Patent Publication Number: US-2020276352-A1

Title: Apparatus and method for air freshening

Description:
FIELD OF THE INVENTION 
     The present invention relates to an apparatus and a method for air freshening in an interior occupancy space. 
     BACKGROUND OF THE INVENTION 
     Devices for dispensing volatile materials are well known and commonly used to deliver a variety of benefits such as freshening, malodor removal or scenting of air in spaces in household and commercial establishments such as rooms, or enclosed spaces such as a vehicle passenger compartment space. For example, air freshening products have been designed for dispensing volatile materials such as a volatile composition comprising one or more volatile materials like perfume oils. The volatile composition may be contained in, for example, a spray bottle and be sprayed into the air of interior spaces as droplets which transition to vapor. However, such products do not continuously freshen (i.e., the volatile composition is only dispensed upon manual activation). Alternatively, volatile compositions may be dispensed through systems which do not require manual actuation such as via evaporating the volatile composition from membrane based, wick based and gel based systems. 
     However, a problem with such air freshening products is often an inconsistency in the evaporation rate of the volatile composition over the product life, i.e. high evaporation rate of the volatile composition at the beginning of product use and low evaporation rate towards end of product life. Specifically, the volatile composition typically comprises a mixture of highly volatile compounds and other volatile compounds which are less volatile (“less volatile compounds”). Highly volatile compounds generally have higher vapor pressures than the less volatile compounds. Specifically, at a given temperature, a highly volatile compound with a higher vapor pressure vaporizes more readily than a less volatile compound with a lower vapor pressure. In use, the highly volatile compounds tend to evaporate more quickly at the beginning of such a product&#39;s use, while the less volatile compounds evaporate later, resulting in an overall inconsistent scent intensity and fragrance character of the volatile composition over the product life. The high initial evaporation rate can result in an overpowering initial scent intensity which can create a perception that the air freshener product has a different scent intensity over the product life or that the product is no longer effective after the initial scent intensity is no longer present. 
     In particular, car vent air fresheners attachable to the car vent provide at least one advantage by quickly providing freshness throughout the car when air flow occurs through the vent and moves past the air freshener. However, it is also a challenge to prevent a “too strong scent intensity” during high air flow conditions such as during use of the air conditioning system or the heater of a heating, ventilation, and air conditioning (HVAC) system or during driving. Further, there is also a continuing need to provide users a “well balanced” scent character that generally include top, middle, and bottom scent “notes.”. Therefore, there exists a need for an apparatus for delivering a volatile composition at a reduced evaporation rate and for controlled release of the volatile composition. There is also a need for an apparatus and method to provide a consistent evaporation rate, scent intensity and/scent character over time. 
     SUMMARY OF THE INVENTION 
     The present invention relates to an apparatus for air freshening in an interior occupancy space, the apparatus comprising: 
     a) a reservoir containing a volatile composition for air freshening and/or malodor removal; 
     b) a composite membrane in fluid communication with the volatile composition; wherein the composite membrane comprises a first side facing the reservoir and a second side opposite the first side; 
     c) wherein at least one of the first side and the second side comprises a diffusion regulating coating, wherein the diffusion regulating coating comprises a hydrophobic/oleophobic material comprising at least one fluoro-alkyl group; 
     d) wherein the volatile composition comprises at least 20% of perfume raw materials by weight of the composition, wherein the at least 20% of perfume raw materials have an average vapor pressure equal to or greater than 0.01 torr at 25 degrees Celsius; 
     e) wherein the apparatus comprises an average vapor release rate from 0.2 mg/hr*cm 2  to 5 mg/hr*cm 2  at an air flow rate of 5 m/s+/−1 m/s and a temperature of 21 degrees Celsius. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG. 1  is a side section view of an apparatus for controlled release of a volatile composition according to the present invention; 
         FIG. 2  is a side section view of the apparatus shown in  FIG. 1  in a vertical orientation when the apparatus is placed on a support; 
         FIGS. 3A to 3C  are side schematic views of different arrangements of a diffusion regulating coating on a composite membrane for an apparatus according to the present invention; 
         FIGS. 4A to 4C  are side schematic views of different structure configurations of materials for a diffusion regulating coating on a composition membrane for an apparatus according to the present invention; 
         FIG. 5  is a perspective view of components of a variation of an apparatus according to the present invention; 
         FIG. 6A  is a side section view of the apparatus shown in  FIG. 5  when it is assembled before activation; 
         FIG. 6B  is a side section view of the apparatus of  FIG. 6A  after activation; 
         FIG. 7  is a front perspective view of the apparatus of  FIGS. 6A and 6B  in use in an automobile environment; 
         FIG. 8  is a graph showing the cumulative amount of a volatile composition of a volatile composition contained in Comparative Example 1 and Inventive Examples 2, 3 and 4 released over time; 
         FIG. 9  is a graph showing a vapor release rate/perfume evaporation rate in milligrams per hour of a volatile composition contained in Comparative Example 1 and Inventive Examples 2, 3 and 4 released over time; 
         FIG. 10  is a graph showing the cumulative amount of a volatile composition contained in Comparative Example 2 and Inventive Examples 5 and 6 released over time; and 
         FIG. 11  is a graph showing a vapor release rate/perfume evaporation rate in milligrams per hour of a volatile composition contained in Comparative Example 2 and Inventive Examples 5 and 6 released over time. 
     
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     The present invention relates to an apparatus and a method for air freshening in an interior occupancy space in a continuous manner. Specifically, the apparatus comprises a reservoir for containing a liquid phase or a solid phase of a volatile composition. The volatile composition comprises a mixture of perfume raw materials which can evaporate at or near room temperature and atmospheric pressure without the need for an external energy source. It has also been surprisingly found that providing a composite membrane with a diffusion regulating coating in the apparatus having the volatile composition at an air vent of an air conditioning system enables controlled release of the volatile composition from the apparatus when the air conditioning system is turned on thereby enabling a reduced average vapor release rate of the volatile composition and reducing the scent intensity of the volatile composition in the interior occupancy space. 
     A technical effect of a volatile composition having the mixture of perfume raw materials and the composite membrane having a diffusion regulating coating is the vapor release rate of the apparatus in combination with the volatile composition can be measurably reduced while using the apparatus on the vent in an interior space such as in an automobile thereby reducing scent intensity rather than relying on adjusting air flow openings in an air freshener. 
     In the following description, the apparatus described is a consumer product, such as a car air freshener, for evaporating a volatile composition in an interior occupancy space of an automobile to deliver a variety of benefits such as freshening, malodor removal or scenting of air in an interior occupancy space such as a vehicle passenger compartment space. However, it is contemplated that the apparatus may be configured for use in a variety of applications to deliver a volatile composition to provide the benefits in interior occupancy spaces such as rooms in household and commercial establishments with air conditioning systems, and the apparatus may include but is not limited to consumer products, such as, for example air freshening products, air fresheners or the like. 
     For the purposes of illustrating the present invention in detail, the invention is described below as a non-energized apparatus having a membrane in fluid communication with the volatile composition. However, it will be appreciated that the apparatus of the present invention can be energized or non-energized. Prior to describing the present invention in detail, the following terms are defined for clarity. Terms not defined should be given their ordinary meaning as understood by a skilled person in the relevant art. 
     “Hydrophilic” as used herein, means that a side of the membrane over which a hydrophilic coating is applied demonstrates a water contact angle of less than 90° using the Kruss Drop Shape Analysis. 
     “Hydrophobic” as used herein, means that a side of the membrane over which a hydrophobic material is applied demonstrates a water contact angle of at least 90° using the Kruss Drop Shape Analysis. 
     “Oleophobic” as used herein, means that a side of the membrane over which a hydrophobic/oleophobic material is applied demonstrates an oil rating of at least 6, such as at least 7 or at least 8, based on AATCC test method 118-2007. 
     “Horizontal orientation” as used herein, refers to a position of an apparatus according to the present invention wherein the membrane is facing the environment in an upward or downward position. 
     “interior occupancy space” refers to a finite volume of space in a residential, commercial or vehicle environment. 
     “Membrane” as used herein, refers to a semi-permeable material which allows some components of matter to pass through but stops other components. Of the components that pass through, the membrane moderates the permeation of components i.e. some components permeate faster than other components. Such components may include molecules, ions or particles. 
     “Microporous membrane” as used herein, refers to a material having a network of pores. 
     “Composite membrane” as used herein, refers to a membrane having two or more different materials. The composite membrane may include a substrate having the two or more different materials applied to the substrate to form the composite membrane. 
     “Non-energized” means that the apparatus is passive and does not require to be powered by a source of external energy. In particular, the apparatus does not need to be powered by a source of heat, gas or electrical current. The apparatus may also be configured as an energized device. An exemplary energized device may be an electrical device. The energy source of the energized device may be an electrical car outlet or battery-operated air freshener having a membrane as described in the following description to transport a volatile composition and/or evaporate a volatile composition therefrom; or other heating devices (e.g. devices powered by chemical reactions such as catalyst fuel systems; solar powered devices, etc.). 
     “Touchpoint” as used herein, refers to a point of contact or interaction between the use of an air freshener (or apparatus) and a consumer of the volatile composition. 
     “Vertical orientation” as used herein, refers to a position of an apparatus according to the present invention wherein the membrane is facing the environment in a forward facing position or in a rear facing position. 
     “Volatile composition” as used herein, refers to a material that is vaporizable at room temperature and atmospheric pressure without the need of an additional energy source. The volatile composition may be configured for various uses such as air freshening, deodorization, odor elimination, malodor counteraction, mood enhancement, aromatherapy aid, scented compositions, non-scented compositions. Further, it is not necessary for all of the component materials of the volatile composition to be volatile. Any suitable volatile composition in any amount or form, including a liquid, solid, gel or emulsion, may be used. Materials suitable for use herein may include non-volatile compounds, such as carrier materials (e.g., water, solvents, etc.). It should also be understood that when the volatile composition is described herein as being “delivered”, “emitted”, or “released”, this refers to the volatization of the volatile component thereof and does not require that the non-volatile components thereof be emitted. 
       FIG. 1  is a side section view of an apparatus  1  according to the present invention in a horizontal orientation when the apparatus  1  is placed on a support. The apparatus  1  can be constructed as a disposable, single-use item or one that it is replenished with a volatile composition. The apparatus  1  comprises a container  10  containing a reservoir  11  having a volatile composition  9 . The container  10  may be made of a substantially vapor impermeable material designed to resist diffusion of a vapor phase of the volatile composition  9 . For example, the container  10  may be made of metal, glass, ceramic, porcelain, tile and plastic including but not limited to thermoplastics and other known materials suitable for thermoforming, injection molding and blow molding. A composite membrane  13  may be disposed within the container  10  and arranged to be in fluid communication with the volatile composition  9 . The apparatus  1  may further include a vapor impermeable substrate  14  adjacent to the membrane  13  wherein the vapor impermeable substrate  14  is configured to prevent release of the volatile composition  9  before use. Specifically, the apparatus  1  comprises an average vapor release rate from 0.2 mg/hr*cm 2  to 5 mg/hr*cm 2  at an air flow rate of 5 m/s and a temperature of 21 degrees Celsius which corresponds to a consumer perceived sensory feeling of a scent intensity that is not overwhelming, i.e. “just nice” scent intensity. 
     Composite Membrane 
     The composite membrane  13  includes a layer of porous material that is vapor permeable and is designed to be capable of wicking liquid, yet prevents free flow of liquid out of the composite membrane  13 . Referring to  FIG. 2 , the composite membrane  13  may comprise a first side  134  facing the reservoir  11  and a second side  136  opposite the first side  134 , wherein the second side  136  faces the atmosphere and away from the reservoir  11 . The first and second sides  134 ,  136  may be comprised in a substrate  12  such as for example a microporous membrane  12  that is uncoated (hereinafter “membrane”). The membrane  12  includes a thermoplastic organic polymer including a polyolefin. The membrane  12  defines a network of interconnecting pores communicating substantially throughout the microporous membrane  12 . Finely divided, particulate filler may be distributed throughout the membrane  12 . Subsequent materials may be applied to the membrane  12  to form a diffusion regulating coating  138  on at least one of the first side  134  and the second side  136  of the membrane  12 . In some examples, only the first side  134  of the membrane  12  receives the materials. In some examples, only the second side  136  of the membrane  12  receives the materials. In some examples, both the first side  134  and the second side  136  of the membrane  12  receive the materials. The diffusion regulating coating  138  may comprise a coating weight of 0.01 to 5.5 g/m 2 , from 0.05 to 2.0 g/m 2 , from 0.05 to 0.5 g/m 2  or different combinations of the upper and lower percentages described above or combinations of any integer in the ranges listed above. 
     Referring to  FIGS. 3A to 3C , the diffusion regulating coating  138  may cover at least a portion of at least one of the first side  134  and the second side  136 . The diffusion regulating coating  138  may be applied to the first side  134  of the membrane  12  (as shown in  FIG. 3A ), on the second side  136  of the membrane  12  (as shown in  FIG. 3B ) or on both first and second sides  134 ,  136  of the membrane  12  (as shown in  FIG. 3C ). 
     At least a part of the diffusion regulating coating  138  comprises a hydrophobic/oleophobic material  2 C comprising at least one fluoro-alkyl group. Without wishing to be bound by theory, a technical effect of providing a hydrophobic/oleophobic material  2 C is this results in an overall reduced vapor release rate in the apparatus  1  when the apparatus  1  is placed on an air vent. 
     In an exemplary embodiment, the diffusion regulating coating  138  may further comprise a polymer material  2 . Referring to  FIG. 4C , the polymer material may be disposed over at least a portion of the at least one of the first side  134  and the second side  136 . Referring to  FIG. 4C , the hydrophobic/oleophobic material  2 C is on the polymer material  2  defining the diffusion regulating coating  138 . 
     The polymer material  2  may be a hydrophilic material or a hydrophobic material. The polymer material  2  may be a hydrophobic material comprises one or more of a polysiloxane, polydimethylsiloxane, polyvinylidene fluoride, polyacrylonitrile and combinations thereof. 
     In an exemplary embodiment, the polymer material  2  is a hydrophilic material, preferably a hydrophilic coating layer  2 B as described hereinafter. 
     A. First Hydrophobic/Oleophobic Material 
     The hydrophobic/oleophobic material  2 C may be a first hydrophobic/oleophobic material  2 C may be applied to the membrane  12  to define the diffusion regulating coating  138 .  FIG. 4A  shows a cross section schematic view of the diffusion regulating coating  138  comprising the first hydrophobic/oleophobic material  2 C. The first hydrophobic/oleophobic material  2 C may be hydrophobic. The side of the membrane  12  over which the first hydrophobic/oleophobic material  2 C is applied may demonstrate a water contact angle of at least 105°, such as at least 110°, at least 115°, at least 120°, at least 125°, at least 130°, at least 135°, at least 140°, or at least 150°. The first hydrophobic/oleophobic material  2 C may be oleophobic. Oleophobic means that the side of the membrane  12  over which the first hydrophobic/oleophobic material  18  is applied demonstrates an oil rating of at least 6, such as at least 7 or at least 8, based on AATCC test method 118-2007. 
     The first hydrophobic/oleophobic material  2 C may be hydrophobic and oleophobic. In some examples, the first hydrophobic/oleophobic material  2 C may form a coating over the membrane  12 . In other examples, the first hydrophobic/oleophobic material  2 C may not form a coating over the membrane  12  but may instead be a surface treatment to the membrane  12 . Surface treatment, in this situation, means that the first hydrophobic/oleophobic material  2 C chemically reacts with the membrane  12  (such as the siliceous filler dispersed throughout the membrane  12 ) so as to form a hydrophobic/oleophobic region of the membrane  12 . 
     The first first hydrophobic/oleophobic material  2 C may include at least one fluoro-alkyl group and/or include a polymer including at least one fluoro-alkyl group. The first hydrophobic/oleophobic material  2 C may be a fluoro-alkyl group containing co-polymer. An exemplary hydrophobic/oleophobic material  2 C comprises one or more of a fluoroalkyl acrylate copolymer, perfluoroalkoxy polymer, polytetrafluoroethylene, fluorinated ethylene-propylene, polyethylenetetrafluoroethylene, perfluoro elastomers, perfluoropolyether, fluorosilicones, fluorosilanes, perfluorosilane and fluoroalkylsilsequioxane. 
     Further, the first hydrophobic/oleophobic material  2 C may be a polyacrylate co-polymer having a fluorinated polymer. In one non-limiting example, the first hydrophobic/oleophobic material  2 C may include products sold under the Unidyne tradename, available from Daikin Industries, Ltd. (Osaka, Japan). The first hydrophobic/oleophobic material  2 C may include any of the fluoro-alkyl group containing polymers or co-polymers described in U.S. Pat. No. 6,013,732 or 8,551,895, which are incorporated herein in their entireties by reference. The first hydrophobic/oleophobic material  2 C may include a polymer including some fluorination in the side chains or ends of the polymer, with the backbone of the polymer being substantially free of fluorine groups (distinguishable from perfluorinated polymers). 
     The first hydrophobic/oleophobic material  2 C may include an alkoxysilane compound having at least one fluoro-alkyl group. The first hydrophobic/oleophobic material  2 C including the alkoxysilane compound having at least one fluoro-alkyl group may interact with the membrane  12  (such as with the siliceous filler) through a condensation reaction with filler and may form a hydrophobic/oleophobic region of the membrane  12 . Non-limiting examples of the alkoxysilane compound having at least one fluoro-alkyl group are (tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane (see Formula I below) or (tridecafluoro-1,1,2,2 tetrahydrooctyl)trimethoxysilane. 
     
       
         
         
             
             
         
       
     
     As shown in  FIG. 4A , the first hydrophobic/oleophobic material  2 C may e applied over the first side  134  of the membrane  12  without any material applied over the second side  136  to define a diffusion regulating coating  138 . Alternatively, the first hydrophobic/oleophobic material  2 C may be applied over the second side  136  of the membrane  12  without any material applied over the first side  134  to define a diffusion regulating coating  138 . Alternatively, the first hydrophobic/oleophobic material  2 C may be applied over the first side  134  of the membrane  12  to define a first diffusion regulating coating  138  with a second material also being applied on the second side  136  (see  FIG. 3C ) to define a second diffusion regulating coating  138 . 
     In exemplary examples, additional material may be applied over top of or underneath the first hydrophobic/oleophobic material  2 C. A hydrophobic/oleophobic material(s), a hydrophilic coating layer(s), a hydrophobic material or some combination thereof may be applied to the membrane  12 . 
     Referring to  FIG. 4B , the first hydrophobic/oleophobic material  2 C is in direct contact with the first side  134  and/or the second side  136  of the membrane  12 . The first hydrophobic/oleophobic material  2 C may be applied to the first side  134  and/or the second side  136  of the membrane  12  using any suitable method such as spray application, curtain coating, dip coating, slot die coating, screen printing, and/or drawn-down coating, e.g., by means of a doctor blade or draw-down bar, techniques. 
     B. Second Hydrophobic/Oleophobic Material 
     Referring to  FIG. 4B , the membrane  12  may be coated with a second hydrophobic/oleophobic material  2 D. The second hydrophobic/oleophobic material  2 D may be applied to the first side  134  of the membrane  12  and/or the second side  136  of the membrane  12  to define a diffusion regulating coating  138  (as shown in  FIGS. 3A to 3C ). The second hydrophobic/oleophobic material  2 D may be hydrophobic. The side (such as the first side  134  or the second side  136 ) of the membrane  12  over which the second hydrophobic/oleophobic material  2 D is applied may demonstrate a water contact angle of at least 105°, such as at least 110°, at least 115°, at least 120°, at least 125°, at least 130°, at least 135°, at least 140°, or at least 150°. The second hydrophobic/oleophobic material  2 D may be chosen from any of the materials of the previously described first hydrophobic/oleophobic material  2 D. 
     Referring to  FIG. 4B , the second hydrophobic/oleophobic material  2 D may be applied over the second side  136  of the membrane  12  opposite the first side  134 , which has the first hydrophobic/oleophobic material  2 C applied thereon. The second hydrophobic/oleophobic material  2 D on the second side  136  may be the same hydrophobic/oleophobic material or a different hydrophobic/oleophobic material from the first hydrophobic/oleophobic material  2 C on the first side  134 . Additional materials may be applied over top of or underneath the second hydrophobic/oleophobic material  2 D. Alternatively, the second hydrophobic/oleophobic material  2 D may be a separate coating in direct contact with the first side  134  and/or the second side  136  of the membrane  12 . 
     The second hydrophobic/oleophobic material  2 D may be applied to the first side  134  and/or the second side  136  of the membrane  12  using any suitable method such as spray application, curtain coating, dip coating, slot die coating, screen printing, and/or drawn-down coating, e.g., by means of a doctor blade or draw-down bar, techniques. In one non-limiting embodiment, the second hydrophobic/oleophobic material  2 D is applied to the second side  136  of the membrane  12  using a draw-down method such that only the second side  136  of the membrane  12  is coated with second hydrophobic/oleophobic material  2 D and not the first side  134 . 
     C. Hydrophilic Coating Layer 
     Referring to  FIG. 4A , the membrane  12  may be coated with at least one hydrophilic coating  2 B. The hydrophilic coating  2 B may be applied to the first side  134  of the membrane and/or the second side  136  of the membrane  12  (as shown in  FIGS. 3A to 3C ). The hydrophilic coating  2 B may be hydrophilic. Hydrophilic means that the side of the membrane  12  over which the hydrophilic coating  2 B is applied demonstrates a water contact angle of less than 90° using the Kruss Drop Shape Analysis. The side of the membrane  12  over which the hydrophilic coating  2 B is applied may demonstrate a water contact angle of less than 85°, such as less than 80°, less than 70°, less than 60°, less than 50°, less than 40°, less than 30°, less than 20°, or less than 10°. The hydrophilic coating  2 B may include one or more of a polyoxazoline, triblock copolymers based on poly(ethylene glycol)-poly(propylene glycol)-poly(ethylene glycol), polyamide, oxidized polyethylene or its derivatives, polyethyleneoxide, polyvinylpyrrolidone, poly(meth)acrylic acid, polyethylene glycol or its derivatives, polypropylene oxide or its derivatives, a copolymer of poly(ethylene glycol) and polyethyleneoxide, polyvinyl alcohol, cellulose or its derivatives, collagen, polypeptides, guar, pectin, polyimide, poly(meth)acrylamide, polysaccharides, zwitterionic polymers, polyampholytes, and polyethylenimine. 
     As shown in  FIG. 4C , the hydrophilic coating  2 B may be applied over the second side  136  of the membrane  12  opposite the first side  134 , and the first hydrophobic/oleophobic material  2 C is applied thereover to define a diffusion regulating coating  138 . Additional materials may be applied over top of or underneath the hydrophilic coating  2 B. In some examples, the hydrophilic coating  2 B is in direct contact with the first side  134  and/or the second side  136  of the membrane  12 . Data demonstrating the reduced vapor release rate of inventive apparatus  1  according to the present invention is illustrated in the Examples described hereinafter with reference to  FIGS. 8 to 11 . 
     The hydrophilic coating  2 B may be applied to the first side  134  and/or the second side  136  of the membrane  12  using any suitable method such as spray application, curtain coating, dip coating, slot die coating, screen printing, and/or drawn-down coating, e.g., by means of a doctor blade or draw-down bar, techniques. 
     In some examples, the membrane  12  may be pre-treated (before any other material is applied to the membrane  12 , such as the first hydrophobic/oleophobic material  2 C, the second hydrophobic/oleophobic material  2 D, or other hydrophilic coating  2 B. The pre-treatment may be applied as a coating to the membrane  12 , and the pre-treatment may be a hydrophilic coating, as previously described. The pre-treatment may improve uniformity of the subsequently applied material(s), such as the hydrophobic/oleophobic materials or other hydrophilic coating(s). The hydrophilic pre-treatment may be applied to the membrane  12  using any suitable method. In one example, the membrane  12  is dipped into a bath including the hydrophilic pretreatment. 
     The hydrophilic pre-treatment may be applied using other art-related methods, such as spray application, curtain coating, slot die coating, screen printing, and/or drawn-down coating, e.g., by means of a doctor blade or draw-down bar, techniques. The hydrophilic pretreatment may be applied to the first side  134 , the second side  136 , or the entire membrane  12 . After the hydrophilic pre-treatment is applied, the pre-treated membrane  12  may be dried prior to any application of subsequent materials. 
     Further, certain characteristics of the composite membrane  13  may be altered by dispersing one or more fillers within the membrane  12 . Fillers can adjust the physical properties of the composite membrane  13 , such as strength, stiffness, and other tensile properties. There are many known filler and plasticizer materials, including, but not limited to, silica, clays, zeolites, carbonates, charcoals, and mixtures thereof. An example of a filled membrane  12  is an ultra-high molecular weight polyethylene (UHMWPE) membrane filled with silica, such as those described in U.S. Pat. No. 7,498,369. Although any suitable fill material and weight percentage may be used, typical fill percentages for silica, may be between about 50% to about 80%, about 60% to about 80%, about 70% to about 80%, or about 70% to about 75% of the total weight of the membrane. Examples of suitable membrane thicknesses include, but are not limited to between about 0.01 mm to about 1 mm, between about 0.1 mm to 0.4 mm, about 0.15 mm to about 0.35 mm, or about 0.25 mm. An exemplary microporous membrane  12  for the composite membrane  13  is described below. 
     Microporous Membrane 
     The microporous membrane  12  may include a thermoplastic organic polymer. In some examples, the thermoplastic organic polymer may be a substantially water-insoluble thermoplastic organic polymer. Substantially water-insoluble means having &lt;50 mg/L solubility in pure water at 25° C. 
     The types of polymers suitable for use in the membrane  12  are numerous. In general, any substantially water-insoluble thermoplastic organic polymer which can be extruded, calendered, pressed, or rolled into film, sheet, strip, or web may be used. The polymer may be a single polymer or it may be a mixture of polymers. The polymers may be homopolymers, copolymers, random copolymers, block copolymers, graft copolymers, atactic polymers, isotactic polymers, syndiotactic polymers, linear polymers, or branched polymers. When mixtures of polymers are used, the mixture may be homogeneous or it may comprise two or more polymeric phases. 
     An example of suitable substantially water-insoluble thermoplastic organic polymers includes thermoplastic polyolefins. The polyolefins may comprise at least 2 weight percent, such as at least 5 weight percent, at least 10 weight percent, at least least 15 weight percent, at least 25 weight percent, at least 35 weight percent, at least 45 weight percent, at least 55 weight percent, at least 65 weight percent, at least 75 weight percent, or at least 85 weight percent of the membrane  12 , based on the total weight of the membrane  12  including particulate filler. The polyolefins may comprise up to 95 weight percent, such as up to 85 weight percent, up to 75 weight percent, up to 65 weight percent, up to 55 weight percent, up to 45 weight percent, up to 35 weight percent, up to 25 weight percent, or up to 15 weight percent of the membrane  12 , based on the total weight of the membrane  12  including particulate filler. The polyolefin may comprise 2 to 95 weight percent of the membrane  12 , based on the total weight of the membrane  12  including particulate filler. Other examples of classes of suitable substantially water-insoluble organic polymers may include poly(halo-substituted olefins), polyesters, polyamides, polyurethanes, polyureas, poly(vinyl halides), poly(vinylidene halides), polystyrenes, poly(vinyl esters), polycarbonates, polyethers, polysulfides, polyimides, polysilanes, polysiloxanes, polycaprolactones, polyacrylates, and polymethacrylates. Contemplated hybrid classes, from which the substantially water-insoluble thermoplastic organic polymers may be selected include, for example, thermoplastic poly(urethane-ureas), poly(ester-amides), poly(silane-siloxanes), and poly(ether-esters). Further examples of suitable substantially water-insoluble thermoplastic organic polymers may include thermoplastic high density polyethylene, low density polyethylene, ultrahigh molecular weight polyethylene, polypropylene (atactic, isotactic, or syndiotactic), poly(vinyl chloride), polytetrafluoroethylene, copolymers of ethylene and acrylic acid, copolymers of ethylene and methacrylic acid, poly(vinylidene chloride), copolymers of vinylidene chloride and vinyl acetate, copolymers of vinylidene chloride and vinyl chloride, copolymers of ethylene and propylene, copolymers of ethylene and butene, poly(vinyl acetate), polystyrene, poly(omegaaminoundecanoic acid), poly(hexamethylene adipamide), poly(epsilon-caprolactam), and poly(methyl methacrylate). The recitation of these classes and example of substantially waterinsoluble thermoplastic organic polymers is not exhaustive, and are provided only for purposes of illustration. 
     Substantially water-insoluble thermoplastic organic polymers may in particular include, for example, poly(vinyl chloride), copolymers of vinyl chloride, or mixtures thereof. In an embodiment, the water-insoluble thermoplastic organic polymer includes an ultrahigh molecular weight polyolefin selected from: ultrahigh molecular weight polyolefin, e.g., essentially linear ultrahigh molecular weight polyolefin) having an intrinsic viscosity of at least 10 deciliters/gram; or ultrahigh molecular weight polypropylene, e.g., essentially linear ultrahigh molecular weight polypropylene) having an intrinsic viscosity of at least 6 deciliters/gram; or mixtures thereof. In a particular embodiment, the water-insoluble thermoplastic organic polymer includes ultrahigh molecular weight polyethylene, e.g., linear ultrahigh molecular weight polyethylene, having an intrinsic viscosity of at least 18 deciliters/gram. 
     Ultrahigh molecular weight polyethylene (UHMWPE) is not a thermoset polymer having an infinite molecular weight, but is technically classified as a thermoplastic. However, because the molecules are substantially very long chains, UHMWPE softens when heated but does not flow as a molten liquid in a normal thermoplastic manner. The very long chains and the peculiar properties they provide to UHMWPE may contribute in large measure to the desirable properties of the membrane  12  made using this polymer. 
     As indicated earlier, the intrinsic viscosity of the UHMWPE is at least about 10 deciliters/gram. Usually the intrinsic viscosity is at least about 14 deciliters/gram. Often the intrinsic viscosity is at least about 18 deciliters/gram. In many cases the intrinsic viscosity is at least about 19 deciliters/gram. Although there is no particular restriction on the upper limit of the intrinsic viscosity, the intrinsic viscosity is frequently in the range of from about 10 to about 39 deciliters/gram, e.g., in the range of from about 14 to about 39 deciliters/gram. In some cases the intrinsic viscosity of the UHMWPE is in the range of from about 18 to about 39 deciliters/gram, or from about 18 to about 32 deciliters/gram. 
     The nominal molecular weight of UHMWPE is empirically related to the intrinsic viscosity of the polymer according to the equation: 
         M (UHMWPE)=5.3×104[η]1.37
 
     where M(UHMWPE) is the nominal molecular weight and [η] is the intrinsic viscosity of the UHMW polyethylene expressed in deciliters/gram. 
     As used herein, intrinsic viscosity is determined by extrapolating to zero concentration the reduced viscosities or the inherent viscosities of several dilute solutions of the UHMWPE where the solvent is freshly distilled decahydronaphthalene to which 0.2 percent by weight, 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid, neopentanetetrayl ester [CAS Registry No. 6683-19-8] has been added. The reduced viscosities or the inherent viscosities of the UHMWPE are ascertained from relative viscosities obtained at 135° C. using an Ubbelohde No. 1 viscometer in accordance with the general procedures of ASTM D 4020-81, except that several dilute solutions of differing concentration are employed. ASTM D 4020-81 is, in its entirety, incorporated herein by reference. 
     In one particular example, the matrix comprises a mixture of substantially linear ultrahigh molecular weight polyethylene having an intrinsic viscosity of at least 10 deciliters/gram, and lower molecular weight polyethylene (LMWPE) having an ASTM D 1238-86 Condition E melt index of less than 50 grams/10 minutes and an ASTM D 1238-86 Condition F melt index of at least 0.1 gram/10 minutes. The nominal molecular weight of LMWPE is lower than that of the UHMWPE. LMWPE is thermoplastic and many different types are known. One method of classification is by density, expressed in grams/cubic centimeter and rounded to the nearest thousandth, in accordance with ASTM D 1248-84 (reapproved 1989), as summarized as follows: 
     
       
         
           
               
               
               
             
               
                 TABLE 1 
               
               
                   
               
               
                 Type 
                 Abbreviation 
                 Density (g/cm3) 
               
               
                   
               
             
            
               
                 Low Density Polyethylene 
                 LDPE 
                 0.910-0.925 
               
               
                 Medium Density Polyethylene 
                 MDPE 
                 0.926-0.940 
               
               
                 High Density Polyethylene 
                 HDPE 
                 0.941-0.965 
               
               
                   
               
            
           
         
       
     
     Any or all of these polyethylenes may be used as the LMWPE in the present invention. For some applications, HDPE, may be used because it ordinarily tends to be more linear than MDPE or LDPE. ASTM D 1248-84 (Reapproved 1989) is, in its entirety, incorporated herein by reference. 
     Processes for making the various LMWPE&#39;s are well known and well documented. They include the high pressure process, the Phillips Petroleum Company process, the Standard Oil Company (Indiana) process, and the Ziegler process. 
     The ASTM D 1238-86 Condition E (that is, 190° C. and 2.16 kilogram load) melt index of the LMWPE is less than about 50 grams/10 minutes. Often the Condition E melt index is less than about 25 grams/10 minutes. Typically, the Condition E melt index is less than about 15 grams/10 minutes. 
     The ASTM D 1238-86 Condition F (that is, 190° C. and 21.6 kilogram load) melt index of the LMWPE is at least 0.1 gram/10 minutes. In many cases the Condition F melt index is at least about 0.5 gram/10 minutes. Typically, the Condition F melt index is at least about 1.0 gram/10 minutes. ASTM D 1238-86 is, in its entirety, incorporated herein by reference. 
     Sufficient UHMWPE and LMWPE should be present in the matrix to provide their properties to the membrane  12 . Other thermoplastic organic polymers may also be present in the matrix so long as their presence does not materially affect the properties of the membrane  12  in an adverse manner. One or more other thermoplastic polymers may be present in the matrix. The amount of the other thermoplastic polymer which may be present depends upon the nature of such polymer. Examples of thermoplastic organic polymers which may optionally be present include, but are not limited to, poly(tetrafluoroethylene), polypropylene, copolymers of ethylene and propylene, copolymers of ethylene and acrylic acid, and copolymers of ethylene and methacrylic acid. If desired, all or a portion of the carboxyl groups of carboxyl containing copolymers may be neutralized with sodium, zinc, or the like. 
     In some examples the UHMWPE and the LMWPE together constitute at least about 65 percent by weight of the polymer of the matrix. In some examples, the UHMWPE and the LMWPE together constitute at least about 85 percent by weight of the polymer of the matrix. In some examples, the other thermoplastic organic polymers are substantially absent so that the UHMWPE and the LMWPE together constitute substantially 100 percent by weight of the polymer of the matrix. In some examples, the UHMWPE constitutes substantially all of the polymer of the matrix (e.g., LMWPE is not included in the formulation). 
     The UHMWPE may constitute at least one percent by weight of the polymer of the matrix. Where the UHMWPE and the LMWPE together constitute 100 percent by weight of the polymer of the matrix of the membrane  12 , the UHMWPE may constitute greater than or equal to 40 percent by weight of the polymer of the matrix, such as greater than or equal to 45 percent by weight, or greater than or equal to 48 percent by weight, or greater than or equal to 50 percent by weight, or greater than or equal to 55 percent by weight of the polymer of the matrix. Also, the UHMWPE may constitute less than or equal to 99 percent by weight of the polymer of the matrix, such as less than or equal to 80 percent by weight, or less than or equal to 70 percent by weight, or less than or equal to 65 percent by weight, or less than or equal to 60 percent by weight of the polymer of the matrix. The level of UHMWPE comprising the polymer of the matrix may range between any of these values inclusive of the recited values. 
     Likewise, where the UHMWPE and the LMWPE together constitute 100 percent by weight of the polymer of the matrix of the membrane  12 , the LMWPE may constitute greater than or equal to 1 percent by weight of the polymer of the matrix, such as greater than or equal to 5 percent by weight, or greater than or equal to 10 percent by weight, or greater than or equal to 15 percent by weight, or greater than or equal to 20 percent by weight, or greater than or equal to 25 percent by weight, or greater than or equal to 30 percent by weight, or greater than or equal to 35 percent by weight, or greater than or equal to 40 percent by weight, or greater than or equal to 45 percent by weight, or greater than or equal to 50 percent by weight, or greater than or equal to 55 percent by weight of the polymer of the matrix. Also, the LMWPE may constitute less than or equal to 70 percent by weight of the polymer of the matrix, such as less than or equal to 65 percent by weight, or less than or equal to 60 percent by weight, or less than or equal to 55 percent by weight, or less than or equal to 50 percent by weight, or less than or equal to 45 percent by weight of the polymer of the matrix. The level of the LMWPE may range between any of these values inclusive of the recited values. 
     It should be noted that for any of the previously described membranes  12  of the present invention, the LMWPE may comprise high density polyethylene. The membrane  12  may also include finely divided, particulate filler distributed throughout, as later described. The membrane  12  may also include minor amounts of other materials. Minor amounts may be less than or equal to 10 percent by weight, based on total weight of the membrane  12 , particulate filler and other materials. The other materials used in processing, may be lubricants, processing plasticizers, organic extraction liquids, water, and the like. Further other materials introduced for particular purposes, such as thermal, ultraviolet and dimensional stability, may optionally be present in the membrane  12  in small amounts, e.g., less than or equal to 15 percent by weight, based on total weight of the membrane  12 , particulate filler, and other materials. Examples of such further materials include, but are not limited to, antioxidants, ultraviolet light absorbers, reinforcing fibers such as chopped glass fiber strand, and the like. The balance of the membrane  12 , exclusive of filler and any coating, printing ink, or impregnant applied for one or more special purposes is essentially the thermoplastic organic polymer. 
     Finely Divided, Particulate Filler 
     As previously mentioned, the membrane  12  may include finely divided, particulate filler distributed through the membrane  12 . In one example, the particulate filler includes siliceous particles having particulate silica. The particulate filler may include an organic particulate material and/or an inorganic particulate material. The particulate filler may or may not be colored. For example, the particulate filler material may be a white or off-white particulate filler material, such as siliceous or clay particulate material. The particulate filler may be substantially water-insoluble filler particles. Substantially water-insoluble means having &lt;50 mg/L solubility in pure water at 25° C. 
     The finely divided substantially water-insoluble filler particles may constitute from 10 to 90 percent by weight of the membrane  12 , the filler particles, and other materials (excluding coating applied to the membrane  12 ). For example, such filler particles may constitute from 20 percent to 90 percent by weight of the membrane  12 , the filler particles, and other materials (excluding coating applied to the membrane  12 ), such as from 30 percent to 70 percent, or such as from 40 percent to 60 percent. 
     The finely divided, particulate filler may be in the form of ultimate particles, aggregates of ultimate particles, or a combination of both. At least about 90 percent by weight of the particulate filler used in preparing the membrane  12  may have gross particle sizes in the range of from 0.5 to about 200 micrometers, such as from 1 to 100 micrometers, as determined by the use of a laser diffraction particle size instrument, LS230 from Beckman Coulton, which is capable of measuring particle diameters as small as 0.04 micrometers. At least 90 percent by weight of the particulate filler may have a gross particle sizes in the range of from 5 to 40, e.g., 10 to 30 micrometers. The sizes of the particulate filler agglomerates may be reduced during processing of the ingredients used to prepare the membrane  12 . Accordingly, the distribution of gross particle sizes in the membrane  12  may be smaller than in the raw filler itself. 
     Non-limiting examples of suitable organic and inorganic particulate filler that may be used in the membrane  12  of the present invention may include those described in U.S. Pat. No. 6,387,519 B1 at column 9, line 4 to column 13, line 62, the cited portions of which are incorporated herein by reference. 
     In a particular embodiment of the present invention, the particulate filler material includes siliceous materials. Non-limiting examples of siliceous fillers that may be used to prepare the microporous material include silica, mica, montmorillonite, kaolinite, nanoclays such as cloisite, which is available from Southern Clay Products (Gonzales, Tex.), talc, diatomaceous earth, vermiculite, natural and synthetic zeolites, calcium silicate, aluminum silicate, sodium aluminum silicate, aluminum polysilicate, alumina silica gels and glass particles. In addition to the siliceous fillers, other finely divided particulate substantially waterinsoluble fillers optionally may also be employed. Non-limiting examples of such optional particulate fillers include carbon black, charcoal, graphite, titanium oxide, iron oxide, copper oxide, zinc oxide, antimony oxide, zirconia, magnesia, alumina, molybdenum disulfide, zinc sulfide, barium sulfate, strontium sulfate, calcium carbonate, and magnesium carbonate. Some of such optional fillers are color-producing fillers and, depending on the amount used, may add a hue or color to the microporous material. In a non-limiting embodiment, the siliceous filler may include silica and any of the aforementioned clays. Non-limiting examples of silicas include precipitated silica, silica gel, fumed silica, and combinations thereof. 
     Silica gel is generally produced commercially by acidifying an aqueous solution of a soluble metal silicate, e.g., sodium silicate, at low pH with acid. The acid employed is generally a strong mineral acid such as sulfuric acid or hydrochloric acid, although carbon dioxide can be used. Inasmuch as there is essentially no difference in density between the gel phase and the surrounding liquid phase while the viscosity is low, the gel phase does not settle out, that is to say, it does not precipitate. Consequently, silica gel may be described as a non-precipitated, coherent, rigid, three-dimensional network of contiguous particles of colloidal amorphous silica. The state of subdivision ranges from large, solid masses to submicroscopic particles, and the degree of hydration from almost anhydrous silica to soft gelatinous masses containing on the order of 100 parts of water per part of silica by weight. 
     Precipitated silica generally is produced commercially by combining an aqueous solution of a soluble metal silicate, ordinarily alkali metal silicate such as sodium silicate, and an acid so that colloidal particles of silica will grow in a weakly alkaline solution and be coagulated by the alkali metal ions of the resulting soluble alkali metal salt. Various acids may be used, including but not limited to mineral acids. Non-limiting examples of acids that may be used include hydrochloric acid and sulfuric acid, but carbon dioxide can also be used to produce precipitated silica. In the absence of a coagulant, silica is not precipitated from solution at any pH. In a non-limiting embodiment, the coagulant used to effect precipitation of silica may be the soluble alkali metal salt produced during formation of the colloidal silica particles, or it may be an added electrolyte, such as a soluble inorganic or organic salt, or it may be a combination of both. 
     Many different precipitated silicas can be employed as the siliceous filler used to prepare the microporous material. Precipitated silicas are well-known commercial materials, and processes for producing them are described in detail in many United States patents, including U.S. Pat. Nos. 2,940,830 and 4,681,750. The average ultimate particle size (irrespective of whether or not the ultimate particles are agglomerated) of precipitated silica used to prepare the microporous material is generally less than 0.1 micrometer, e.g., less than 0.05 micrometer or less than 0.03 micrometer, as determined by transmission electron microscopy. Precipitated silicas are available in many grades and forms from PPG Industries, Inc. (Pittsburgh, Pa.). These silicas are sold under the Hi-Sil trademark. 
     For purposes of the present invention, the finely divided particulate siliceous filler can make up at least 50 percent by weight, e.g., at least 65 or at least 75 percent by weight, or at least 90 percent by weight of the particulate filler material. The siliceous filler may make up from 50 to 90 percent by weight, e.g., from 60 to 80 percent by weight, of the particulate filler, or the siliceous filler may make up substantially all (over 90 percent by weight) of the particulate filler. 
     The particulate filler, e.g., the siliceous filler, typically has a high surface area, which allows the filler to carry much of the processing plasticizer composition used to produce the microporous material of the present invention. High surface area fillers are materials of very small particle size, materials that have a high degree of porosity, or materials that exhibit both of such properties. The surface area of the particulate filler, e.g., the siliceous filler particles, can range from 20 to 1000 square meters per gram, e.g., from 25 to 400 square meters per gram, or from 40 to 200 square meters per gram, as determined by the Brunauer, Emmett, Teller (BET) method according to ASTM D 1993-91. The BET surface area is determined by fitting five relative pressure points from a nitrogen sorption isotherm measurement made using a Micromeritics Tri Star3000™ instrument. A FlowPrep-060™ station can be used to provide heat and continuous gas flow during sample preparation. Prior to nitrogen sorption, silica samples are dried by heating to 160° C. in flowing nitrogen (PS) for 1 hour. The surface area of any non-siliceous filler particles used may also be within one of these ranges. The filler 
     particles may be substantially water-insoluble and may also be substantially insoluble in any organic processing liquid used to prepare the microporous material. Substantially waterinsoluble means having &lt;50 mg/L solubility in pure water at 25° C. Substantially insoluble in an organic processing liquid means having &lt;50 mg/L solubility in the organic processing liquid. This may facilitate retention of the particulate filler within the microporous material. The membrane  12  may also include a network of interconnecting pores, which communicate substantially throughout the membrane  12 . On a coating-free, printing ink free and impregnant-free basis, pores typically constitute from 35 to 95 percent by volume, based on the total volume of the membrane  12 , when made by the processes as further described herein. The pores may constitute from 60 to 75 percent by volume of the membrane  12 , based on the total volume of the microporous material. As used herein, the porosity (also known as void volume) of the membrane  12 , expressed as percent by volume, is determined according to the following equation:
 
Porosity=100[1−d1/d2] where, d1 is the density of the sample, which is determined from the sample weight and the sample volume as ascertained from measurements of the sample dimensions; and d2 is the density of the solid portion of the sample, which is determined from the sample weight and the volume of the solid portion of the sample. The volume of the solid portion of the microporous material is determined using a Quantachrome stereopycnometer (Quantachrome Instruments (Boynton Beach, Fla.)) in accordance with the operating manual accompanying the instrument.
 
     The volume average diameter of the pores of the membrane  12  is determined by mercury porosimetry using an Autoscan mercury porosimeter (Quantachrome Instruments (Boynton Beach, Fla.)) in accordance with the operating manual accompanying the instrument. The volume average pore radius for a single scan is automatically determined by the porosimeter. In operating the porosimeter, a scan is made in the high pressure range (from 138 kilopascals absolute to 227 megapascals absolute). If 2 percent or less of the total intruded volume occurs at the low end (from 138 to 250 kilopascals absolute) of the high pressure range, the volume average pore diameter is taken as twice the volume average pore radius determined by the porosimeter. Otherwise, an additional scan is made in the low pressure range (from 7 to 165 kilopascals absolute) and the volume average pore diameter is calculated according to the equation: 
         d= 2[ v 1 r 1/ w 1+ v 2 r 2/ w 2]/[ v 1/ w 1+ v 2/ w 2] 
     where, d is the volume average pore diameter; v1 is the total volume of mercury intruded in the high pressure range; v2 is the total volume of mercury intruded in the low pressure range; r1 is the volume average pore radius determined from the high pressure scan; r2 is the volume average pore radius determined from the low pressure scan; w3 is the weight of the sample subjected to the high pressure scan; and w2 is the weight of the sample subjected to the low pressure scan. 
     Generally on a coating-free, printing ink-free and impregnant-free basis, the volume average diameter of the pores (mean pore size) of the membrane  12  may be up to 0.5 micrometers, such as up to 0.3 micrometers, or up to 0.2 micrometers. The average diameter of the pores may be at least 0.02 micrometers, such as at least 0.04 micrometers, or at least 0.05 micrometers. The volume average diameter of the pores, on this basis, may range between any of these values, inclusive of the recited values. For example, the volume average diameter of the pores of the membrane  12  may range from 0.02 to 0.15 micrometers, or from 0.02 to 0.1 micrometers, or from 0.02 to 0.075 micrometers, in each case inclusive of the recited values. 
     In the course of determining the volume average pore diameter by means of the above described procedure, the maximum pore radius detected may also be determined. This is taken from the low pressure range scan, if run; otherwise it is taken from the high pressure range scan. The maximum pore diameter of the microporous material is typically twice the maximum pore radius. 
     Coating, printing and impregnation processes may result in filling at least some of the pores of the membrane  12 . In addition, such processes may also irreversibly compress the membrane  12 . Accordingly, the parameters with respect to porosity, volume average diameter of the pores, and maximum pore diameter are determined for the membrane  12  prior to application of one or more of these processes. The membrane  12 , including the finely divided, particulate filler and/or other materials (excluding coating applied to the membrane  12 ) may have a density between 0.4 g/cm3 and 1.0 g/cm3. The density can range between any of the above-stated values, inclusive of the recited values. As used herein and in the claims, the density of the membrane  12  is determined by measuring the weight and volume of a sample of the microporous material. 
     The porosity of the membrane  12  may be measured in terms of the rate of air flow through a sample, herein measured and reported as Gurley porosity. The Gurley porosity of the membrane  12 , including the finely divided, particulate filler and/or other materials (excluding coating applied to the membrane  12 ) may be greater than 15 seconds, such as greater than 100 seconds, greater than 200 seconds, greater than 300 seconds, greater than 400 seconds, or greater than 500 seconds. Gurley porosity is determined using a Gurley densometer, model 4340, manufactured by GPI Gurley Precision Instruments of (Troy, N.Y.) The Gurley porosity reported was a measure of the rate of air flow through a sample or it&#39;s resistance to an air flow through the sample. The unit of measure is a “Gurley second” and represents the time in seconds to pass 100 cc of air through a 1 inch square (6.4×10-4 m2) area using a pressure differential of 4.88 inches of water (12.2×102 Pa). Lower values equate to less air flow resistance (more air is allowed to pass freely). The measurements were completed using the procedure listed in the manual, MODEL 4340 Automatic Densometer and Smoothness Tester Instruction Manual. TAPPI method T 460 om-06-Air Resistance of Paper may also be referenced for the basic principles of the measurement. 
     Volatile Composition 
     In an exemplary embodiment, the volatile composition  9  may be configured such that the composition  9  comprises at least 20% of perfume raw materials having an average vapor pressure at 25 degrees Celsius of greater than or equal to 0.01 torr. 
     The volatile composition  9  may comprise one or more perfume compounds, or a mixture of perfume compounds. The volatile composition  9  can be in the form of perfume oil and can include one or more essential oils, volatile organic compounds, or mixtures thereof. Furthermore, the volatile composition  9  can include synthetically or naturally formed materials. Examples include, but are not limited to: oil of bergamot, bitter orange, lemon, mandarin, caraway, cedar leaf, clove leaf, cedar wood, geranium, lavender, orange, origanum, petitgrain, white cedar, patchouli, neroili, rose absolute, and the like. 
     The volatile composition  9  may alternatively be in the form of a crystalline solid, which has the ability to sublime into the vapor phase at ambient temperatures or be used to fragrance a liquid. Any suitable crystalline solid in any suitable amount or form may be used. For example, suitable crystalline solids include but are not limited to: vanillin, ethyl vanillin, coumarin, tonalid, calone, heliotropene, musk xylol, cedrol, musk ketone benzohenone, raspberry ketone, methyl naphthyl ketone beta, phenyl ethyl salicylate, veltol, maltol, maple lactone, proeugenol acetate, evemyl, and the like. 
     In the case of air freshener or fragrances, different volatile materials can be used together that are similar, related, complementary, and/or contrasting. In addition to volatile materials, the apparatus  1  may include any known compounds configured to neutralize odors. 
     The volatile composition may, optionally, include odor masking agents, odor blocking agents, and/or diluents. “Odor blocking” refers to the ability of a compound to dull the human sense of smell. “Odor-masking” refers to the ability of a compound to mask or hide a malodorous compound. Odor-masking may include a compound with a non-offensive or pleasant smell that is dosed such it limits the ability to sense a malodorous compound. Odor-masking may involve the selection of compounds which coordinate with an anticipated malodor to change the perception of the overall scent provided by the combination of odorous compounds. Exemplary diluents include dipropylene glycol methyl ether, and 3-methoxy-3-methyl-1-butanol, and mixtures thereof. The volatile composition may also, optionally, include perfume raw materials that solely provide a hedonic benefit (i.e. perfume raw materials which do not prevent mold yet provide a pleasant fragrance). The volatile composition  9  may be comprised in an apparatus  1  as shown in the figures according to the present invention. For the purposes of illustrating the present invention in detail, the invention is described below in connection with automobiles. However, it will be appreciated that the invention may be implemented in any interior occupancy space employing an HVAC system. 
     Referring to  FIG. 1 , the vapor impermeable substrate  14  may be releasably attached to a periphery of the membrane  13  to form a removeable cover for the apparatus  1 . The vapor impermeable substrate  14  may be rupturable to allow the volatile composition  12  to pass through when ruptured. For example, as shown in  FIGS. 6A and 6B , the vapor impermeable substrate  14  may be a rupturable substrate disposed adjacent to the composite membrane  13  and attached to an inner periphery of the container  10  to form a sealed reservoir adjacent the membrane  13 . 
     The apparatus  1  may be configured for use in any desired orientation, including but not limited to a vertical orientation such as shown in  FIG. 2 .  FIG. 2  shows a side schematic view of the apparatus  1  of  FIG. 1  wherein the apparatus  1  is substantially the same as the apparatus  1  of  FIG. 1  except that when the apparatus  1  is in use, the membrane  13  comprises a first side  134  disposed in fluid communication with the volatile composition  12  and a second side  136  facing the environment and away from the volatile composition  12  when the vapor impermeable substrate  14  is removed when the user needs to activate the apparatus  1 . 
     The method of the present invention may be directed to a method of controlled release of a volatile composition in an interior occupancy space, the method comprising the steps of: 
     operably connecting an apparatus  1  of the present invention to a mounting portion; and attaching the mounting portion to an air vent  33 . 
     The apparatus  1  of the present invention can be configured for use in a variety of applications to deliver a volatile composition  9  to the atmosphere and/or a surface. 
     Accordingly, the specific physical properties of the membrane  13  may be chosen based on the specific desired use of the apparatus  1 , designed to be activated by peeling off the vapor impermeable substrate  14  or by rupturing the vapor impermeable substrate  14 . Examples of suitable physical parameters of the vapor impermeable substrate  14  suitable for an apparatus  1  designed to be activated by rupturing the vapor impermeable substrate  14  will be described hereinafter in the description. 
     The vapor impermeable substrate  14  may be made of any material that can be ruptured with a pre-determined applied force, with or without the presence of an element, such as rupture element, to aid in such rupture. In embodiments where the vapor impermeable substrate  40  is intended to contain the volatile composition when the apparatus  1  is not in use, the vapor impermeable substrate  40  may be made from any suitable barrier material that reduces or prevents evaporation of the volatile composition  12 . Such materials may be impermeable to vapors and liquids. Suitable barrier materials for the vapor impermeable substrate  40  include, but are not limited to coated or uncoated films, such as polymeric films, webs, foils, and composite materials such as foil/polymeric film laminates. An example of a foil that may be used as a barrier material is a micron aluminum foil including a nitrocellulose protective lacquer, a polyurethane primer, and a 15 g/m2 polyethylene coating (Lidfoil 118-0092), available from Alcan Packaging. Suitable polymeric films include, but are not limited to, polyethylene terephtalate (PET) films, acrylonitrile copolymer barrier films such as, for example, those sold under the tradename Barex® by INOES, ethylene vinyl alcohol films, and combinations thereof. It is also contemplated that coated barrier films may be utilized as the vapor impermeable substrate  14 . Such coated barrier films include, but are not limited to, metallized PET, metalized polypropylene, silica or alumina coated film. 
       FIG. 5  is a perspective view of components in a variation of an apparatus  1  according to the present invention. The apparatus  1  of  FIG. 5  comprise substantially the same features as the apparatus  1  of  FIG. 1  with additional components described as follows. 
     Referring to  FIG. 5 , the apparatus  1  comprises a housing  40  having a front cover  42  and a rear frame  44 , the front cover  42  and the rear frame  44  defining an interior space. The rear frame  44  may comprise a pair of lugs  48  disposed adjacent a frame opening  46  and extending from the rear frame  44 . The lugs  48  may be shaped and sized to engage with pins  25  extending from a mounting portion  23 . The mounting portion  23  may be attached to, movably attached to, rotatably attached to, or pivotally attached to the apparatus  1 . In an exemplary example, the mounting portion  23  may be an actuator  23  configured to be movable relative to the housing  40  for activating the apparatus  1 . In that example, the rear frame  44  may be provided with the frame opening  46  located substantially in the center of the rear frame  44 . The mounting portion  23  may be configured as a movable or resilient clip for attaching the apparatus  1  to an air vent  33  as shown in  FIG. 7 . 
     When the volatile composition  12  is a liquid volatile composition, the apparatus  1  may comprise a rupturable vapor impermeable substrate  14  sealably attached to and covering the reservoir  11  to prevent the volatile composition  12  from being released until the apparatus  1  is activated. The rupturable vapor impermeable substrate  14  may be ruptured to release the volatile composition  12  by actuating a rupture mechanism  50  positioned adjacent to the rupturable vapor impermeable substrate  14 . The rupture mechanism  50  comprises a movable member  52  movably attached to an outer frame  53  by a resilient member  54 . The resilient member  54  may be formed of one or more springs. One or more rupture elements  56  are arranged within the rupture mechanism  50  to puncture holes in the rupturable vapor impermeable substrate  14 . The rupture element  56  may be a pin. The composite membrane  13  may be sealably attached to a flange  57  located at the periphery  58  of the container  10 . The composite membrane  13  encloses the container  10 , the volatile composition  12 , the rupturable vapor impermeable substrate  14 , and the rupture mechanism  50 . The composite membrane  13  may be configured to flex when a pressure or an actuation force is applied on the composite membrane  13  through the mounting portion  23 . 
       FIGS. 6A and 6B  show the apparatus  1  of  FIG. 5  in its assembled form with the volatile composition  12  and in a first position before activation ( FIG. 6A ) and a second position after activation ( FIG. 6B ). Referring to  FIG. 6A , to activate the apparatus  1 , a user rotates the mounting portion  23  relative to the housing  40  to move the composite membrane  13  and at least a portion of the rupture element  56  toward and to puncture the rupturable vapor impermeable substrate  14  and release at least a portion of the volatile composition  9  from the container  10  such that the portion of the volatile composition  9  evaporates from the apparatus  1 . It will be appreciated that the mounting portion  23  may be configured using known mechanical methods to move linearly or in a rotary motion so as to move the composite membrane  13  and at least a portion of the rupture element  56  toward and to puncture the rupturable vapor impermeable substrate  14 . Once the rupturable vapor permeable substrate  14  is pierced, the volatile composition  9  flows out of the container  10 , wets the composite membrane  13  and is then delivered to the atmosphere surroundings through evaporation from the composite membrane  13  via the second side  136 . The composite membrane  13  is configured to prevent the liquid phase of the volatile composition  9  from flowing out of the composite membrane  13  but enables vaporization of a vapor phase of the volatile composition  9  from the second side  136  so that the volatile composition  9  is delivered to the environment. 
     The following examples are intended to more fully illustrate the present invention and are not to be construed as limitations of the present invention since many variations thereof are possible without departing from the scope of the present invention. All parts, percentages and ratios used herein are expressed as percent weight unless otherwise specified. 
     EXAMPLES 
     Test equipment/materials and test volatile compositions are first described under Materials, then Test Methods are provided, and lastly results are discussed. Data is provided demonstrating the apparatus  1  of the present invention having reduced vapor release rate when used in an air conditioning system. Equipment and materials used in the Test Methods described hereinafter are listed in Table 2 below. The inventive and comparative examples are provided in Table 3 below. The volatile compositions used in the examples are prepared using conventional methods. 
     Materials 
       
     
       
         
           
               
             
               
                 TABLE 2 
               
             
            
               
                   
               
               
                 Equipment/Materials 
               
            
           
           
               
               
            
               
                 Example 
                 Materials/Details 
               
               
                   
               
               
                 Fan (Example to simulate fan of 
                 SONA 7″ Desk &amp; Clip fan Model No. SFD1218 
               
               
                 an air conditioning system in an 
                 VOLT 220-240 V 50 Hz 
               
               
                 automobile) 
                 Watt 25 W 
               
               
                 Anemometer for measuring air 
                 Testo 425 Thermal Anemometer 
               
               
                 flow rate 
               
               
                 Comparative Air Freshener 
                 Air Freshener Components as shown in FIG. 5 
               
               
                 Example 1 (“Comparative 
                 Microporous membrane (Commercially available as Teslin 
               
               
                 Example 1”) 
                 HD1100) of Table 4 
               
               
                   
                 Volatile composition 1 
               
               
                 Comparative Air Freshener 
                 Air Freshener Components as shown in FIG. 5 
               
               
                 Example 2 (“Comparative 
                 Microporous membrane (Commercially available from 
               
               
                 Example 2”) 
                 PPG Industries as Teslin HD1100) of Table 4 
               
               
                   
                 Inventive Volatile composition 1 of Table 3 
               
               
                 Inventive Air Freshener Example 
                 Air Freshener Components as shown in FIG. 5 
               
               
                 2 (“Inventive Example 2”) 
                 Composite membrane sample 1 of Table 4 
               
               
                   
                 Inventive Volatile composition 1 of Table 3 
               
               
                 Inventive Air Freshener Example 
                 Air Freshener Components as shown in FIG. 5 
               
               
                 (“Inventive Example 3”) 
                 Composite membrane sample 2 of Table 4 
               
               
                   
                 Volatile composition 1 of Table 3 
               
               
                 Inventive Air Freshener Example 
                 Air Freshener Components as shown in FIG. 5 
               
               
                 (“Inventive Example 4”) 
                 Composite membrane sample 3 of Table 4 
               
               
                   
                 Volatile composition 1 of Table 3 
               
               
                 Inventive Air Freshener Example 
                 Air Freshener Components as shown in FIG. 5 
               
               
                 (“Inventive Example 5”) 
                 Composite membrane sample 2 of Table 4 
               
               
                   
                 Volatile composition 2 of Table 3 
               
               
                 Inventive Air Freshener Example 
                 Air Freshener Components as shown in FIG. 5 
               
               
                 (“Inventive Example 6”) 
                 Composite membrane sample 3 of Table 4 
               
               
                   
                 Volatile composition 2 of Table 3 
               
               
                   
               
            
           
         
       
     
     Air Freshener Example Preparation 
     Inventive Examples are prepared according to the following steps:
         1. Using a heat sealer at 380 deg F., 50 psig and 3 s, attach the uncoated side of the composite membrane on a polyethylene-based thermoform container having a reservoir (see container  10  of  FIG. 5 ). The effective membrane area (evaporative surface area) of the composite membrane is 7 cm 2 .   2. Add 2.4 ml of a volatile composition to the prepared membrane sealed thermoform container.   3. Place the thermoform reservoir containing the volatile composition inside an apparatus as shown in  FIG. 5 .       

     Comparative Examples are prepared according to the above steps and differs in that the membrane used is uncoated. 
     For the test methods/calculations described hereinafter, any volatile composition suitable for use in air fresheners or vapor phase systems may be employed. For illustrative purposes as well as for the subsequent examples, the volatile composition is a perfume composition as shown in the formulation of Table 3 below. The volatile composition, however, may constitute any number of materials suitable for air freshening as long as at least 20% of the perfume raw materials have an average vapor pressure greater than or equal to 0.01 torr at 25 degrees Celsius. 
     
       
         
           
               
               
               
             
               
                 TABLE 3 
               
             
            
               
                   
               
               
                 Perfume Raw Materials 
                 Inventive Volatile 
                 Inventive Volatile 
               
            
           
           
               
               
               
               
            
               
                 Vapor 
                 Vapor 
                 Composition 1 
                 Composition 2 
               
               
                 Pressure 
                 Pressure 
                 % of perfume raw 
                 % of perfume raw 
               
               
                 25° C. 
                 25° C. 
                 materials by weight 
                 materials by weight 
               
               
                 Low 
                 High 
                 of the composition 
                 of the composition 
               
               
                   
               
            
           
           
               
               
               
               
            
               
                 0.00001 
                 0.001 
                 0.078 
                 0.932 
               
               
                 0.001 
                 0.01 
                 16.833 
                 13.992 
               
               
                 0.01 
                 0.1 
                 30.538 
                 38.505 
               
               
                 0.1 
                 0.3 
                 29.028 
                 25.969 
               
               
                 0.3 
                 10 
                 23.523 
                 20.602 
               
               
                   
               
            
           
         
       
     
     Preparation of Composite Membranes 
     Table 4 describes the comparative membrane (non-coated membrane) and inventive composite membrane (coated membrane) examples which are evaluated in Examples I and II. 
     
       
         
           
               
               
               
               
             
               
                   
                 TABLE 4 
               
               
                   
                   
               
               
                   
                 First Side 134 
                 Second Side 136 
                 Substrate/Membrane 12 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                 Composite 
                 Uncoated 
                 Coating Structure: Material 2B on 
                 Teslin HD1100 
               
               
                 Membrane 
                   
                 Substrate followed by Material 2C 
               
               
                 Sample 1 
                   
                 on Material 2B as shown in FIG. 4C 
               
               
                 Membrane 
                   
                 Material 2B: SELVOL ® 325 
               
               
                 Structure as 
                   
                 polyvinyl alcohol, Sekisui 
               
               
                 shown in 
                   
                 Specialty Chemicals America 
               
               
                 FIG. 3B 
                   
                 (Dallas, TX) 
               
               
                   
                   
                 Coating Weight of 2B: Not 
               
               
                   
                   
                 disclosed by manufacturer 
               
               
                   
                   
                 Material 2C: UNIDYNE ® 8112 
               
               
                   
                   
                 Daikin America, Inc)] 
               
               
                   
                   
                 Material Coating weight of 2C: not 
               
               
                   
                   
                 disclosed by manufacturer 
               
               
                 Composite 
                 Uncoated 
                 Coating Structure: Material 2B on 
                 Teslin HD1100 
               
               
                 Membrane 
                   
                 Substrate followed by Material 2C 
               
               
                 Sample 2 
                   
                 on Material 2B as shown in FIG. 4C 
               
               
                 Membrane 
                   
                 Material 2B: SELVOL ® 325 
               
               
                 Structure as 
                   
                 polyvinyl alcohol, Sekisui 
               
               
                 shown in 
                   
                 Specialty Chemicals America 
               
               
                 FIG. 3B 
                   
                 (Dallas, TX) 
               
               
                   
                   
                 Coating weight 
               
               
                   
                   
                 Material 2C: UNIDYNE ® 8112 
               
               
                   
                   
                 Daikin America, Inc)] 
               
               
                   
                   
                 Material Coating weights not 
               
               
                   
                   
                 disclosed by manufacturer 
               
               
                 Composite 
                 Uncoated 
                 Coating Structure: Material 2B on 
                 Teslin HD1100 
               
               
                 Membrane 
                   
                 Substrate followed by Material 2C 
               
               
                 Sample 3 
                   
                 on Material 2B as shown in FIG. 4C 
               
               
                 Membrane 
                   
                 Material 2B: SELVOL ® 325 
               
               
                 Structure as 
                   
                 polyvinyl alcohol, Sekisui 
               
               
                 shown in 
                   
                 Specialty Chemicals America 
               
               
                 FIG. 3B 
                   
                 (Dallas, TX) 
               
               
                   
                   
                 Material 2C: UNIDYNE ® 8112 
               
               
                   
                   
                 Daikin America, Inc)] 
               
               
                   
                   
                 Material Coating weights not 
               
               
                   
                   
                 disclosed by manufacturer 
               
               
                 Commercially 
                 Uncoated 
                 Uncoated 
                 Teslin HD1100 
               
               
                 Available 
               
               
                 Membrane 
               
               
                 Teslin 
               
               
                 HD1100 
               
               
                   
               
            
           
         
       
     
     In Example III, Membrane Comparative Examples are left uncoated, or coated with hydrophilic coatings only. Comparative Example 11 (“CE-11”) and Comparative Example 12 (“CE-12”) are both treated with Composition 2A as described above. CE-12 is coated on Side A (corresponding to first side  134  of  FIG. 2 ) with an additional hydrophilic solution, 2B, which is applied in the same manner as described for composition 2C above. Comparative Example 13 is provided, which is a PVDF membrane fused with a super hydrophobic composition. This material is commercially available as DURAPEL® GVSP, available from MilliporeSigma (Billerica, Mass.). 
     Composite membranes are prepared according to the following steps: 
     Step 1. Preparation of Coating Solutions 
     Hydrophilic Coating Composition 2A 
     Poly (2-ethyl-2-oxazoline), (20 g, weight average molecular weight (Mw)˜50,000) is dispersed in cool water (910 g) under mild agitation in a 4000 mL beaker. The mixture is stirred for 4 hours, followed by addition of PLURONIC®17R2 (10 g, a Block Copolymer Surfactant available from BASF (Ludwigshafen, Germany)) and 2-butoxyethanol (60 g), after which the resultant solution is stirred for an additional 30 minutes. 
     Hydrophilic Coating Composition 2B 
     SELVOL® 325 (4 g, polyvinyl alcohol available from Sekisui Specialty Chemicals America (Dallas, Tex.)) is dispersed in cool water (96 g) under mild agitation in a 300 mL beaker using a 1 inch (2.54 cm) paddle stirrer driven by an electric stir motor. The mixture is heated to 190° F. (87.8° C.) and stirred for approximately 25 minutes until completely dissolved. The resultant solution is cooled to room temperature with stirring. 
     Hydrophobic/Oleophobic Coating Composition 2C 
     UNIDYNE® 8112 (15 g, available from Daikin America, Inc. (Orangeburg, N.Y.)) is dispersed in cool water (85 g) under mild agitation in a 400 mL beaker. 
     Step 2. Coating Procedures 
     All membranes/substrate  12  are cut to 8.5×11-inch [0.22×0.28 m] sheets prior to treatment with any coating composition. In each case, the 8.5×11-inch [0.22×0.28 m] sheet is placed on a clean glass surface and taped along the short side. 
     Each of the composite membrane samples are prepared according to the following steps:
         1. Each substrate is taped on a balance prior to placing the sheet, Side B facing up, on a clean glass surface and using tape to adhere the top corners of the sheet to the glass.   2. A piece of clear 10 mil thick polyester 11 inch (0.28 m)×3 inch (0.08 m) is positioned to overlap across the top edge of the sheet and affixed to the glass surface with tape.   3. A wire wrapped metering rod #3 from Diversified Enterprises is placed on the polyester near the top edge.   4. A 10 to 20 mL quantity of coating is deposited as a bead strip (approximately ¼ inch (0.64 cm) wide) directly next to and touching the metering rod using a disposable pipette.   5. The bar is drawn down across the sheet at approximately a constant rate.   6. The resultant wet sheet is removed from the glass surface, immediately placed on the previously tared balance, weighed, then placed in a forced air oven and dried at 95° C. for 2 minutes.   7. The dried sheet is removed from oven and the same coating procedure was repeated on Side B such that the membrane  12  is coated with hydrophilic composition 2B on second side  136  only (Side B) first and hydrophobic/oleophobic composition 2C is applied to the hydrophilic composition 2B on the side  136  to form a diffusion regulating coating  138 .   8. The coated microporous material is then clamped on an aluminum frame which is fitted with a gasket to prevent the film from shrinking during drying.   9. The framed membrane is then dried in an oven at 95° C. for 15 minutes.       

     It will be appreciated that the above coating procedure can be modified to achieve the composite membranes as described in Example III or as described hereinafter in the description. 
     Test Methods/Calculation(s) 
     A. Physical Properties Testing of Membranes 
     Each of the membranes, treated membranes (“composite membranes”), and comparative untreated membranes are characterized by testing the physical properties described below according to the test methods described hereinafter. 
     A1. Gurley Porosity Test Method 
     The Gurley Porosity Test Method is performed on dry membrane samples. Porosity is determined using a Gurley Precision Densometer, model 4340, manufactured by GPI Gurley Precision Instruments (Troy, N.Y.). The Porosity reported is a measure of the rate of air flow through a sample or it&#39;s resistance to an air flow through the sample. The unit of measure is a “Gurley second” and represents the time in seconds to pass 100 cc of air through a 1 inch square area using a pressure differential of 4.88 inches of water. Lower values equate to less air flow resistance (more air is allowed to pass freely, e.g., more porous). The measurements are completed using the procedure listed in the manual, MODEL 4340 Automatic Densometer and Smoothness Tester Instruction Manual. TAPPI method T 460 om-06-Air Resistance of Paper can also be referenced for the basic principles of the measurement. 
     A2. Density Test Method 
     The density of the above-described examples is determined by dividing the average weight of two specimens measuring 4.5×5 inches (11.43 cm×12.7 cm) that is cut from each sample by the average volume of those specimens. 
     A3. Pore size Test Method 
     The volume average diameter of the pores of the microporous material is determined by mercury porosimetry using an Autoscan mercury porosimeter (Quantachrome Instruments (Boynton Beach, Fla.)) in accordance with the operating manual accompanying the instrument. The volume average pore radius for a single scan is determined automatically by the porosimeter. In operating the porosimeter, a scan is made in the high pressure range (from 138 kilopascals absolute to 227 megapascals absolute). If 2 percent or less of the total intruded volume occurs at the low end (from 138 to 250 kilopascals absolute) of the high pressure range, the volume average pore diameter is taken as twice the volume average pore radius determined by the porosimeter. Otherwise, an additional scan is made in the low pressure range (from 7 to 165 kilopascals absolute) and the volume average pore diameter is calculated according to the equation: 
         d= 2[ v 1 r 1/ w 1+ v 2 r 2/ w 2]/[ v 1/ w 1+ v/w 2] 
     where, 
     d is the volume average pore diameter; v 1 is the total volume of mercury intruded in the high pressure range; v 2 is the total volume of mercury intruded in the low pressure range; r1 is the volume average pore radius determined from the high pressure scan; r2 is the volume average pore radius determined from the low pressure scan; w1 is the weight of the sample subjected to the high pressure scan; and w2 is the weight of the sample subjected to the low pressure scan. 
     A4. Contact Angle Test Method 
     The contact angle is measured on a VCA 2500XE video contact angle system, available from AST Products, Inc. (Billerica, Mass.) using 1 microliter of ultrapure water. On all samples, contact angle is measured on Side A. 
     A5. Oil Rating Test Method 
     The oil rating is measured with AATCC test method 118-2007. In cases where Sides A and B are different, the oil rating is measured on Side A wherein Side A is a side of the test membrane exposed to the interior of the reservoir. 
     B. Membrane Performance Test Methods 
     A testing apparatus is used for evaluating the following performance parameters of the test membranes. Components of an exemplary embodiment of the testing apparatus is described below wherein the testing apparatus is a holder assembly used for evaporation rate and performance testing of a membrane. 
     B1. Assembly of Testing Apparatus 
     The holder assembly consists of a front clamp with a ring gasket, a back clamp, test reservoir cup, and four screws. The test reservoir cup is fabricated from a clear thermoplastic polymer, having interior dimensions defined by a circular diameter at the edge of the open face of approximately 4 centimeters and a depth of no greater than 1 centimeter. The open face is used to determine the volatile material transfer rate. Each clamp of the holder assembly has a 1.5 inch (3.8 cm) diameter circular opening to accommodate the test reservoir cup and provide an opening to expose the membrane under test. When placing a membrane under test, the back clamp of the holder assembly is placed on top of a cork ring. The test reservoir cup is placed in the back clamp and charged with an amount of benzyl acetate as described below, used to simulate fragrance compositions. 
     The front clamp of the holder is carefully placed over the entire assembly, with the screw holes aligned and so as not to disturb the membrane disk. The screws are attached and tightened enough to prevent leaking. The ring gasket creates a seal. Five replicates are assembled for each membrane tested. 
     Air Flow Conditions 
     Examples tested under “non-restricted” conditions are placed laboratory chemical fume hood having approximate dimensions of 5 feet (1.52 m) (height)×5 (1.52 m) feet (width)×2 (0.61 m) feet (depth). The glass doors of the fume hood are pulled down, and the air flow through the hood are adjusted so as to have eight (8) turns (or turnovers) of hood volume per hour. 
     Examples tested under “restricted” conditions are placed in a HDPE enclosed box, having approximate dimensions of 11 inches (0.28 m) (height)×19 inches (0.48 m) (width)×11 inches (0.28 m) (depth). Enclosing the container is an 11×19 inch (0.28×0.48 m) cardboard sheet, wrapped with duct tape. 
     B2. Volatile Material Transfer Rate Test 
     A volatile material transfer rate of a membrane is evaluated according to the following steps: 
     1. Each holder assembly is weighed to obtain an initial weight of the entire charged assembly. 
     2. The assembly is then placed upright such that the membrane is oriented vertically and benzyl acetate is in direct contact with at least a portion of the test membrane. 
     3. The upright (vertically oriented) assembly is placed in an environment defined below according to the airflow, maintained at 25°±5° C. The humidity within in environment is ambient. 
     4. The test reservoirs are weighed every 24 hours for a minimum of 14 days. 
     5. The calculated weight loss of benzyl acetate over the entire time period, in combination with the elapsed time and surface area of the microporous sheet exposed to the interior of the test reservoir, is used to determine the volatile material transfer rate of the microporous sheet, in units of mg/(hour*cm2). 
     6. The average evaporation rate is converted to volatile material transfer rate according to the following formula: 
       Average Evaporation Rate (mg/hr)/12.5 cm2=Volatile Material Transfer Rate (mg/(hour*cm2)) 
     7. The average of all evaluations over time for all replicates is used to determine the average evaporation rate of a test reservoir. 
     B3. Sweat Rating 
     A sweat rating of a test membrane is evaluated according to the following steps: 
     1. Concurrent with the volatile material transfer rate testing, every 24 hours for at least 14 days, the exterior membrane surface on each assembly is visually inspected for liquid accumulation. 
     2. The sweat rating used a numbering system, with “0” being no liquid accumulation; “1” being liquid accumulation on the substrate alone; “2” having liquid accumulation on the substrate and the ring gasket of the holder; and “3” having liquid accumulation on the substrate, seal and bottom metal lip of the holder. 
     3. The average of all evaluations over time for all replicates is used to determine the average sweat rating of a test membrane. 
     C. Apparatus/Air Freshener Performance Test Methods 
     C1. Air Freshener on Vent Vapor Release Rate Test Method (AF on Vent Test Method) 
     The vapor release rate of Air freshener Samples are evaluated according to the following steps: 
     1. Measure the initial total sample weight. 
     2. Clip the sample on a desktop fan such that a coated side ( 2 C on  2 B) of the test membrane faces the fan with the fan operating at an air velocity of 3 to 6 m/s (approximately average air velocity of 5 m/s) for 2 hours to simulate an on-vent state when the fan of an air conditioning system is turned on. The desktop fan is selected to simulate the fan of an air condition system such as for example in an automobile. 
     3. The fan with the sample clipped thereon is placed in a 2.0 m×3.4 m×2.8 m room. The conditions of the room are: 
     Air velocity—10 air changes per hour (ACH), velocity˜0.1 m/s, 
     Air Temperature—21 deg C. 
     Relative Humidity—40% RH. 
     4. Remove the sample from the fan and measure sample weight corresponding to an on-vent condition “ON” state in which the fan is turned on. 
     5. Place the sample in a room at 21 deg C., 60% RH and 10ACH for 22 hours (to simulate an off vent condition in which the fan is not turned on). 
     6. Remove the sample from the room and measure sample weight so as to obtain a sample weight corresponding to an off-vent condition, i.e. when the apparatus is not placed on the vent (“OFF” state). 
     7. Repeat Steps 4 to 6 above on a daily basis. 
     8. Measure change in sample weight and calculate perfume evaporation rates over 30 days. 
     9. Determine the cumulative weight loss of the volatile composition as described thereinafter using the recorded times with their corresponding weights. 
     10. Calculate the time average vapor release rate of the volatile composition as described hereinafter using the recorded times and their corresponding weights. 
     C2. Cumulative Weight Loss Calculation Method 
     A cumulative weight loss at a time after activation is calculated following formula (1) 
       Cumulative Weight Loss at  T   x   =W cum Tx   =W   Ti   −W   Tx   (1)
 
     wherein 
     W Ti =initial weight of volatile composition (mg) prior to activation 
     W Tx =weight of volatile composition (mg) at a designated time (days) after activation 
     C3. Average Vapor Release Rate Calculation Method 
     An average vapor release rate of the air freshener is calculated using formula (2). 
     Time average vapor release rate, 
     
       
         
           
             
               
                 
                   V 
                   = 
                   
                     
                       
                         W 
                         1 
                       
                       - 
                       
                         W 
                         2 
                       
                     
                     
                       ( 
                       
                         
                           t 
                           2 
                         
                         - 
                         
                           t 
                           1 
                         
                       
                       ) 
                     
                   
                 
               
               
                 
                   ( 
                   2 
                   ) 
                 
               
             
           
         
       
     
     wherein, 
     t 1 =a first time period after activation 
     t 2 =a second time period after activation 
     W 1 =weight of the volatile composition at t 1    
     W 2 =weight of the volatile composition at t 2 . 
     Example I 
     In this example, inventive air fresheners based on the apparatus of  FIG. 5  and the volatile composition of Table 3 (“Inventive Examples 2, 3, and 4”) and comparative air freshener based on the apparatus of  FIG. 5  and the volatile composition of Table 3 (“Comparative Example 1”) are evaluated according to the Vapor Release Rate Test Method described hereinbefore under Test Methods. Tables 5, 6 and 7 below show a cumulative weight loss and vapor release rate of volatile composition from inventive air fresheners 2, 3, 4 and comparative air freshener 1.  FIG. 8  and  FIG. 9  are corresponding graphs of Tables 5, 6 and 7. 
     
       
         
           
               
               
               
             
               
                   
                 TABLE 5 
               
             
            
               
                   
                   
               
               
                   
                 Comparative Example (Ex.) 1 
                 Inventive Example (Ex.) 2 
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                   
                   
                   
                   
                 Area 
                   
                   
                 Area 
               
               
                   
                   
                   
                   
                 normalized 
                   
                   
                 normalized 
               
               
                   
                 On Vent 
                 Cumulative 
                 Perfume 
                 perfume 
                 Cumulative 
                 Perfume 
                 perfume 
               
               
                   
                 (“ON”) 
                 perfume 
                 evaporation 
                 evaporation 
                 perfume 
                 evaporation 
                 evaporation 
               
               
                   
                 Off Vent 
                 evaporation 
                 rate 
                 rate 
                 evaporation 
                 rate 
                 rate 
               
               
                 Day 
                 (“OFF”) 
                 (mg) 
                 (mg/h) 
                 (mg/h*cm 2 ) 
                 (mg) 
                 (mg/h) 
                 (mg/h*cm 2 ) 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                 0 
                 OFF 
                 0 
                 0 
                 0.00 
                 0 
                 0 
                 0.00 
               
               
                 0.08 
                 ON 
                 106 
                 53.00 
                 7.57 
                 43 
                 21.50 
                 3.07 
               
               
                 1.00 
                 OFF 
                 121 
                 0.68 
                 0.10 
                 62 
                 0.86 
                 0.12 
               
               
                 1.08 
                 ON 
                 237 
                 58.00 
                 8.29 
                 122 
                 30.00 
                 4.29 
               
               
                 2.00 
                 OFF 
                 252 
                 0.68 
                 0.10 
                 139 
                 0.77 
                 0.11 
               
               
                 2.08 
                 ON 
                 358 
                 53.00 
                 7.57 
                 193 
                 27.00 
                 3.86 
               
               
                 3.00 
                 OFF 
                 373 
                 0.68 
                 0.10 
                 212 
                 0.86 
                 0.12 
               
               
                 3.08 
                 ON 
                 492 
                 59.50 
                 8.50 
                 275 
                 31.50 
                 4.50 
               
               
                 4.00 
                 OFF 
                 509 
                 0.77 
                 0.11 
                 295 
                 0.91 
                 0.13 
               
               
                 4.08 
                 ON 
                 608 
                 49.50 
                 7.07 
                 345 
                 25.00 
                 3.57 
               
               
                 6.00 
                 OFF 
                 632 
                 0.52 
                 0.07 
                 379 
                 0.74 
                 0.11 
               
               
                 6.08 
                 ON 
                 728 
                 48.00 
                 6.86 
                 432 
                 26.50 
                 3.79 
               
               
                 7.00 
                 OFF 
                 744 
                 0.73 
                 0.10 
                 448 
                 0.73 
                 0.10 
               
               
                 7.08 
                 ON 
                 846 
                 51.00 
                 7.29 
                 504 
                 28.00 
                 4.00 
               
               
                 9.00 
                 OFF 
                 865 
                 0.41 
                 0.06 
                 532 
                 0.61 
                 0.09 
               
               
                 9.08 
                 ON 
                 965 
                 50.00 
                 7.14 
                 587 
                 27.50 
                 3.93 
               
               
                 11.00 
                 OFF 
                 989 
                 0.52 
                 0.07 
                 622 
                 0.76 
                 0.11 
               
               
                 11.08 
                 ON 
                 1074 
                 42.50 
                 6.07 
                 669 
                 23.50 
                 3.36 
               
               
                 15.00 
                 OFF 
                 1125 
                 0.54 
                 0.08 
                 735 
                 0.70 
                 0.10 
               
               
                 15.17 
                 ON 
                 1268 
                 35.75 
                 5.11 
                 822 
                 21.75 
                 3.11 
               
               
                 17.00 
                 OFF 
                 1287 
                 0.43 
                 0.06 
                 850 
                 0.64 
                 0.09 
               
               
                 17.08 
                 ON 
                 1359 
                 36.00 
                 5.14 
                 896 
                 23.00 
                 3.29 
               
               
                 20.00 
                 OFF 
                 1393 
                 0.49 
                 0.07 
                 943 
                 0.67 
                 0.10 
               
               
                 20.08 
                 ON 
                 1456 
                 31.50 
                 4.50 
                 988 
                 22.50 
                 3.21 
               
               
                 21.00 
                 OFF 
                 1461 
                 0.23 
                 0.03 
                 1001 
                 0.59 
                 0.08 
               
               
                 21.08 
                 ON 
                 1519 
                 29.00 
                 4.14 
                 1041 
                 20.00 
                 2.86 
               
               
                 22.00 
                 OFF 
                 1528 
                 0.41 
                 0.06 
                 1053 
                 0.55 
                 0.08 
               
               
                 22.21 
                 ON 
                 1643 
                 23.00 
                 3.29 
                 1143 
                 18.00 
                 2.57 
               
               
                 26.00 
                 OFF 
                 1654 
                 0.12 
                 0.02 
                 1169 
                 0.29 
                 0.04 
               
               
                 26.13 
                 ON 
                 1721 
                 22.33 
                 3.19 
                 1238 
                 23.00 
                 3.29 
               
               
                 29.00 
                 OFF 
                 1732 
                 0.16 
                 0.02 
                 1275 
                 0.54 
                 0.08 
               
               
                 29.08 
                 ON 
                 1773 
                 20.50 
                 2.93 
                 1324 
                 24.50 
                 3.50 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
             
               
                   
                 TABLE 6 
               
             
            
               
                   
                   
               
               
                   
                 Inventive Example (Ex.) 3 
               
            
           
           
               
               
               
               
               
            
               
                   
                   
                   
                   
                 Area 
               
               
                   
                   
                   
                   
                 normalized 
               
               
                   
                 On Vent 
                 Cumulative 
                 Perfume 
                 perfume 
               
               
                   
                 (“ON”)/ 
                 Perfume 
                 evaporation 
                 evaporation 
               
               
                   
                 Off Vent 
                 evaporation 
                 rate 
                 rate 
               
               
                 Day 
                 (“OFF”) 
                 (mg) 
                 (mg/h) 
                 (mg/h*cm 2 ) 
               
               
                   
               
            
           
           
               
               
               
               
               
            
               
                 0 
                 OFF 
                 0 
                 0 
                 0.00 
               
               
                 0.08 
                 ON 
                 13 
                 6.50 
                 0.93 
               
               
                 1.00 
                 OFF 
                 30 
                 0.77 
                 0.11 
               
               
                 1.08 
                 ON 
                 48 
                 9.00 
                 1.29 
               
               
                 2.00 
                 OFF 
                 65 
                 0.77 
                 0.11 
               
               
                 2.08 
                 ON 
                 81 
                 8.00 
                 1.14 
               
               
                 3.00 
                 OFF 
                 100 
                 0.86 
                 0.12 
               
               
                 3.08 
                 ON 
                 122 
                 11.00 
                 1.57 
               
               
                 4.00 
                 OFF 
                 140 
                 0.82 
                 0.12 
               
               
                 4.08 
                 ON 
                 156 
                 8.00 
                 1.14 
               
               
                 6.00 
                 OFF 
                 193 
                 0.80 
                 0.11 
               
               
                 6.08 
                 ON 
                 210 
                 8.50 
                 1.21 
               
               
                 7.00 
                 OFF 
                 229 
                 0.86 
                 0.12 
               
               
                 7.08 
                 ON 
                 249 
                 10.00 
                 1.43 
               
               
                 9.00 
                 OFF 
                 279 
                 0.65 
                 0.09 
               
               
                 9.08 
                 ON 
                 300 
                 10.50 
                 1.50 
               
               
                 11.00 
                 OFF 
                 338 
                 0.83 
                 0.12 
               
               
                 11.08 
                 ON 
                 355 
                 8.50 
                 1.21 
               
               
                 15.00 
                 OFF 
                 429 
                 0.79 
                 0.11 
               
               
                 15.17 
                 ON 
                 461 
                 8.00 
                 1.14 
               
               
                 17.00 
                 OFF 
                 493 
                 0.73 
                 0.10 
               
               
                 17.08 
                 ON 
                 512 
                 9.50 
                 1.36 
               
               
                 20.00 
                 OFF 
                 562 
                 0.71 
                 0.10 
               
               
                 20.08 
                 ON 
                 582 
                 10.00 
                 1.43 
               
               
                 21.00 
                 OFF 
                 596 
                 0.64 
                 0.09 
               
               
                 21.08 
                 ON 
                 611 
                 7.50 
                 1.07 
               
               
                 22.00 
                 OFF 
                 625 
                 0.64 
                 0.09 
               
               
                 22.21 
                 ON 
                 661 
                 7.20 
                 1.03 
               
               
                 26.00 
                 OFF 
                 690 
                 0.32 
                 0.05 
               
               
                 26.13 
                 ON 
                 721 
                 10.33 
                 1.48 
               
               
                 29.00 
                 OFF 
                 766 
                 0.65 
                 0.09 
               
               
                 29.08 
                 ON 
                 789 
                 11.50 
                 1.64 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
             
               
                   
                 TABLE 7 
               
             
            
               
                   
                   
               
               
                   
                 Inventive Example (Ex.) 4 
               
            
           
           
               
               
               
               
               
            
               
                   
                   
                   
                   
                 Area 
               
               
                   
                   
                   
                   
                 normalized 
               
               
                   
                 On Vent 
                 Cumulative 
                 Perfume 
                 perfume 
               
               
                   
                 (“ON”)/ 
                 perfume 
                 evaporation 
                 evaporation 
               
               
                   
                 Off Vent 
                 evaporation 
                 rate 
                 rate 
               
               
                 Day 
                 (“OFF”) 
                 (mg) 
                 (mg/h) 
                 (mg/h*cm 2 ) 
               
               
                   
               
            
           
           
               
               
               
               
               
            
               
                 0 
                 OFF 
                 0 
                 0 
                 0 
               
               
                 0.08 
                 ON 
                 4 
                 2.00 
                 0.29 
               
               
                 1.00 
                 OFF 
                 6 
                 0.09 
                 0.01 
               
               
                 1.08 
                 ON 
                 12 
                 3.00 
                 0.43 
               
               
                 2.00 
                 OFF 
                 19 
                 0.32 
                 0.05 
               
               
                 2.08 
                 ON 
                 25 
                 3.00 
                 0.43 
               
               
                 3.00 
                 OFF 
                 33 
                 0.36 
                 0.05 
               
               
                 3.09 
                 ON 
                 38 
                 2.00 
                 0.29 
               
               
                 4.00 
                 OFF 
                 46 
                 0.37 
                 0.05 
               
               
                 4.08 
                 ON 
                 51 
                 2.50 
                 0.36 
               
               
                 7.00 
                 OFF 
                 78 
                 0.39 
                 0.06 
               
               
                 7.08 
                 ON 
                 84 
                 3.00 
                 0.43 
               
               
                 8.00 
                 OFF 
                 92 
                 0.36 
                 0.05 
               
               
                 8.08 
                 ON 
                 98 
                 3.00 
                 0.43 
               
               
                 9.00 
                 OFF 
                 106 
                 0.36 
                 0.05 
               
               
                 9.08 
                 ON 
                 110 
                 2.00 
                 0.29 
               
               
                 10.00 
                 OFF 
                 120 
                 0.45 
                 0.06 
               
               
                 10.08 
                 ON 
                 125 
                 2.50 
                 0.36 
               
               
                 11.00 
                 OFF 
                 135 
                 0.45 
                 0.06 
               
               
                 11.08 
                 ON 
                 139 
                 2.00 
                 0.29 
               
               
                 14.00 
                 OFF 
                 168 
                 0.41 
                 0.06 
               
               
                 14.08 
                 ON 
                 174 
                 3.00 
                 0.43 
               
               
                 15.00 
                 OFF 
                 182 
                 0.36 
                 0.05 
               
               
                 15.08 
                 ON 
                 187 
                 2.50 
                 0.36 
               
               
                 16.00 
                 OFF 
                 197 
                 0.45 
                 0.06 
               
               
                 16.08 
                 ON 
                 202 
                 2.50 
                 0.36 
               
               
                 17.00 
                 OFF 
                 211 
                 0.41 
                 0.06 
               
               
                 17.08 
                 ON 
                 215 
                 2.00 
                 0.29 
               
               
                 21.00 
                 OFF 
                 252 
                 0.39 
                 0.06 
               
               
                 21.08 
                 ON 
                 259 
                 3.50 
                 0.50 
               
               
                 22.00 
                 OFF 
                 267 
                 0.36 
                 0.05 
               
               
                 22.08 
                 ON 
                 273 
                 3.00 
                 0.43 
               
               
                 23.00 
                 OFF 
                 282 
                 0.41 
                 0.06 
               
               
                 23.08 
                 ON 
                 287 
                 2.50 
                 0.36 
               
               
                 24.00 
                 OFF 
                 295 
                 0.36 
                 0.05 
               
               
                 24.08 
                 ON 
                 300 
                 2.50 
                 0.36 
               
               
                 25.00 
                 OFF 
                 309 
                 0.41 
                 0.06 
               
               
                 25.08 
                 ON 
                 314 
                 2.50 
                 0.36 
               
               
                 28.00 
                 OFF 
                 340 
                 0.37 
                 0.05 
               
               
                 28.08 
                 ON 
                 345 
                 2.50 
                 0.36 
               
               
                 29.00 
                 OFF 
                 354 
                 0.41 
                 0.06 
               
               
                 29.08 
                 ON 
                 359 
                 2.50 
                 0.36 
               
               
                 30.00 
                 OFF 
                 369 
                 0.45 
                 0.06 
               
               
                   
               
            
           
         
       
     
     As described hereinbefore, each of Inventive Examples 2, 3 and 4 comprise a composite membrane comprising a hydrophobic/oleophobic coating  2 C and a hydrophilic coating  2 B. By having the combination of a volatile composition  9  and a composite membrane  13  having a hydrophobic/oleophobic coating  2 C and the hydrophilic coating  2 B, the overall cumulative perfume evaporation of each of the Inventive Samples is reduced relative to a cumulative perfume evaporation of the uncoated microporous membrane (Comparative Example 1) as illustrated in  FIG. 8 . 
     Referring to Tables 5, 6 and 7, the vapor release rates or perfume evaporation rates of Inventive Examples 2, 3 and 4 are reduced by 58% to 96% relative to a vapor release rate/perfume evaporation rate of Comparative Example 1 (without a composite membrane but using a non-coated membrane) at Day 0.08 when there is high air flow (for example at an average air flow rate of 5 m/s) across the membrane surface (i.e. when the samples were placed on the fan for 2 hours as described in the Vapor Release Rate Test Method). A sample calculation of a percentage reduction of the vapor release rate at Day 0.08 (“ON”/Fan turned on) for Inventive Examples 2, 3 and 4 relative to the Comparative Example 1 are shown below. 
     
       
         
           
               
               
               
               
               
             
               
                   
               
               
                   
                   
                 Inventive 
                 Inventive 
                 Inventive 
               
               
                   
                   
                 Ex. 2 
                 Ex. 3 
                 Ex. 4 
               
               
                   
                 Comparative 
                 (Composite 
                 (Composite 
                 (Composite 
               
               
                 Day 0.08 (“ON”) 
                 Ex. 1 
                 Membrane 1) 
                 Membrane 2) 
                 Membrane 3) 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
            
               
                 mg/h 
                 53 
                 21.5 
                 6.5 
                 2 
               
               
                 Difference in mg/hr relative 
                 — 
                 31.5 
                 46.5 
                 51 
               
               
                 to Comparative Ex. 1 
               
               
                 % reduction relative 
                 — 
                 58% 
                 87% 
                 96% 
               
               
                 to Comparative Ex. 1 
               
               
                 mg/h*cm2 
                 7.57 
                 3.07 
                 0.93 
                 0.29 
               
               
                   
               
            
           
         
       
     
     Accordingly, a technical effect of the present invention is it provides overall reduced perfume evaporation rates when the apparatus according to the present invention is subject to high air flow conditions such as placed in a car when the car is moving or when placed on vent in fluid communication with a fan of the air conditioning system (“ON”—there is high air flow) thereby corresponds to reduced scent intensity in the interior space when the fan of the air conditioning system is turned on. 
     Example II 
     Inventive Examples 5 and 6 and Comparative Example 2 are evaluated according to the Vapor Release Rate Test Method described hereinbefore under Test Methods. Table 8 below show a cumulative weight loss, vapor release rate, and of volatile composition from Comparative Example 2. Table 9 below show a cumulative weight loss, vapor release rate, and of volatile composition from Inventive Examples 5, 6.  FIG. 10  and  FIG. 11  are corresponding graphs of 
     Tables 8 and 9. 
     
       
         
           
               
               
             
               
                   
                 TABLE 8 
               
             
            
               
                   
                   
               
               
                   
                 Comparative Example 2 
               
            
           
           
               
               
               
               
               
            
               
                   
                   
                   
                   
                 Area 
               
               
                   
                   
                   
                   
                 normalized 
               
               
                   
                 On Vent 
                 Cumulative 
                 Perfume 
                 perfume 
               
               
                   
                 (“ON”)/ 
                 perfume 
                 evaporation 
                 evaporation 
               
               
                   
                 Off Vent 
                 evaporation 
                 rate 
                 rate 
               
               
                 Day 
                 (“OFF”) 
                 (mg) 
                 (mg/h) 
                 (mg/h*cm 2 ) 
               
               
                   
               
            
           
           
               
               
               
               
               
            
               
                 0 
                 OFF 
                 0 
                 0 
                 0 
               
               
                 0.08 
                 ON 
                 138 
                 69.00 
                 9.86 
               
               
                 1.00 
                 OFF 
                 158 
                 0.91 
                 0.13 
               
               
                 1.08 
                 ON 
                 270 
                 56.00 
                 8.00 
               
               
                 2.00 
                 OFF 
                 291 
                 0.95 
                 0.14 
               
               
                 2.08 
                 ON 
                 376 
                 42.50 
                 6.07 
               
               
                 3.00 
                 OFF 
                 394 
                 0.82 
                 0.12 
               
               
                 3.08 
                 ON 
                 486 
                 46.00 
                 6.57 
               
               
                 4.00 
                 OFF 
                 500 
                 0.64 
                 0.09 
               
               
                 4.08 
                 ON 
                 582 
                 41.00 
                 5.86 
               
               
                 7.00 
                 OFF 
                 620 
                 0.54 
                 0.08 
               
               
                 7.08 
                 ON 
                 715 
                 47.50 
                 6.79 
               
               
                 8.00 
                 OFF 
                 732 
                 0.77 
                 0.11 
               
               
                 8.08 
                 ON 
                 833 
                 50.50 
                 7.21 
               
               
                 9.00 
                 OFF 
                 849 
                 0.73 
                 0.10 
               
               
                 9.08 
                 ON 
                 985 
                 68.00 
                 9.71 
               
               
                 10.00 
                 OFF 
                 1000 
                 0.68 
                 0.10 
               
               
                 10.08 
                 ON 
                 1103 
                 51.50 
                 7.36 
               
               
                 11.00 
                 OFF 
                 1112 
                 0.41 
                 0.06 
               
               
                 11.08 
                 ON 
                 1194 
                 41.00 
                 5.86 
               
               
                 14.00 
                 OFF 
                 1222 
                 0.40 
                 0.06 
               
               
                 14.08 
                 ON 
                 1309 
                 43.50 
                 6.21 
               
               
                 15.00 
                 OFF 
                 1323 
                 0.64 
                 0.09 
               
               
                 15.08 
                 ON 
                 1459 
                 68.00 
                 9.71 
               
               
                 16.00 
                 OFF 
                 1468 
                 0.41 
                 0.06 
               
               
                 16.08 
                 ON 
                 1520 
                 26.00 
                 3.71 
               
               
                 17.00 
                 OFF 
                 1527 
                 0.32 
                 0.05 
               
               
                 17.08 
                 ON 
                 1572 
                 22.50 
                 3.21 
               
               
                 21.00 
                 OFF 
                 1599.8 
                 0.30 
                 0.04 
               
               
                 21.08 
                 ON 
                 1641 
                 20.60 
                 2.94 
               
               
                 22.00 
                 OFF 
                 1648 
                 0.32 
                 0.05 
               
               
                 22.08 
                 ON 
                 1690 
                 21.00 
                 3.00 
               
               
                 23.00 
                 OFF 
                 1694 
                 0.18 
                 0.03 
               
               
                 23.08 
                 ON 
                 1729 
                 17.50 
                 2.50 
               
               
                 24.00 
                 OFF 
                 1734 
                 0.23 
                 0.03 
               
               
                 24.08 
                 ON 
                 1766 
                 16.00 
                 2.29 
               
               
                 25.00 
                 OFF 
                 1770 
                 0.18 
                 0.03 
               
               
                 25.08 
                 ON 
                 1795 
                 12.50 
                 1.79 
               
               
                 28.00 
                 OFF 
                 1806 
                 0.16 
                 0.02 
               
               
                 28.08 
                 ON 
                 1835 
                 14.50 
                 2.07 
               
               
                 29.00 
                 OFF 
                 1838 
                 0.14 
                 0.02 
               
               
                 29.08 
                 ON 
                 1888 
                 25.00 
                 3.57 
               
               
                 30.00 
                 OFF 
                 1890 
                 0.09 
                 0.01 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
             
               
                   
                 TABLE 9 
               
             
            
               
                   
                   
               
               
                   
                 Inventive Example 5 
                 Inventive Example 6 
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                   
                   
                   
                   
                 Area 
                   
                   
                 Area 
               
               
                   
                   
                   
                   
                 normalized 
                   
                   
                 normalized 
               
               
                   
                 On Vent 
                 Cumulative 
                 Perfume 
                 perfume 
                 Cumulative 
                 Perfume 
                 perfume 
               
               
                   
                 (“ON”)/ 
                 perfume 
                 evaporation 
                 evaporation 
                 Perfume 
                 evaporation 
                 evaporation 
               
               
                   
                 Off Vent 
                 evaporation 
                 rate 
                 rate 
                 evaporation 
                 rate 
                 rate 
               
               
                 Day 
                 (“OFF”) 
                 (mg) 
                 (mg/h) 
                 (mg/h*cm 2 ) 
                 (mg) 
                 (mg/h) 
                 (mg/h*cm 2 ) 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                 0 
                 OFF 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
               
               
                 0.08 
                 ON 
                 14 
                 7.00 
                 1.00 
                 4 
                 2.00 
                 0.29 
               
               
                 1.00 
                 OFF 
                 22 
                 0.36 
                 0.05 
                 3 
                 0 
                 0.00 
               
               
                 1.08 
                 ON 
                 36 
                 7.00 
                 1.00 
                 8 
                 2.50 
                 0.36 
               
               
                 2.00 
                 OFF 
                 50 
                 0.64 
                 0.09 
                 14 
                 0.27 
                 0.04 
               
               
                 2.08 
                 ON 
                 61 
                 5.50 
                 0.79 
                 16 
                 1.00 
                 0.14 
               
               
                 3.00 
                 OFF 
                 77 
                 0.73 
                 0.10 
                 22 
                 0.27 
                 0.04 
               
               
                 3.08 
                 ON 
                 89 
                 6.00 
                 0.86 
                 27 
                 2.50 
                 0.36 
               
               
                 4.00 
                 OFF 
                 102 
                 0.59 
                 0.08 
                 31 
                 0.18 
                 0.03 
               
               
                 4.08 
                 ON 
                 113 
                 5.50 
                 0.79 
                 34 
                 1.50 
                 0.21 
               
               
                 7.00 
                 OFF 
                 153 
                 0.57 
                 0.08 
                 52 
                 0.26 
                 0.04 
               
               
                 7.08 
                 ON 
                 167 
                 7.00 
                 1.00 
                 57 
                 2.50 
                 0.36 
               
               
                 8.00 
                 OFF 
                 178 
                 0.50 
                 0.07 
                 64 
                 0.32 
                 0.05 
               
               
                 8.08 
                 ON 
                 193 
                 7.50 
                 1.07 
                 69 
                 2.50 
                 0.36 
               
               
                 9.00 
                 OFF 
                 208 
                 0.68 
                 0.10 
                 75 
                 0.27 
                 0.04 
               
               
                 9.08 
                 ON 
                 224 
                 8.00 
                 1.14 
                 81 
                 3.00 
                 0.43 
               
               
                 10.00 
                 OFF 
                 240 
                 0.73 
                 0.10 
                 88 
                 0.32 
                 0.05 
               
               
                 10.08 
                 ON 
                 259 
                 9.50 
                 1.36 
                 90 
                 1.00 
                 0.14 
               
               
                 11.00 
                 OFF 
                 272 
                 0.59 
                 0.08 
                 95 
                 0.23 
                 0.03 
               
               
                 11.08 
                 ON 
                 288 
                 8.00 
                 1.14 
                 98 
                 1.50 
                 0.21 
               
               
                 14.00 
                 OFF 
                 320 
                 0.46 
                 0.07 
                 118 
                 0.29 
                 0.04 
               
               
                 14.08 
                 ON 
                 333 
                 6.50 
                 0.93 
                 123 
                 2.50 
                 0.36 
               
               
                 15.00 
                 OFF 
                 344 
                 0.50 
                 0.07 
                 128 
                 0.23 
                 0.03 
               
               
                 15.08 
                 ON 
                 360 
                 8.00 
                 1.14 
                 132 
                 2.00 
                 0.29 
               
               
                 16.00 
                 OFF 
                 376 
                 0.73 
                 0.10 
                 138 
                 0.27 
                 0.04 
               
               
                 16.08 
                 ON 
                 397 
                 10.50 
                 1.50 
                 142 
                 2.00 
                 0.29 
               
               
                 17.00 
                 OFF 
                 409 
                 0.55 
                 0.08 
                 148 
                 0.27 
                 0.04 
               
               
                 17.08 
                 ON 
                 427 
                 9.00 
                 1.29 
                 151 
                 1.50 
                 0.21 
               
               
                 21.00 
                 OFF 
                 481 
                 0.57 
                 0.08 
                 178 
                 0.29 
                 0.04 
               
               
                 21.08 
                 ON 
                 493 
                 6.00 
                 0.86 
                 182 
                 2.00 
                 0.29 
               
               
                 22.00 
                 OFF 
                 506 
                 0.59 
                 0.08 
                 189 
                 0.32 
                 0.05 
               
               
                 22.08 
                 ON 
                 520 
                 7.00 
                 1.00 
                 193 
                 2.00 
                 0.29 
               
               
                 23.00 
                 OFF 
                 531 
                 0.50 
                 0.07 
                 199 
                 0.27 
                 0.04 
               
               
                 23.08 
                 ON 
                 543 
                 6.00 
                 0.86 
                 203 
                 2.00 
                 0.29 
               
               
                 24.00 
                 OFF 
                 555 
                 0.55 
                 0.08 
                 209 
                 0.27 
                 0.04 
               
               
                 24.08 
                 ON 
                 567 
                 6.00 
                 0.86 
                 213 
                 2.00 
                 0.29 
               
               
                 25.00 
                 OFF 
                 579 
                 0.55 
                 0.08 
                 219 
                 0.27 
                 0.04 
               
               
                 25.08 
                 ON 
                 590 
                 5.50 
                 0.79 
                 223 
                 2.00 
                 0.29 
               
               
                 28.00 
                 OFF 
                 624 
                 0.49 
                 0.07 
                 240 
                 0.24 
                 0.03 
               
               
                 28.08 
                 ON 
                 637 
                 6.50 
                 0.93 
                 245 
                 2.50 
                 0.36 
               
               
                 29.00 
                 OFF 
                 649 
                 0.55 
                 0.08 
                 251 
                 0.27 
                 0.04 
               
               
                 29.08 
                 ON 
                 660 
                 5.50 
                 0.79 
                 255 
                 2.00 
                 0.29 
               
               
                 30.00 
                 OFF 
                 671 
                 0.50 
                 0.07 
                 261 
                 0.27 
                 0.04 
               
               
                   
               
            
           
         
       
     
     Inventive Examples 5 and 6 use composite membranes comprising a hydrophilic material and a hydrophobic and oleophobic material to define the diffusion regulating coating. A sample calculation of a percentage reduction of the vapor release rate at Day 0.08 (“ON”/Fan turned on) for Inventive Examples 5 and 6 relative to the Comparative Example 2 are shown below. 
     
       
         
           
               
               
               
               
             
               
                   
               
               
                   
                   
                 Inventive 
                 Inventive 
               
               
                   
                   
                 Ex. 5 
                 Ex. 6 
               
               
                   
                 Comparative 
                 (Composite 
                 (Composite 
               
               
                 Day 0.08 (“ON”) 
                 Ex. 2 
                 Membrane 2) 
                 Membrane 3) 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
            
               
                 mg/h 
                 69 
                 7 
                 2 
               
               
                 Reduction mg/h relative 
                 — 
                 62 
                 67 
               
               
                 to Comparative Ex 2 
               
               
                 % reduction relative 
                 — 
                 89% 
                 97% 
               
               
                 to Comparative Ex 2 
               
               
                 mg/h*cm2 
                 9.86 
                 1.00 
                 0.29 
               
               
                   
               
            
           
         
       
     
     Accordingly, a technical effect of the present invention is it provides overall reduced perfume evaporation rates (vapor release rates) when the apparatus according to the present invention is subject to high air flow conditions such as for example when the car is moving or when placed on vent in fluid communication with a fan of the air conditioning system (“ON”—there is high air flow) thereby corresponds to reduced scent intensity in the interior space when the fan of the air conditioning system is turned on. 
     Example III 
     Physical and/or performance characteristics of a membrane (such as a composite membrane) based on a desired vapor release rate of the apparatus  1  (such as for example a vapor release rate in the range of equal to or greater than 0.2 mg/hr*cm 2  to 5 mg/hr*cm 2  at an average air flow rate of 5 m/s) may be determined by the Gurley Porosity, Density, Pore Size, Contact Angle, Oil Rating, Volatile Material Transfer Rate, and Sweat Rating Test Methods respectively described hereinbefore. 
     Table 10 shows different combinations of a composite membrane having different treatments that define one or more diffusion regulating coatings for the composite membrane in an apparatus according to the present invention. Table 11 shows the compositions of filled microporous membranes before coating (substrate). Table 11 shows vapor material transfer rates of each of the composite membranes of Table 10. 
     
       
         
           
               
               
               
               
               
               
               
               
               
             
               
                 TABLE 10 
               
               
                   
               
               
                   
                   
                 Side A 
                 Side B 
                   
                   
                   
                   
                   
               
               
                 Composite 
                   
                 (first side 
                 (second side 
                 Porosity, 
                   
                 Mean 
                 Contact 
                 Oil 
               
               
                 Membrane 
                 Substrate 
                 134 of 
                 136 of 
                 Gurley 
                 Density 
                 pore size 
                 Angle 
                 Rating 
               
               
                 Example 
                 Example 
                 FIG. 2) 
                 FIG. 2) 
                 (sec) 
                 (g/cm3) 
                 (microns) 
                 (Side A) 
                 (Side A) 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 4 
                 3 
                 2C 
                 — 
                 8477 
                 0.9 
                 0.03 
                 107 
                 7 
               
               
                 5 
                 1 
                 2A/2C 
                 2A 
                 1297 
                 0.57 
                 0.05 
                 118 
                 7 
               
               
                 6 
                 3 
                 2A/2C 
                 2A 
                 8477 
                 0.9 
                 0.03 
                 107 
                 7 
               
               
                 7 
                 3 
                 2A/2C 
                 2A/2C 
                 3096 
                 0.74 
                 0.04 
                 115 
                 7 
               
               
                 CE-8  
                 1 
                 — 
                 — 
                 1297 
                 0.55 
                 0.05 
                 114 
                 2 
               
               
                 CE-9  
                 2 
                 — 
                 — 
                 5959 
                 0.66 
                 0.04 
                 116 
                 2 
               
               
                 CE-10 
                 3 
                 — 
                 — 
                 8477 
                 0.74 
                 0.03 
                 105 
                 2 
               
               
                 CE-11 
                 2 
                 2A 
                 2A 
                 5959 
                 0.66 
                 0.05 
                 &lt;20 
                 2 
               
               
                 CE-12 
                 1 
                 2A/2B 
                 2A 
                 1297 
                 0.56 
                 0.05 
                 51 
                 3 
               
               
                 CE-13 
                 DURAPEL ® 
                 — 
                 — 
                 150 
                 0.67 
                 0.44 2   
                 153 
                 6 
               
               
                   
                 GVSP 1   
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
             
               
                   
                 TABLE 11 
               
               
                   
                   
               
               
                   
                   
                 Substrate 
                 Substrate 
                 Substrate 
               
               
                   
                 Ingredients (wt. %) 
                 Example 1 
                 Example 2 
                 Example 3 
               
               
                   
                   
               
             
            
               
                   
                 GUR ® 4170 3   
                 9.08 
                 — 
                 — 
               
               
                   
                 GUR ® 4130 4   
                 — 
                 9.16 
                 9.60 
               
               
                   
                 FINA ® 1288 5   
                 — 
                 9.16 
                 8.75 
               
               
                   
                 HI-SIL ® 135 6   
                 31.77  
                 30.89  
                 24.86 
               
               
                   
                 TIPURE ® R-103 7   
                 1.40 
                 1.28 
                 1.71 
               
               
                   
                 CaCO3 
                 — 
                 — 
                 10.03 
               
               
                   
                 Calcium stearate 
                 0.41 
                 0.26 
                 0.27 
               
               
                   
                 CYANOX ® 1790 8   
                 0.33 
                 0.26 
                 0.18 
               
               
                   
                 TUFFLO ® 6056 9   
                 57.01  
                 49.00  
                 44.59 
               
               
                   
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
             
               
                   
                 TABLE 12 
               
             
            
               
                   
                   
               
               
                   
                 Volatile Material Transfer Rate (mg/(hr*cm 2 ) 
                   
               
            
           
           
               
               
               
               
               
            
               
                 Composite 
                   
                 Quarter 
                 Quarter 
                 Sweat Rating 
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Membrane 
                 Full 
                 Full 
                 Charge 
                 Charge 
                 Full 
                 Full 
               
               
                 Example 
                 Non-restricted 
                 Restricted 
                 Non-restricted 
                 Restricted 
                 Non-restricted 
                 restricted 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 4 
                 0.33 
                 0.06 
                 0.27 
                 0.05 
                 0 
                 0 
               
               
                  5A 
                 0.28 
                 0.04 
                 0.18 
                 0.04 
                 0 
                 0 
               
               
                 5B (Side B 
                 0.29 
                 0.05 
                 0.20 
                 0.03 
                 0 
                 0 
               
               
                 is exposed 
               
               
                 to reservoir) 
               
               
                 6 
                 0.33 
                 0.05 
                 0.27 
                 0.05 
                 0 
                 0 
               
               
                 7 
                 0.18 
                 0.06 
                 0.25 
                 0.03 
                 0 
                 0 
               
               
                 CE-8  
                 0.3 
                 0.12 
                 0.17 
                 0.04 
                 2.15 
                 2.4 
               
               
                 CE-9  
                 0.31 
                 0.03 
                 0.19 
                 0.04 
                 0 
                 0.8 
               
               
                 CE-10 
                 0.29 
                 0.04 
                 0.3 
                 0.04 
                 0 
                 0.47 
               
               
                 CE-11 
                 0.38 
                 0.07 
                 0.3 
                 0.06 
                 0 
                 0.3 
               
               
                 CE-12 
                 0.25 
                 0.04 
                 0.17 
                 0.03 
                 0.14 
                 0.25 
               
               
                 CE-13 
                 0.1 
                 &lt;&lt;0.01 10   
                 0.1 
                 &lt;&lt;0.01 
                 0 
                 N/A 
               
               
                   
               
            
           
         
       
     
     Results in Table 12 show that providing a composite membrane with a hydrophilic coating  2 A and a hydrophobic/oleophobic coating  2 C (Example 7) provides a reduction in the vapor release rate of the composite membrane (0.18 mg/hr*cm2) by approximately 60% relative to an uncoated membrane (CE-10) having a vapor release rate of 0.29 mg/hr*cm2.  1 A PVDF porous membrane with a superhydrophobic surface, available from MilliporeSigma (Billerica, Mass.). 2  Durapel GVSP has a reported mean pore size of 0.22 micron. Data in Table 9 is as measured according to the Test Methods described hereinbefore. 3  An Ultra High Molecular Weight Polyethylene (UHMWPE), available from Celanese Corporation (Irving, Tex.) 4  An Ultra High Molecular Weight Polyethylene (UHMWPE), available from Celanese Corporation (Irving, Tex.) 5  High Density Polyethylene (HDPE), available from Total Petrochemicals USA Inc. (Houston, Tex.) 6  Precipitated silica available from PPG Industries, Inc. (Pittsburgh, Pa.) 7  Rutile titanium dioxide available from The Chemours Company (Wilmington, Del.) 8  A phenolic antioxidant available from Cytec Solvay Group (Woodland Park, N.J.) 9  A process oil available from PPC Lubricants (Jonestown, Pa.) 10  Over a 14 day period, no measurable change in weight was observed under restricted conditions, indicating that the membrane was not operating as a vapor permeable membrane. Thus, a sweat rating was not relevant. 
     The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as “40 mm” is intended to mean “about 40 mm.” 
     Every document cited herein, including any cross referenced or related patent or application and any patent application or patent to which this application claims priority or benefit thereof, is hereby incorporated herein by reference in its entirety unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art with respect to any invention disclosed or claimed herein or that it alone, or in any combination with any other reference or references, teaches, suggests or discloses any such invention. Further, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern. 
     While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.