compound, a polyamine, a polys, a polyacetal (or a polyoxymethylene), Polysulfides, polyphenylene sulfides, polyvinyl alcohols, copolymers thereof, combinations thereof, and combinations thereof. The above battery separator, wherein the substantially circular hole has at least one of a depth ratio in a range of about 0.75 to 1.25 and a ball diameter factor in a range of about 25 to 8 Torr. A porous membrane comprising: at least one porous polymer membrane produced by a dry stretching process, the method comprising the steps of: extruding a polymer into at least one monolayer nonporous precursor, and biaxially pulling Extending the non-porous precursor, the biaxial stretching comprises machine direction stretching and transverse direction stretching, the transverse direction stretching comprising synchronously controlled machine direction relaxation; and having substantially circular holes having a porosity of at least about 40 %, the ratio of the machine direction tensile strength to the transverse direction tensile strength is in the range of about 至5 to 5 ' 'Gore is less than about 300' and the average flow pore size is at least about 〇.〇1 μm and the water hole size is at least about 0.04 μm. At least one of a battery separator, a filter film, a humidity control film, a gas and/or liquid separation film, a film selectively passing moisture and blocking liquid water, and a multilayer film structure, which comprises the above film. In a device requiring humidity control, the improvement includes the above film. In the filtration device, the improvement includes the above film. 201137000 In a temperature influencing device, the improvement includes the above film. A method of making a microporous film comprising the steps of: extruding a polymer into a non-porous precursor, and biaxially stretching the non-porous precursor, the biaxial stretching comprising machine direction stretching and lateral direction Directional stretching, which includes synchronously controlled machine direction slack. The above method wherein the polymer excludes any pore forming material for subsequent removal of any oil to form pores or to promote pore formation. The above method, wherein the polymer is a semi-crystalline polymer. The above method, wherein the polymer is selected from the group consisting of polyolefins, fluorocarbons, polyamines, polyesters, polyacetals (or polyacetals), polysulfides , polyvinyl alcohols, copolymers thereof, and combinations thereof. The above method further comprises the steps of: annealing the non-porous precursor after extrusion and prior to biaxial stretching. The above method, wherein the annealing is carried out in a temperature range of Tm - 80 ° C to Tm - 10 ° C. The above method, wherein the biaxial stretching comprises the steps of: stretching in the machine direction, and then stretching in the transverse direction, including simultaneous machine direction relaxation. The above method wherein heat or cold or both are stretched in the machine direction. The above method, wherein the temperature <Tm-50 ° C for cold machine direction drawing. The above method, wherein the temperature <Tm-10 ° C in the direction of the hot machine pull 71 201137000 stretch. The above method wherein the total machine direction stretch is in the range of 50-500%. The above method, wherein the total transverse direction stretching is in the range of from 100 to 1200%. The above method wherein the machine direction relaxation is within the range of 5-80%. A film comprising: a microporous polymer film produced by a dry stretching process and having substantially circular pores, and the ratio of machine direction tensile strength to transverse direction tensile strength is in the range of 0.5 to 6.0 . The above film, wherein the microporous polymer film has an average pore size in the range of 0.03 to 0.30 μm. The above film, wherein the microporous polymer film has a porosity in the range of 20 to 80%. The above film, wherein the substantially circular hole has a depth ratio in a range of about 0.75 to 1.25 and a ball diameter factor in a range of at least about 0.25 to 8.0. The above film, wherein the transverse tensile strength is > 250 kg/cm 2 . A battery separator comprising the above film. A multilayer film structure comprising the above film. An air filter, a cleaner comprising the above film. In the method of filtering out particulate matter from a gas, the improvement includes the above film. 72 201137000 A gas filtering medium comprising the above film. A battery separator comprising a nonwoven sheet having high temperature melt integrity and the above film. A battery made of the above separator. In the porous film, the improvement includes at least one of the following: a hole shape other than the slit, a circular hole, a hole as shown in one of Figures 6-8 and 13-54, as in the 13th- The pores shown in one of the figures 50, such as those shown in one of Figures 6-8 and 13-50, the properties shown in one of Tables I, II or III, increase Transverse tensile strength in the transverse direction, balanced MD and TD physical properties, high performance associated with moisture transport and head pressure, reduced Gore, high porosity with balanced physical properties, and pore structure (including pore size and pore size distribution) Consistency, improved durability, composites of such films with other porous materials; composites or laminates of such films, films or layers with porous nonwovens; coated films, coextruded films, laminated films Film with desired moisture transport or moisture vapor transport, head performance and physical strength properties; no loss of useful film characteristics in a more physical and harsh environment, film moisture transport performance and macroscopic properties The nature of the binding composition, is hydrophobic, highly permeability, chemical and mechanical stability, tensile strength, and combinations thereof having south. At least the selected microporous film is produced by a dry stretching process and has substantially circular pores, and the ratio of machine direction tensile strength to transverse direction tensile strength is in the range of 0.5 to 6.0. The method of making the aforementioned microporous film may comprise the steps of: extruding a polymer into a non-porous precursor, and biaxially stretching the non-porous precursor, the biaxial stretching comprising machine direction stretching and Transverse 73 201137000 Stretched in the direction, which includes the machine direction slack for synchronous control. At least selected specific examples of the invention may be directed to biaxially oriented porous membranes, composites comprising biaxially oriented porous membranes, biaxially oriented microporous membranes, biaxially oriented macroporous membranes, battery separators, filter media, humidity control Media, flat membranes, liquid retention media and the like, related methods, methods of manufacture, methods of use, and the like. The present invention may be embodied in other specific forms without departing from the spirit and scope of the invention. Furthermore, all numerical ranges set forth herein are to be construed as a &quot BRIEF DESCRIPTION OF THE DRAWINGS 3 Fig. 1 is a photograph of a single layer of silgaide® (SEM surface micrograph), which is a conventional dry stretch type polypropylene battery separator. Fig. 2 is a photograph of a dry stretch type film (single layer film) of the prior art. Fig. 3 is a photograph of a dry stretch type film (multilayer film, several layers laminated and then stretched) of the prior art. Figure 4 is a photograph of a single layer of siggaide® (SEM surface photomicrograph), which is a wet process type polyethylene battery separator. Fig. 5A is a photograph of a particle-stretched film (SEM surface photomicrograph). Figure 5B is a photograph of a particle-stretched film (SEM cross-section photomicrograph). Fig. 6 is a photograph (SEM surface micrograph) of a film (single layer film, biaxial orientation method) according to an embodiment of the present invention. 74 201137000 Fig. 7 is a photograph (SEM surface micrograph) of a film (multilayer film '-layered layer and then stretched 'biaxial orientation method) according to the present invention. Fig. 8 is a photograph (read surface micrograph) of a film (multilayer film, several layers of co-extrusion and then stretching, biaxial orientation method) according to still another specific example of the present invention. Fig. 9 is a schematic representation of a typical TD stretching method according to at least one specific example of the method for producing a biaxially oriented film of the present invention. Figure 10 is a photograph of a conventional Sergeant @2500 film (pp single layer, dry stretching method) at 20,000X magnification (SEM surface micrograph). Figure 11 is a photograph of the film of Figure 10 at 5,000x magnification (SEM surface photomicrograph). Figure 12 is a photograph of the film of Figures 10 and 11 at 2〇, 〇〇〇χ magnification (SEM cross-section photomicrograph). Figures 13 and 14 are respective photographs of a film sample ΡΡ (ΡΡ single layer, collapsed bubble, biaxial orientation method) according to another film embodiment of the present invention (SEM surface Α at 20,000 Χ and 5,000 Χ magnification) (upper) photomicrograph). Figures 15 and 16 are separate photographs of film sample B of Figures 13 and 14 (SEM surface B (bottom) photomicrograph at 20,000X and 5,000X magnification). Figures 17 and 18 are photographs of film samples B of Figures 13 through 16 (SEM cross-section micrographs at 20, OOOX and 5,000X magnification). Figures 19, 20 and 21 are still further photographs of another film or composite according to the present invention (PP single layer [sample non-woven PP, laminated [hot + pressure]) film sample C (in 2〇) , 〇〇〇χ, 5, 〇〇〇X and 1, under the magnification of 75 201137000 SEM surface A (upper) photomicrograph). Figures 22, 23 and 24 are separate photographs of film sample C of Figures 19 to 21 (SEM surface B (bottom) photomicrographs at 2 〇, OOOX, 5, 〇〇〇χ and 1,000 χ magnification ). Figures 25 and 26 are separate photographs of film sample C of Figures 19 through 24 (SEM cross-section micrographs at 20,000X and 5,000X magnification). Figure 27 is a photograph of a film sample C (inverted) having a non-woven PP layer on the upper side of Figs. 19 to 26 (SEM cross-sectional micrograph at 615X magnification). Fig. 27A is a photograph of a portion of the single layer PP layer of the film sample C of Fig. 27 (SEM cross section photomicrograph at 3,420X magnification) (note the rectangle in Fig. 27). Figures 28 and 29 are separate photographs of Film Sample A (single layer PP 'non-collapsed bubble, biaxial orientation method) according to another film embodiment of the present invention (SEM at 20,000X and 5,000X magnification) Surface A (upper) photomicrograph). Figures 30 and 31 are individual photographs of Film Sample A of Figures 28 and 29 (SEM surface B (bottom) photomicrograph at 20,000X and 5,000X magnification). Figures 32, 33 and 34 are film or composite samples G according to another embodiment of the present invention (PP single layer, non-collapsed bubbles, biaxial orientation method [Sample A] / non-woven PP 'layer [hot + Individual photographs of pressure]) (micrographs of SEM surface Α (top) at 2 〇, 〇〇〇χ, 5,000 Χ and Ι, ΟΟΟΧ magnification). Figures 35, 36 and 37 are separate photographs of film samples G of Figures 32 to 34 (SEM surface B (bottom) photomicrographs at 2〇, OOOX, 5,000X and ΐ, 〇〇〇χ magnification) . 76 201137000 Figures 38 and 39 are separate photographs of film samples G of Figures 32 to 37 (SEM cross-section micrographs at 20,000X and 3,420X magnification). Figure 40 is a photograph of a film sample G (inverted) having a non-woven pp layer on the upper side of Figs. 32 to 39 (SEM cross-sectional micrograph at 615X magnification). Fig. 40A is a photograph of a portion of the single layer PP layer of the film sample g of Fig. 40 (SEM cross section photomicrograph at 3,420X magnification) (note the rectangle in Fig. 4). 41 and 42 are respective photographs of film sample E (PP monolayer, collapsed bubble, biaxial orientation method) according to still another film example of the present invention (SEM surface at 20,000X and 5,000X magnification) A (upper) photomicrograph). Figures 43 and 44 are separate photographs of film samples e of Figures 41 and 42 (SEM surface B (bottom) photomicrographs at 20,000X and 5,000X magnification). Figures 45 and 46 are separate photographs of film sample E of Figures 41 to 44 (SEM cross-section micrographs at 20,000X and 5,000X magnification). 4th and 7th are respective photographs of film sample F (single layer PP, non-collapsed bubble, biaxial orientation method) according to another film embodiment of the present invention (at 20,000X and 5,000X magnification) SEM Surface A (upper) photomicrograph) 〇 49 and 50 are separate photographs of film sample F of Figures 47 and 48 (SEM surface B (bottom) photomicrograph at 20,000X and 5,000X magnification) ). Figures 51 and 52 are separate photographs of film sample D (co-extruded PP/PE/PP three layers, collapsed bubbles, biaxial orientation method) according to still another film embodiment of the present invention (at 20,000) SEM table 77 at X and 5,000X magnification 201137000 Face A (upper) photomicrograph). Figures 53 and 54 are separate photographs of film sample D of Figures 51 and 52 (SEM surface B (bottom) photomicrograph at 20,000X and 5,000X magnification). [Main component symbol description] (none) 78

Claims (1)

201137000 VII. Patent Application Range: 1. A porous film comprising: at least one porous polymer film produced by a dry stretching method, the method comprising the steps of: extruding a polymer into at least one single layer; a porous precursor, and biaxially stretching the nonporous precursor, the biaxial stretching comprising machine direction stretching and transverse direction stretching> the transverse direction stretching comprising simultaneous controlled machine direction relaxation; a substantially circular hole having a porosity of about 40% to 90%, a ratio of machine direction tensile strength to transverse direction tensile strength in the range of about 0.5 to 5.0, Gurley less than about 100, and an average flow pore size of at least about 0.04 microns, the water hole size is at least about 0.07 microns and the head pressure is greater than about 140 psi. 2. The film of claim 1, wherein the machine direction stretching of the biaxial stretching comprises a step of transverse direction stretching and simultaneous machine direction stretching, and wherein the biaxial stretching further comprises lateral direction relaxation. step. 3. The film of claim 2, wherein the biaxial stretching of the non-porous precursor further comprises an additional machine direction stretching step. 4. The film of claim 1, wherein the dry stretching method further comprises the step of: stretching in a machine direction to form a porous intermediate prior to the biaxial stretching. 5. The film of claim 1 wherein the non-porous precursor 79 201137000 biaxial stretching comprises machine direction stretching, additional transverse direction stretching and synchronous machine direction stretching, and lateral direction relaxation. 6. The method of claim 1, wherein the dry stretching method comprises the following steps: stretching in a machine direction, followed by performing a biaxial stretching of the machine direction including the transversely controlled stretching in the transverse direction, Two transverse direction stretching and simultaneous machine direction stretching, followed by lateral direction relaxation. 7. The porous polymer film further having a thickness of at least about 8 microns, a transverse tensile strength of at least about 3 kilograms per square centimeter per square centimeter, and a standard deviation of the average flow pore size of less than about 0.025, water intrusion pressure of at least about 8 psi/w and wvtr of at least about 8,000 gram per square meter-day. 8. The film of claim 1, wherein the porous polymer film further has a transverse direction shrinkage of less than about 1. 〇〇/〇 at 90 °C. 9. The film of claim 1, wherein the porous polymer film further has a transverse direction contraction of 1〇5. (: less than about 1.5%. 10. The film of the first aspect of the patent application, the porous polymer film further has a transverse direction shrinkage of 120. (: less than about 3.0%. 11) The film of the first aspect, the porous polymer film further having a thickness in the range of about 8 micrometers to 80 micrometers. 12. The film according to claim 2, wherein the non-porous precursor is a blown film and a slit film. 13. The film of claim 3, wherein the non-porous precursor is a single layer 80 201137000 precursor formed by at least one of a single layer extrusion and a multilayer extrusion. For example, please refer to the film of the first patent range, wherein the non-porous precursor is a multilayer precursor formed by at least co-extruding and laminating. The porous polymer comprises polypropylene, polyethylene, blends thereof, and combinations thereof. 16) The film of the patent application, wherein the precursor is a single layer precursor and one of the multilayer precursors. 17. Film as claimed in item 1 of the patent application Wherein the film further comprises at least one non-woven, woven or woven layer bonded to the at least one side of the porous polymer film. 18. The film of claim 4, wherein the film has substantially circular holes The porosity is about 40% to 90%, the ratio of the tensile strength in the machine direction to the tensile strength in the transverse direction is in the range of about 至5 to 5 ,, the ^ is less than about 100, and the average flow pore diameter is at least about 4 μm. The water pore size is at least about 〇·〇 7 μm and the head pressure is greater than about 14 〇 psi. 19. The film according to the patent application, wherein the polymer is selected from the group consisting of: Hydrocarbons, fluorocarbons, polyamines, polystyrenes, poly-reduced (or poly-methyl), polysulfides, polyphenylene sulfides, polyethylenes, copolymers thereof, And a group thereof, wherein the porous polymer film further has a porosity of about 65% to 90%, and a ratio of _ direction resistance (four degrees) to transverse direction tensile strength is The range is about L〇 to 5 〇, Gore is less than about 2〇, and the average flow aperture is at least about 0.0. 5 microns, having a water hole size of at least about (10) microns and a head pressure of greater than about 145 psi. The film of claim 1 wherein the substantially circular aperture has a depth ratio in the range of about 0.75 to 1.25. The inner and ball diameter factor is at least one of a range of about 0.25 to 8.0. 22. at least one filter film, a humidity control film, a gas and/or liquid separation film, a film that selectively passes moisture and blocks liquid water, and A multilayer film structure comprising the film of the first aspect of the invention. The film of claim 1, wherein the biaxial stretching step of the dry stretching method comprises simultaneous biaxial stretching, plural separation, stacking A non-porous precursor layer disposed, wherein the layers are not bonded together during the stretching process. 24. The film of claim 1, wherein the biaxial stretching step of the dry stretching method comprises simultaneous biaxial stretching of a plurality of bonded, superposed non-porous precursor layers, wherein all layers are stretched Bonded together during the process. 25. A battery separator comprising: at least one porous polymer film produced by a dry stretching process comprising the steps of: extruding a polymer into at least one single layer nonporous precursor, and Biaxially stretching the non-porous precursor, the biaxial stretching comprising machine direction stretching and transverse direction stretching, the transverse direction stretching comprising simultaneous controlled machine direction relaxation; and having substantially circular holes, pores The degree is about 40% to 70%, the ratio of the machine direction tensile strength to the transverse direction tensile strength is in the range of about 0.5 to 5.0, the Gurley is less than about 300, the average flow pore diameter is at least about 0.0182, 2011, 37,000 microns, and the water hole size is at least about 0.04 microns. 26. The battery separator of claim 25, wherein the substantially circular aperture has at least one of a depth ratio in the range of about 0.75 to 1.25 and a ball diameter factor in the range of about 0.25 to 8.0. 83