Abstract:
Bedding products may utilize unique microporous films imparting bidirectional, micro particle and fluid penetration barrier properties, which may or may not contain active ingredient, while maintaining exceptional air permeability. A thin, microporous film with a unique sponge like cellular structure may prevent the migration of dust mites, dust mite feces, other micro particle allergens, pathogens and biological organisms from the interstices of the product to the sleep surface of the product, adversely affecting user health and comfort. Active ingredients such as anti microbial agents, metal oxides, and other materials may be used within the high capacity microporous structure of the film, and may provide customizable functionalities while maintaining barrier performance and superior air permeability. The micro structured film can be applied as a coating or a laminate to mattress or pillow ticking, a foam mattress construction, a comforter, duvet, mattress pad and/or other components of bedding products.

Description:
BACKGROUND 
       [0001]    Comfortable bedding materials often have high air permeability. The ability to ‘breathe’ allows heat and perspiration to be removed from a person, enhancing the person&#39;s sleep. However, dust mites and byproducts may be able to pass through air permeable articles such as mattress ticking, sheets, and other bedding components. Dust mites and their feces may adversely affect a person&#39;s health and ability to sleep well. 
       SUMMARY 
       [0002]    Bedding products may utilize unique microporous films imparting bidirectional, micro particle and fluid penetration barrier properties, which may or may not contain active ingredient, while maintaining exceptional air permeability. A thin, microporous film with a unique sponge like cellular structure may prevent the migration of dust mites, dust mite feces, other micro particle allergens, pathogens and biological organisms through the interstices of the product to the sleep surface of the product, adversely affecting user health and comfort. The porous film may hold a hydrostatic head and provide a barrier to damaging external fluid penetration. Active ingredients such as anti microbial agents, metal oxides, and other materials may be used within the high capacity microporous structure of the film, and may provide customizable functionalities while maintaining barrier performance and superior air permeability. The micro structured film can be applied as a coating or a laminate to mattress or pillow ticking, a foam mattress construction, a comforter, duvet, mattress pad and/or other components of bedding products. 
         [0003]    This Summary is provided to introduce a selection of concepts in a simplified form that are further described below in the Detailed Description. This Summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter. 
     
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         [0004]    In the drawings, 
           [0005]      FIG. 1  is a diagram illustration of an embodiment showing a cross-section of reinforced porous material. 
           [0006]      FIG. 2  is a flowchart illustration of an embodiment showing a method for forming a porous material. 
           [0007]      FIG. 3  is a diagram illustration of an embodiment showing a process for continuous manufacturing of reinforced porous material. 
           [0008]      FIG. 4  is a diagram illustration of an embodiment showing a process for a dip method of continuous manufacturing of reinforced porous material. 
           [0009]      FIG. 5  is a diagram illustration of an embodiment showing a one-sided laminating method for manufacturing a reinforced porous film. 
           [0010]      FIG. 6  is a diagram illustration of an embodiment showing a two-sided laminating method for manufacturing a reinforced porous film. 
           [0011]      FIG. 7  is a flowchart illustration of an embodiment showing a method for forming a porous material with a loading material. 
           [0012]      FIG. 8  is a diagram illustration of an embodiment showing a laminate construction with porous film. 
           [0013]      FIG. 9  is a diagram illustration of an embodiment showing a cross-sectional view of a mattress construction with a quilted top. 
           [0014]      FIG. 10  is a diagram illustration of an embodiment showing a cross-sectional view of a second mattress construction with a quilted top. 
       
    
    
     DETAILED DESCRIPTION 
       [0015]    A reinforced porous film may be constructed through various processes and using various formulations to be used in different applications for bedding components. The film may have a pore structure that may enable high amounts of airflow, but where the pores are small enough to prohibit dust mites and dust mite feces from travelling through the thickness of the film. 
         [0016]    In some applications, the porous film may be loaded with various materials that may prevent or inhibit fungal or bacterial growth, repel insects, or otherwise prevent microbes or pests from passing through. Some applications may include materials that may absorb environmental pathogens. Such materials may be included in the porous film by including the materials during the formation of the porous material or after the porous material has been formed. 
         [0017]    Applications for such film may be in mattress and pillow ticking, sheets, duvets, duvet covers, comforter covers, and other bedding components. 
         [0018]    A reinforced porous film may be created by several methods. Porous films by nature may be structurally weak, especially films with high porosity. A reinforced film may be considerably more structurally sound than an unreinforced film. Increased mechanical properties may help during handling and manufacturing of the film into various products, as well as increased structural properties of an end product. 
         [0019]    One method for producing a reinforced porous film may be to create the porous material with a reinforcement. For example, a solution used to create the porous material may be cast or sprayed onto the reinforcement. In another example, the reinforcement may be dipped into the solution. 
         [0020]    Another method for producing a reinforced porous film may be to form a porous film and subsequently bond the porous film to a reinforcement. The bonding may be accomplished using mechanical interlocking, heat fusing, adhesives, or any other mechanism. 
         [0021]    The reinforcement may be any type of woven or nonwoven material, perforated film, or any other web material. For the purposes of this specification, any references to any type of reinforcing web shall be interpreted to mean any type of reinforcing web, including nonwoven and woven reinforcement. 
         [0022]    Specific embodiments of the subject matter are used to illustrate specific inventive aspects. The embodiments are by way of example only, and are susceptible to various modifications and alternative forms. The appended claims are intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the claims. 
         [0023]    Throughout this specification, like reference numbers signify the same elements throughout the description of the figures. 
         [0024]    When elements are referred to as being “connected” or “coupled,” the elements can be directly connected or coupled together or one or more intervening elements may also be present. In contrast, when elements are referred to as being “directly connected” or “directly coupled,” there are no intervening elements present. 
         [0025]      FIG. 1  is a schematic diagram of an embodiment  100  showing a cross section of porous material that may be formed using a solution of a polymer dissolved in a solvent and a miscible pore forming agent that has a higher surface energy. The porous material  102  and  104  is shown on both sides of a web  106 . 
         [0026]      FIG. 1  is not to scale and is a schematic diagram. In some embodiments, the porous material  102  and  104  may impregnate the non-woven web  106 . Such embodiments may have partial impregnation or complete impregnation of porous material  102  and  104  into the thickness of the non-woven web  106 . Some embodiments may have mechanical or chemical adhesion of the porous material  102  and  104  to the surface of the non-woven web  106 . Other embodiments may vary in cross section based on the specific manufacturing process used and may have full impregnation or very little mechanical interlocking between the layers. 
         [0027]    Embodiment  100  may be manufactured by several different methods. In some cases, the porous material  102  and  104  may be formed separately and bonded to the non-woven reinforcement  106 . In other cases, the porous material  102  and  104  may be formed from a solution that may be applied to the reinforcement  106  in a liquid form and processed to yield the porous material  102  and  104  with the reinforcement  106 . 
         [0028]      FIG. 2  is a flowchart diagram of an embodiment  200  showing a method for forming a porous material. Embodiment  200  is a general method, examples of which are discussed below. 
         [0029]    In block  202 , a solution may be formed with a polymer dissolved in a first liquid and a second liquid that may act as a pore forming agent. The liquids may be selected based on boiling points or volatility and surface tension so that when processed, the polymer is formed with a high porosity. Examples of such liquids are discussed below. 
         [0030]    After forming the solution in block  202 , the solution is applied to a carrier in block  204 . The carrier may be any type of material. In some cases, a flat sheet of porous material may be cast onto a table top, which acts as a carrier in a batch process. In other cases, a film such as a polymer film, treated or untreated kraft paper, aluminum foil, or other backing or carrier material may be used in a continuous process. In such cases, a porous film may be manufactured and attached to a reinforcing web in a secondary process. In still other cases, the carrier material may be a nonwoven, woven, perforated, or other reinforcing web. In such cases, the solution may be applied by dipping, spraying, casting, extruding, pouring, spreading, or any other method of applying the solution. 
         [0031]    The reinforcing web may be any type of reinforcement, including polymer based nonwoven webs, paper products, and fiberglass. In some cases, a woven material may be used with natural or manmade fibers, while in other cases, a solid film may be perforated and used as a reinforcing web. 
         [0032]    In block  206 , enough of the primary liquid may be removed so that the dissolved polymer may begin to gel. In some embodiments, some, most, or substantially all of the primary liquid may be removed in block  206 . As the polymer begins to gel, the mechanical structure of the material may begin to take shape and the porosity may begin to form. During this time, the material may have some mechanical properties so that different mechanisms may be used to remove any remaining primary liquid and the secondary liquid. 
         [0033]    The secondary liquid may be removed in block  208 . During the gelling process of block  206 , the differences in surface tension between the various materials may allow the secondary liquid to coalesce and form droplets, around which the polymer may gel as the first liquid is removed. After or as the polymer solidifies, the second liquid may be removed. In some cases, the boiling point or volatility of the two liquids may be selected so that the primary liquid evaporates prior to the secondary liquid. 
         [0034]    The mechanisms for removing the primary and secondary liquids may be any type of suitable mechanism for removing a liquid. In many cases, the primary liquid may be removed by a unidirectional mass transfer mechanism such as evaporation, wicking, blotting, mechanical compression or others. Some methods may use bidirectional mass transfer such as rinsing or washing. In some cases, one method may be used to remove the primary liquid and a second method may be used for the secondary liquid. For example, the primary liquid may be at least partially removed by evaporation while the remaining primary liquid and secondary liquid may be removed by rinsing or mechanically squeezing the material. 
         [0035]    Three embodiments are presented below of formulations and methods of production for porous material. 
         [0036]    In a first embodiment, the porous material may be formed by first forming a layer of a polymer solution on a substrate, wherein the polymer solution may comprise two miscible liquids and a polymer material dissolved therein, wherein the two miscible liquids may comprise (i) a principal solvent liquid that may have a surface tension at least 5% lower than the surface energy of the polymer and (ii) a second liquid that may have a surface tension at least 5% greater than the surface energy of the polymer. Second, a gelled polymer may be produced from the layer of polymer solution under conditions sufficient to provide a non-wetting, high surface tension solution within the layer of polymer solution; and, thirdly, rapidly removing the liquid from the film of gelled polymer by unidirectional mass transfer without dissolving the gelled polymer to produce the strong, highly porous, microporous polymer  102  and  104 . 
         [0037]    In a second embodiment, the porous material  104  may be produced using a method comprising: 
         [0038]    (i) preparing a solution of one or more polymers in a mixture of a principal liquid which is a solvent for the polymer and a second liquid which is miscible with the principal liquid, wherein (i) the principal liquid may have a surface tension at least 5% lower than the surface energy of the polymer, (ii) the second liquid may have a surface tension at least 5% higher than the surface energy of the polymer, (iii) the normal boiling point of the principal liquid is less than 125° C. and the normal boiling point of the second liquid is less than about 160° C., (iv) the polymer may have a lower solubility in the second liquid than in the principal liquid, and (v) the solution may be prepared at a temperature less than about 20° C. above the normal boiling point of the principal liquid and while precluding any substantial evaporation of the principal liquid; 
         [0039]    (ii) reducing the temperature of the solution by at least 5° C. to between the normal boiling point of the principal liquid and the temperature of the substrate upon the solution is to be cast; 
         [0040]    (iii) casting the polymer solution onto a high surface energy substrate to form a liquid coating thereon, said substrate having a surface energy greater than the surface energy of the polymer; and 
         [0041]    (iv) removing the principal liquid and the second liquid from the coating by unidirectional mass transfer without use of an extraction bath, (ii) without re-dissolving the polymer, and (iii) at a maximum air temperature of less than about 100° C. within a period of about 5 minutes, to form the strong, highly porous, thin, symmetric polymer membrane. 
         [0042]    In a third embodiment, the porous material  104  may be produced by a method comprising: 
         [0043]    (i) dissolving about 3 to 20% by weight of a polymer in a heated multiple liquid system comprising (a) a principal liquid which is a solvent for the polymer and (b) a second liquid to form a polymer solution, wherein (i) the principal liquid may have a surface tension at least 5% lower than the surface energy of the polymer, (ii) the second liquid may have a surface tension at least 5% greater than the surface energy of the polymer; and (iii) the polymer may have a lower solubility in the second liquid than it has in the principal solvent liquid; 
         [0044]    (ii) reducing the temperature of the solution by at least 5° C. to between the normal boiling point of the principal liquid and the temperature of the substrate upon which it will be cast; 
         [0045]    (iii) casting a film of the fully dissolved solution onto a substrate which may have a higher surface energy than the surface energy of the polymer; 
         [0046]    (iv) precipitating the polymer to form a continuous gel phase while maintaining at least 70% of the total liquid content of the initial polymer solution, said precipitation caused by a means selected from the group consisting of cooling, extended dwell time, solvent evaporation, vibration, or ultrasonics; and 
         [0047]    (v) removing the residual liquids without causing dissolution of the continuous gel phase by unidirectional mass transfer without any extraction bath, at a maximum film temperature which is less than the normal boiling point of the lowest boiling liquid, and within a period of about 5 minutes, to form a strong, highly porous, thin, symmetric polymer membrane. 
         [0048]    The preceding embodiments are examples of different methods by which a porous material may be formed from a liquid solution to a porous polymer. Different embodiments may be used to create the porous material  102  and  104  and such embodiments may contain additional steps or fewer steps than the embodiments described above. Other embodiments may also use different processing times, concentrations of materials, or other variations. 
         [0049]    Each of the embodiments of porous material  102  and  104  may begin with the formation of a solution of one or more soluble polymers in a liquid medium that comprises two or more dissimilar but miscible liquids. To form highly porous products, the total polymer concentration may generally be in the range of about 3 to 20% by weight. Lower polymer concentrations of about 3 to 10% may be preferred for the preparation of membranes having porosities greater than 70%, preferably greater than 75%, and most preferably greater than 80% by weight. Higher polymer concentrations of about 10 to 20% may be more useful to prepare slightly lower porosity membranes, i.e. about 60 to 70%. 
         [0050]    A suitable temperature for forming the polymer solution may generally range from about 40° C. up to about 20° above the normal boiling point of the principal liquid, preferably about 40 to 80° C., more preferably about 50° C. to about 70° C. A suitable pressure for forming the polymer solution may generally range from about 0 to about 50 psig. In some embodiments, the polymer solution may be formed in a vacuum. Preferably a sealed pressurized system is used. 
         [0051]    The material  102  may be formed in the presence of at least two dissimilar but miscible liquids to form the polymer solution from which a polymer film may be cast. The first “principal” liquid may be a better solvent for the polymer than the second liquid and may have a surface tension at least 5%, preferably at least 10%, lower than the surface energy of the polymer involved. The second liquid may be a solvent or a non-solvent for the polymer and may have a surface tension at least 5%, preferably at least 10%, greater than the surface energy of the polymer. 
         [0052]    The principal liquid may be at least 70%, preferably about 80 to 95%, by weight of the total liquid medium. The principal liquid may dissolve the polymer at the temperature and pressure at which the solution may be formed. The dissolution may generally take place near or above the boiling temperature of the principal liquid, usually in a sealed container to prevent evaporation of the principal liquid. The principal liquid may have a greater solvent strength for the polymer than the second liquid. Also, the principal liquid may have a surface tension at least about 5%, preferably at least about 10%, lower than the surface energy of the polymer. The lower surface tension may lead to better polymer wetting and hence greater solubilizing power. 
         [0053]    The second liquid, which may generally represent about 1 to 10% by weight of the total liquid medium, may be miscible with the first liquid. The second liquid may or may not dissolve the polymer as well as the first liquid at the selected temperature and pressure. The second liquid may have a higher surface tension than the surface energy of the polymer. Preferably, the second liquid may or may not wet the polymer at the gelation temperature though it may wet the polymer at more elevated temperatures. 
         [0054]    Table A and Table B identify some specific principal and second liquids that may be used with typical polymers, especially including PVDF. PVDF may be used as a homopolymer or as a copolymer with hexofloropropolyne. Table A lists liquids that have at least some degree of solubility towards PVDF (surface energy of 35 dyne/cm), which may produce the dissolved polymer solution in the first step of the process. Ideally, a liquid may be selected from Table A that has solubility limits between 1% and 50% by weight of polymer at a temperature within the range of about 20 and 90° C. The liquids in Table B, on the other hand, may have lower polymer solubility than those in Table A, but may be selected because they have a higher surface tension than both the principal liquid and the polymers that may be dissolved in the solution made with liquid(s) from Table A. 
         [0055]    Tables A and B represent typical examples of suitable liquids that may be used to create a porous material  102  and  104 . Other embodiments may use different liquids as a principal liquid or second liquid. 
         [0056]    Examples of suitable liquids for use as the principal liquid, along with their boiling point and surface tensions are provided in Table A below. The table is arranged in order of increasing boiling point, which is a useful parameter for achieving rapid gelling and removal of the liquid during the film formation step. In some applications, a lower boiling point may be preferred. 
         [0000]    
       
         
               
               
               
             
               
               
               
             
           
               
                 TABLE A 
               
               
                   
               
               
                   
                 Normal Boiling 
                 Surface Energy, 
               
               
                 Principal Liquid 
                 Point, EC 
                 dynes/cm 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 methyl formate 
                 31.7 
                 24.4 
               
               
                 acetone (2-propanone) 
                 56 
                 23.5 
               
               
                 methyl acetate 
                 56.9 
                 24.7 
               
               
                 Tetrahydrofuran 
                 66 
                 26.4 
               
               
                 ethyl acetate 
                 77 
                 23.4 
               
               
                 methyl ethyl ketone (2-butanone) 
                 80 
                 24 
               
               
                 Acetonitrile 
                 81 
                 29 
               
               
                 dimethyl carbonate 
                 90 
                 31.9 
               
               
                 1,2-dioxane 
                 100 
                 32 
               
               
                 Toluene 
                 110 
                 28.4 
               
               
                 methyl isobutyl ketone 
                 116 
                 23.4 
               
               
                   
               
             
          
         
       
     
         [0057]    Examples of suitable liquids for use as the second liquid, along with their boiling point and surface tensions are provided in Table B below. This table is arranged in order of increasing surface tension as higher surface tension may result in optimum pore size distributions during the gelling and liquid removal steps of the process. 
         [0000]    
       
         
               
               
               
               
             
               
               
               
               
             
           
               
                   
                 TABLE B 
               
               
                   
                   
               
               
                   
                   
                 Normal boiling 
                 Surface Energy, 
               
               
                   
                 Second Liquid 
                 point, ° C. 
                 dynes/cm 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 nitromethane 
                 101 
                 37 
               
               
                   
                 bromobenzene 
                 156 
                 37 
               
               
                   
                 formic acid 
                 100 
                 38 
               
               
                   
                 pyridine 
                 114 
                 38 
               
               
                   
                 ethylene bromide 
                 131 
                 38 
               
               
                   
                 3-furaldehyde 
                 144 
                 40 
               
               
                   
                 bromine 
                 59 
                 42 
               
               
                   
                 tribromomethane 
                 150 
                 42 
               
               
                   
                 quinoline 
                 24 
                 43 
               
               
                   
                 nitric acid (69%) 
                 86 
                 43 
               
               
                   
                 water 
                 100 
                 72.5 
               
               
                   
                   
               
             
          
         
       
     
         [0058]    The porous material may be formed by using a liquid medium for forming the polymer solution. The liquid medium may be rapidly removable at a sufficiently low temperature so that the second liquid may be removed without re-dissolving the polymer during the liquid removal process. The liquid medium may or may not be devoid of plasticizers. The liquids that form the liquid medium may be relatively low boiling point materials. In many embodiments, the liquids may boil at temperatures less than about 125° C., preferably about 100° C. and below. Somewhat higher boiling point liquids, i.e. up to about 160° C., may be used as the second liquid if at least about 60% of the total liquid medium is removable at low temperature, e.g. less than about 50° C. The balance of the liquid medium can be removed at a higher temperature and/or under reduced pressure. Suitable removal conditions depend upon the specific liquids, polymers, and concentrations utilized. 
         [0059]    Preferably the liquid removal may be completed within a short period of time, e.g. less than 5 minutes, preferably within about 2 minutes, and most preferably within about 1.5 minutes. Rapid low temperature liquid removal, preferably using air flowing at a temperature of about 80° C. and below, most preferably at about 60° C. and below, without immersion of the membrane into another liquid has been found to produce a membrane with enhanced uniformity. The liquid removal may be done in a tunnel oven with an opportunity to remove and/or recover flammable, toxic or expensive liquids. The tunnel oven temperature may be operated at a temperature less than about 90° C., preferably less than about 60° C. 
         [0060]    The polymer solution may become supersaturated in the process of film formation. Generally cooling of the solution will cause the supersaturation. Alternatively, the solution may become supersaturated after film formation by means of evaporation of a portion of the principal liquid. In each of these cases, a polymer gel may be formed while there is still sufficient liquid present to generate the desired high void content in the resulting polymer film when that remaining liquid is subsequently removed. 
         [0061]    After the polymer solution has been prepared, it may then be formed into a thin film. The film-forming temperature may be preferably lower than the solution-forming temperature. The film-forming temperature may be sufficiently low that a polymer gel may rapidly form. That gel may then be stable throughout the liquid removal procedure. A lower film-forming temperature may be accomplished, for example, by pre-cooling the substrate onto which the solution is deposited, or by self-cooling of the polymer solution by controlled evaporation of a small amount of the principal liquid. 
         [0062]    The film-forming step may occur at a lower temperature (and often at a lower pressure) than the solution-forming step. Commonly, it may occur at or about room temperature. However, it may occur at any temperature and pressure if the gelation of the polymer is caused by means other than cooling, such as by slight drying, extended dwell time, vibrations, or the like. Application as a thin film may allow the polymer to gel in a geometry defined by the interaction of the liquids of the solution. 
         [0063]    The thin film may be formed by any suitable means. Extrusion or flow through a controlled orifice or by flow through a doctor blade may be commonly used. The substrate onto which the solution may be deposited may have a surface energy higher than the surface energy of the polymer. Examples of suitable substrate materials (with their surface energies) include copper (44 dynes/cm), aluminum (45 dynes/cm), glass (47 dynes/cm), polyethylene terephthalate (44.7 dynes/cm), and nylon (46 dynes/cm). In some cases a metal, metalized, or glass surface may be used. More preferably the metalized surface is an aluminized polyalkylene such as aluminized polyethylene and aluminized polypropylene. 
         [0064]    In view of the thinness of the films, the temperature throughout may be relatively uniform, though the outer surface may be slightly cooler than the bottom layer. Thermal uniformity may enable the subsequent polymer precipitation to occur in a more uniform manner. 
         [0065]    The films may be cooled or dried in a manner that prevents coiling of the polymer chains. Thus the cooling/drying may be conducted rapidly, i.e. within about 5 minutes, preferably within about 3 minutes, most preferably within about 2 minutes, because a rapid solidification of the spread polymer solution facilitates retention of the partially uncoiled orientation of the polymer molecules when first deposited from the polymer solution. 
         [0066]    The process may entail producing a film of gelled polymer from the layer of polymer solution under conditions sufficient to provide a non-wetting, high surface tension solution within the layer of polymer solution. Preferably gelation of the polymer into a continuous gel phase occurs while maintaining at least 70% of the total liquid content of the initial polymer solution. More particularly, the precipitation of the gelled polymer is caused by a means selected from a group consisting of cooling, extended dwell time, solvent evaporation, vibration, or ultrasonics. Then, the balance of the liquids may be removed by a unidirectional process, usually by evaporation, from the formed film to form a strong micro-porous membrane of geometry controlled by the combination of the two liquids in the medium. In some embodiments, a liquid bath may be used to extract the liquids from the membrane. In other embodiments, the liquid materials may evaporate at moderate temperatures, i.e. at a temperature lower than that used for the polymer dissolution to prepare the polymer solution. The reduced temperature may be accomplished by the use of cool air or even the use of forced convection with cool to slightly warmed air to promote greater evaporative cooling. 
         [0067]    The interaction among the two liquids (with their different surface tension characteristics) and the polymer (with a surface energy intermediate the surface tensions of the liquids) may yield a membrane with high porosity and relatively uniform pore size throughout its thickness. The surface tension forces may act at the interface between the liquids and the polymer to give uniformity to the cell structure during the removal step. The resulting product may be a solid polymeric membrane with relatively high porosity and uniformity of pore size. The strength of the membrane in some embodiments may be surprisingly high, due to the more linear orientation of polymer molecules. 
         [0068]    The ratio of the principal liquid to the second liquid at the point of gelation may be adjusted such that the surface tension of the composite liquid phase may be greater than the surface energy of the polymer. The calculation of the composite liquid surface tension can be predicted based upon the mol fractions of liquids, as defined in “Surface Tension Prediction for Liquid Mixtures,” AIChE Journal, vol 44, no. 10, p. 2324, 1998, the subject matter of which is incorporated herein by reference. 
         [0069]    Thermodynamic calculations show that adiabatic cooling of a solution can be significant initially and that the temperature gradient through such a film is very small. The latter may be considered responsible for the exceptional uniformity obtained using these methods. 
         [0070]    The polymers used to produce the microporous membranes of the present invention may be organic polymers. Accordingly, the microporous polymers comprise carbon and a chemical group selected from hydrogen, halogen, oxygen, nitrogen, sulfur and a combination thereof. In a preferred embodiment, the composition of the microporous polymer may include a halogen. Preferably, the halogen is selected from the group consisting of chloride, fluoride, and a mixture thereof. 
         [0071]    Suitable polymers for use herein may be include semi-crystalline or a blend of at least one amorphous polymer and at least one crystalline polymer. 
         [0072]    Preferred semi-crystalline polymers may be selected from the group consisting of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polyvinyl chloride, polyvinylidene chloride, chlorinated polyvinyl chloride, polymethyl methacrylate, and mixtures of two or more of these semi-crystalline polymers. 
         [0073]    In some embodiments, the products produced by the processes described herein may be used as a battery separator. For this use, the polymer may comprise a polymer selected from the group consisting of polyvinylidene fluoride (PVDF), polylvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), polyvinyl chloride, and mixtures thereof. Still more preferably the polymer may comprise at least about 75% polyvinylidene fluoride. 
         [0074]    The “MacMullin” or “McMullin” Number measures resistance to ion flow is defined in U.S. Pat. No. 4,464,238, the subject matter of which is incorporated herein by reference. The MacMullin Number is “a measure of resistance to movement of ions. The product of MacMullin Number and thickness defines an equivalent path length for ionic transport through the separator. The MacMullin Number appears explicitly in the one-dimensional dilute solution flux equations which govern the movement of ionic species within the separator; it is of practical utility because of the ease with which it is determined experimentally.” The lower a MacMullin Number the better for battery separators, the better. Products using these techniques may have a low MacMullin number, i.e. about 1.05 to 3, preferably about 1.05 to less than 2, most preferably about 1.05 to about 1.8. 
         [0075]    Good tortuosity is an additional attribute of some embodiments. A devious or tortuous flow path with multiple interruptions and fine pores may act as a filter against penetration of invading solids. Tortuosity of the flow path can be helpful to prevent penetration by loose particles from an electrode or to minimize growth of dendrites through a separator that might cause electrical shorts. This characteristic cannot be quantified, except by long-term use, but it can be observed qualitatively by viewing a cross-section of the porosity. 
         [0076]    Some embodiments may be generally uniform and symmetric, i.e. the substrate side pores may be substantially similar in size to the central and the air side pores. Pores varying in diameter by a factor of about 5 or less may be sufficiently uniform for the membranes to function in a symmetric manner. 
         [0077]    Where additional strength or stiffness may be needed for handling purposes, micro- or nano-particles can be added to the formulation with such particulates residing within the polymer phase. A few such additives include silica aerogel, talc, and clay. 
         [0078]      FIG. 3  is a diagram illustration of an embodiment  300  showing a process for continuous manufacturing of reinforced porous material. Embodiment  300  is an example of a general process that may be used to form porous material directly in a reinforced web, such as a nonwoven web, woven web, or perforated film. 
         [0079]    A web  302  may be unwound with an unwinding mechanism  304  and moved in the direction of travel  301 . Various reinforcement webs may be used, including woven and nonwoven. In many embodiments, a nonwoven web may be preferred from a cost standpoint. 
         [0080]    As the web  302  is being moved in the direction  301 , solution  302  may be applied to the web  302  with an applicator  308 . The applicator  308  may apply a wet solution  306  to form an uncured solution  310 . 
         [0081]    In some embodiments, a carrier material may be used to facilitate handling of the web and may provide a bottom surface against which the liquid solution  306  may be supported while in the uncured state. Such carrier material may include treated kraft paper, various polymeric films, metal films, metalized carriers, or other material. Some embodiments may use a carrier material in subsequent manufacturing steps and may include the carrier material with the cured porous material  314  on the take up mechanism  316 . In other embodiments, the carrier material may be stripped from the cured porous material  314  before the take up mechanism  316 . In still other embodiments, a continuous recirculating belt or screen may be used beneath the web  302  during processing. 
         [0082]    The embodiment  300  illustrates a manufacturing sequence that may be predominantly horizontal. In other embodiments, a vertical manufacturing process may have a direction of travel in either vertical direction, either up or down. A vertical direction of travel may enable a porous material to evenly form on two sides of a reinforcement web. Such an embodiment may have an applicator system that may apply solution to both sides of a reinforcement web. Horizontal manufacturing processes, such as embodiment  300 , may result in a final product that may be asymmetrical, with the reinforcement web being located off the centerline of the thickness of the material. 
         [0083]    The applicator  308  may be any mechanism by which the solution  306  may be applied to the web  302 . In some embodiments, the solution  306  may be continuously cast, sprayed, extruded, or otherwise applied. Some embodiments may use a doctor blade or other mechanism to distribute the solution  306 . 
         [0084]    The thickness of the resulting reinforced porous material may be adjusted by controlling the amount of solution  306  that is applied to the web  302  and the speed of the web during application, among other variables. 
         [0085]    Some embodiments may includes various additional processes, such as air knives, calendering, rolling, or other processing before, during, or after the solution  306  has formed into a solid porous polymer material. 
         [0086]    The uncured solution  310  may be transferred through a tunnel oven  312  or other processes in order to form a cured porous material  314 , which may be taken up with a take up mechanism  316 . 
         [0087]    The tunnel oven  312  may have different zones for applying various temperature profiles to the uncured solution  310  in order to form a porous material. In many cases, an initial lower temperature may be used to evaporate a portion of a primary liquid and begin formation of a solid polymer structure. A higher temperature may be used to remove a second liquid and remaining primary liquid. 
         [0088]    In some embodiments, the tunnel oven  312  may provide air transfer using heated or cooled air to facilitate curing. 
         [0089]    Embodiment  300  is an example of a continuous process for manufacturing a reinforced porous material by forming the porous material by introducing a wet solution directly onto the reinforcement media. Other embodiments may include casting a porous material directly onto a reinforced web in a batch mode, such as casting on non-moving table surface. 
         [0090]      FIG. 4  is a diagram illustration of an embodiment  400  showing a dip method for continuous manufacturing of reinforced porous material. 
         [0091]    A web  402  is unwound from an unwinding mechanism  404  and passed through a solution  406  in a bath  408  to form a web with uncured solution  410 . The bath  408  may be ultrasonically activated to remove air and promote wetting of the reinforcement by the solution. The web may pass through a curing zone  412  in which may remove a primary and secondary liquid while forming a polymer with a porous structure. The cured material on a web  414  may be taken up in a take up reel  416 . 
         [0092]    Embodiment  400  is an example of a continuous process for forming a porous material directly onto a reinforcement web. By controlling the viscosity of the solution  406  and the speed of operation, a controlled thickness of porous material may be formed. In some embodiments, a doctor blade, calendering mechanism, air knives, or other mechanisms may be used to provide additional control over the thickness of the uncured or cured material. 
         [0093]    The curing zone  412  may be any type of mechanism by which the uncured material  410  may be cured. Some embodiments may process the material through various heated or cooled zones, apply various rinses, process the material through a pressurized or vacuum environment, or provide some mechanical processing such as calendering, squeezing, or some other process. Each embodiment may have particular processing performed based on the selection of polymer, the formulation of the solution  406 , and the construction of the reinforcing web  402 . 
         [0094]    In some embodiments, the reinforcing web  402  may have various treatments applied prior to coming in contact with the solution  406 . For example, a sizing or other liquid material may be applied to the web  402 . One example may be to pretreat the web  402  with a dilute version of the solution  406  or a solution with a different solvent/polymer combination. In some cases, such a pretreatment may cause the reinforcing web  402  to swell or otherwise improve the bonding of the porous material to the web  402 . Other examples may include applying a corona or spray to the web  402  to partially oxidize the surface of the web  402 . Another example may be to apply an electric charge to the web  402  and an opposite charge to the bath  408 . Still another example may be to ionize the surface of the reinforcing web  402 . Such pretreatment processes may be used with any method for manufacturing a reinforced porous film. 
         [0095]    Ultrasonic activation of the solution  406  and reinforcing web  402  may enhance bonding and penetration of the solution  406  into the web. 
         [0096]    Ultrasonic activation may be used to supplement any type of mechanism by which a pore forming polymer solution may be applied to a reinforcing web. In some embodiments, ultrasonic energy may be introduced to the solution, while in other embodiments, ultrasonic energy may be applied to the reinforcing web before or after the solution is applied. In embodiment  400 , ultrasonic energy may be applied to the bath  408  or to the reinforcing web  402  prior to entering the bath  408 . Some embodiments may introduce ultrasonic energy to the web after the solution is applied by using an ultrasonic horn directed toward the web. 
         [0097]      FIG. 5  is a diagram illustration of an embodiment  500  showing a method for laminating reinforced porous film. Embodiment  500  shows a single cured porous film  502  being joined to one side of a reinforced web  506 . 
         [0098]    The porous film  502  may be unwound from an unwinding mechanism  504  and brought into contact with a reinforcement web  506  that is unwound from a second unwinding mechanism  508 . The two plies may be joined by the rollers  510  to form a reinforced porous film  512  that may be wound onto a take up reel  514 . 
         [0099]    Embodiment  500  is a method and apparatus for laminating a porous film  504  with a reinforcement web  506 . In some embodiments, an applicator  516  may be used to deliver ionic charge, adhesive, heat, or any other material or processing at the nip point of the joining process. 
         [0100]    An adhesive may be used to join the two layers. In some embodiments, the adhesive may contain a solvent that may enable a portion of either or both the polymer from the porous material or the reinforcement web to melt or dissolve and fuse with the other layer. In some cases, a polymer mixture may be used in forming the porous material with one of the polymers in the mixture selected to dissolve in an adhesive to facilitate the bonding to the reinforcement web. Another type of adhesive may contain a dissolved polymer that gels between the two layers to join the layers together. Another adhesive may be heat activated and may partially melt to join the layers. 
         [0101]    When adhesives are used, some embodiments may apply a coating of adhesive across one or both of the surfaces to be joined. Other embodiments may apply spots of adhesive in various locations or patterns. 
         [0102]    The applicator  516  may apply heat to one or more surfaces to be joined. In some embodiments, the heat may enable a portion of one or more of the materials to be joined to melt and fuse with the other. Such heat may be applied in conjunction with an adhesive. 
         [0103]    In some embodiments, the porous film  502  and reinforcement web  506  may be joined together by mechanical interlocking. Such interlocking may be created by applying pressure between the rollers  510 . 
         [0104]    In some cases, the porous film  502  may be transferred through a portion of the manufacturing process using a carrier film or other material. In such a case, the carrier film may be removed prior to entering the rollers  510 . 
         [0105]      FIG. 6  is a diagram illustration of an embodiment  600  showing a laminating method for two-sided lamination of porous film onto a central reinforced web. Embodiment  600  may use similar processing to that of embodiment  500 , with the addition of a second layer of porous film added so that the reinforcing web is in the center of the laminate. 
         [0106]    A first porous film  602  may be unwound from an unwinding mechanism  604 , and similarly a second porous film  606  may be unwound from unwinding mechanism  608 . A reinforcement web  610  is unwound from an unwinding mechanism  612  and laminated between the porous film layers  602  and  606  at the rollers  612  to form a laminate  614  that is taken up by a take up reel  616 . 
         [0107]    Embodiment  600  may join the layers of porous film and a reinforcement web by any mechanism whatsoever. In some cases, mechanical interlocking may be used, while in other cases, applicators  620  may apply heat and/or adhesives or other bonding agent or processing that may facilitate bonding. 
         [0108]    An adhesive may be used to join the various layers. In some embodiments, the adhesive may contain a solvent that may enable a portion of either or both the polymer from the porous material or the reinforcement web to melt or dissolve and fuse with the other layer. In some cases, a polymer mixture may be used in forming the porous material with one of the polymers in the mixture selected to dissolve in an adhesive to facilitate the bonding to the reinforcement web. Another type of adhesive may contain a dissolved polymer that gels between the two layers to join the layers together. Another adhesive may be heat activated and may partially melt to join the layers. 
         [0109]    When adhesives are used, some embodiments may apply a coating of adhesive across one or both of the surfaces to be joined. Other embodiments may apply spots of adhesive in various locations or patterns. 
         [0110]    The applicator  620  may apply heat to one or more surfaces to be joined. In some embodiments, the heat may enable a portion of one or more of the materials to be joined to melt and fuse with the other. Such heat may be applied in conjunction with an adhesive. 
         [0111]      FIG. 7  is a flowchart illustration of an embodiment  700  showing a method for creating a loaded porous material. The loading may be any nonstructural material that may perform various functions. 
         [0112]    In some cases, a loading may be passive and perform a function without changing state or engaging in a chemical reaction. In other cases, an active loading may undergo a chemical reaction or otherwise change state. 
         [0113]    Loading may be applied using two different application mechanisms. In one mechanism, a loading may be incorporated into the porous material solution and may become bound into the structure of the porous material. In another mechanism, a loading may be applied to the porous material after formation and may be captured within the pores of the porous material. 
         [0114]    In some embodiments, a two part loading material may be used. In such an embodiment, a first material may be incorporated into the solution and may be captured within the porous structure. A second part of the loading material may be applied to the formed porous material and the second part may interact with the first part to create the loading. In some cases, the second part may react with the first part or otherwise cause the first part to undergo a chemical transformation. 
         [0115]    The illustration of  FIG. 7  is a similar process as  FIG. 2 , with the addition of loading material prior to and/or after porous material formation. 
         [0116]    The solution is formed in block  202  as described above. 
         [0117]    Loading material may be added to the solution in block  702 . The loading material may be dissolved in the solution of block  202  or may be a particulate that may be suspended in the solution. 
         [0118]    The solution may be applied to a carrier in block  204 , and enough of the primary solution may be removed in block  206  to begin gelation. The secondary liquid may be removed in block  208 . 
         [0119]    Loading material may be added in block  704  which may be after the porous material is formed. In such a case, the loading material may be infused within the porous structure in several manners. In some cases, the loading material may be dissolved in a solution which may permeate the porous material. The solution may be dried, leaving a residue of loading material. 
         [0120]    In some cases, a particulate loading material may be infused into the porous structure as a dry material or with a liquid carrier. 
         [0121]    In some embodiments, other mechanisms for depositing a loading material may include vacuum deposition mechanisms, surface treatments, or other mechanisms. In some embodiments, the loading material may be applied through the porous structure, while in other cases, the loading material may be applied to the outer surface of the porous structure. 
         [0122]      FIG. 8  is a diagram illustration of a cross sectional view of an embodiment  800  showing a laminate construction that may be used in the manufacture of bedding items. Embodiment  800  is a simplified illustration of a multilayer laminate that may include a microporous film made from PVDF or other polymer.  FIG. 8  is not to scale. 
         [0123]    Embodiment  800  is an example of a laminate that may be used for mattress ticking, pillow ticking, bed sheets, duvet covers, mattress pads, pillow cases, and other bedding materials. 
         [0124]    The microporous film may serve as an effective dust mite barrier. An average dust mite may have a size of 0.42 mm and may leave fecal matter that may be 0.02 mm in size. The microporous film may be manufactured to have pores in the range of 0.01 mm or smaller, and some embodiments may have average pore size as small as 0.005 mm or smaller. 
         [0125]    In many embodiments, a microporous film may have high tortuosity that may inhibit or prevent dust mites or dust mite fecal matter from traversing the film and coming into contact with a person. 
         [0126]    In some embodiments, the microporous film may be infiltrated or coated with various anti-microbial agents that may inhibit mold, mildew, bacteria, or other unwanted organisms. In some embodiments, the microporous film may be infiltrated or coated with an insecticide or other agent that may kill or deter insects or other pests such as dust mites. Such materials may be added to the porous film by dipping or spraying the film after manufacturing the film. In some embodiments, the materials may be added to the porous film by incorporating the materials in the solution prior to forming the porous film. 
         [0127]    In embodiments with anti-pathogen properties such as anti-microbial properties described above, additives such as iodine, silver, silver oxide, silver nitrate, zinc, zinc sterate, copper glutamate, copper chloride, or other materials may be added to the microporous film. Such materials may be added to the polymer solution prior to forming the microporous film or by applying the materials after formation. Another material that may be added during formation may be an ultraviolet barrier may be created by adding zinc oxide to the microporous film. 
         [0128]    Embodiment  800  is an example of a three layer laminate that has a decorative outer layer  802 , a porous film layer  804 , and a protective inner layer  806 . The laminate of embodiment  800  may be used as an exterior or interior layer in mattresses, pillows, duvets, and other bedding. The laminate of embodiment  800  may be used in sheets, duvet covers, pillow cases, or similar products. 
         [0129]    The laminate of embodiment  800  may have a decorative outer layer  802  that may be a woven fabric, for example, that may be visible when the laminate is constructed into a product. 
         [0130]    The inner layer  806  may be a decorative material and may be visible when constructed into a product. In some such embodiments, the inner layer  806  may be a similar or the same material as the outer layer  802 . 
         [0131]    In some embodiments, the inner layer  806  may be manufactured into a product where the inner layer  806  may not be visible. In such embodiments, the inner layer  806  may have different properties than the outer layer  802 . For example, the inner layer  806  may be more tightly woven to prevent down or feathers from penetrating the laminate. The inner layer  806  may be manufactured with a higher strength material than the outer layer  802 , which may survive stitching and other manufacturing processes better than the outer layer  802 . 
         [0132]    The decorative outer layer  802  may be laminated to the porous film layer using several different methods. In some cases, the porous film layer  804  may be formed directly onto the decorative outer layer  802  or the protective inner layer  806 . In some embodiments, the porous film layer  804  may be heat laminated or bonded to either or both the outer layer  802  or inner layer  806 . 
         [0133]    In cases where heat laminating is used, the lamination process may be performed on the entire surface between the porous film layer  804  and one or both of the other layers. In some embodiments with heat laminating, the lamination may be performed in a discontinuous pattern, such as spots of lamination that are spaced apart. In such embodiments, two layers may be joined together and may have a majority of the surface area between the layers free from lamination. For example, some embodiments may have a laminated area that is 10%, 1% or even less than the total surface area of the laminate. 
         [0134]    Some embodiments may have the porous film layer  804  formed onto one of the layers as a reinforcement material, such as the inner layer  806  and may have the remaining layer laminated or bonded to the porous film layer  804 . 
         [0135]    Some embodiments may have a microporous layer formed directly onto the outer layer, where the outer layer may act as a reinforcement member for the microporous material as described above. In some such embodiments, the polymer solution used to make the microporous material may be applied to the external material such that the solution fully or partially wets the external material. When the solution fully wets through the thickness of the external material, the outer exposed surface of the external material may be changed from the unprocessed state. When the solution does not wet through the thickness of the external material, the microporous material may be formed in the internal side of the material and the external or visible surface may not be changed from the unprocessed state. 
         [0136]    In some embodiments, bedding products may be manufactured with two or three layers being sewn together with no lamination. Such products may have one of the layers as a porous film layer  804  that may or may not be constructed with a reinforcement web. 
         [0137]      FIG. 9  is a diagram illustration of a cross section of an embodiment  900  showing a mattress construction with a quilted top. Embodiment  900  is a simplified illustration of a construction that shows the placement of a porous film layer on the outer portion of a quilted assembly.  FIG. 9  is not to scale. 
         [0138]    Embodiment  900  is an example of a quilted construction. A decorative outer layer  902  may have a porous film layer  904  on the outer surface of a quilt constructed with an inner quilt layer  906  and quilting batting  908 . The quilted assembly may be attached to a mattress body  910 . 
         [0139]    The quilted assembly of the decorative outer layer  902 , porous film  904 , inner layer  908 , and quilting batting  908  may be used as a mattress pad, duvet, or other quilted product, in addition to being assembled to a mattress body  910 . 
         [0140]    The quilting batting  908  may be any type of batting or filler. In some cases, the batting may be a spun polymer fiber. In some cases, the batting may be down, feathers, or some other filler material. 
         [0141]    The mattress body  910  may be any type of mattress construction, such as foam, spring coils, or other mattress assembly. 
         [0142]    Embodiment  900  illustrates the porous film layer  904  next to or attached to the outer layer  902 . In some embodiments, the porous film layer  904  may be laminated or joined to the outer layer  902  in a continuous or discontinuous manner. In some embodiments, the porous film layer  904  may not be attached to the outer layer  902  except at points where the quilted assembly may be stitched or otherwise joined together. 
         [0143]    With the porous film layer  904  placed next to the outer layer  902 , the porous film layer  904  may serve as an effective dust mite barrier from dust mites that may be resident in the quilting batting  908 . 
         [0144]    In many embodiments, the porous film layer  904  may act as a water barrier, which may lower the humidity inside the mattress assembly of embodiment  900 . A lower humidity level may lower the survival of dust mites or other pests within the assembly. When the porous film layer  904  acts as a water barrier, liquid spills, incontinence, and liquid damage to the assembly of embodiment  900  may be minimized or prevented. In some cases, the water barrier of the porous film layer  904  may make cleanup of spills or incontinence much easier than if the porous film were not present. 
         [0145]      FIG. 10  is a diagram illustration of a cross section of an embodiment  1000  showing a mattress construction with a quilted top. Embodiment  1000  is a simplified illustration of a construction that shows the placement of a porous film layer on an inner portion of a quilted assembly.  FIG. 10  is not to scale. 
         [0146]    Embodiment  1000  is similar to embodiment  900  with the exception that the porous film layer is placed on the inner portion of the quilted assembly. 
         [0147]    Embodiment  1000  is an example of a quilted construction. A decorative outer layer  1002  may be quilted to a laminate of a porous film layer  1004  and an inner layer material  1006 . Quilting batting  1008  may be captured by the inner layers  1004  and  1006  and the outer layer  1002 . The quilted assembly may be attached to a mattress body  1010 . 
         [0148]    The quilting batting  1008  may be any type of batting or filler. In some cases, the batting may be a spun polymer fiber, cotton, or other material. In some cases, the batting may be down, feathers, or some other filler material. 
         [0149]    The mattress body  1010  may be any type of mattress construction, such as foam, spring coils, or other mattress assembly. Some mattress cores may include batting, foam, metal springs, or other materials. 
         [0150]    Embodiment  1000  illustrates the porous film layer  1004  next to or attached to the inner layer  1006 . In some embodiments, the porous film layer  1004  may be laminated or joined to the inner layer  1006  in a continuous or discontinuous manner. In some embodiments, the porous film layer  1004  may not be attached to the inner layer  1002  except at points where the quilted assembly may be stitched or otherwise joined together. 
         [0151]    Embodiment  1000  is similar to embodiment  900  but with the porous film layer placed on the opposite side of the quilting batting  1008 . Embodiment  1000  may be used in cases where the properties of a dust mite barrier are desired. Some embodiments of a porous film layer  1004  may be noisy when manipulated. By placing the porous film material towards the inside of the mattress assembly, less distortion or manipulation will occur for the porous film and less noise may propagate through the assembly to the end user. 
         [0152]    The foregoing description of the subject matter has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the subject matter to the precise form disclosed, and other modifications and variations may be possible in light of the above teachings. The embodiment was chosen and described in order to best explain the principles of the invention and its practical application to thereby enable others skilled in the art to best utilize the invention in various embodiments and various modifications as are suited to the particular use contemplated. It is intended that the appended claims be construed to include other alternative embodiments except insofar as limited by the prior art.