Vapor-permeable, substantially water-impermeable multilayer article

Information

  • Patent Grant
  • 11383504
  • Patent Number
    11,383,504
  • Date Filed
    Thursday, October 22, 2020
    4 years ago
  • Date Issued
    Tuesday, July 12, 2022
    2 years ago
Abstract
This disclosure relates to an article that includes a nonwoven substrate, a first film supported by the nonwoven substrate, and a second film such that the first film is between the nonwoven substrate and the second film. The first film includes a first polymer and a pore-forming filler. The difference between a surface energy of the first film and a surface energy of the nonwoven substrate is at most about 10 mN/m. The second film includes a second polymer capable of absorbing and desorbing moisture and providing a barrier to aqueous fluids.
Description
TECHNICAL FIELD

This disclosure relates to vapor-permeable, substantially water-impermeable multilayer articles, as well as related products and methods.


BACKGROUND

Films that allow passage of gases at moderate to high transmission rates are often called breathable. The gases most commonly used to demonstrate a film's breathability are water vapor (also referred to herein as moisture vapor or moisture) and oxygen. The moisture vapor transmission test and oxygen transmission test measure the mass or volume of gas transported across the cross-section of a film in a given unit of time at a defined set of environmental conditions. Breathable films can be classified either as microporous films or monolithic films (which are not porous).


A breathable film can be laminated onto a nonwoven substrate to form a vapor-permeable, substantially water-impermeable multilayer article. A vapor-permeable, substantially water-impermeable multilayer article can refer to an article that allows the passage of a gas but substantially does not allow the passage of water.


SUMMARY

The inventors have unexpectedly discovered that a vapor-permeable, substantially water-impermeable multilayer article containing a microporous breathable film (e.g., a film containing the same type of polymer used in the nonwoven substrate) between a monolithic breathable film and a nonwoven substrate can improve the adhesion of the monolithic breathable film to the nonwoven substrate while maintaining the moisture vapor transmission rate (MVTR) of the entire article. Such an article can be suitable for use as a construction material (e.g., a housewrap or a roofwrap).


In one aspect, this disclosure features an article that includes a nonwoven substrate, a first film supported by the nonwoven substrate, and a second film. The first film is between the nonwoven substrate and the second film, and includes a first polymer and a pore-forming filler. The difference between a surface energy of the first film and a surface energy of the nonwoven substrate is at most about 10 mN/m. The second film includes a second polymer capable of absorbing and desorbing moisture and providing a barrier to aqueous fluids.


In another aspect, this disclosure features an article that includes a nonwoven substrate, a first film supported by the nonwoven substrate, and a second film. The first film is between the nonwoven substrate and the second film and includes a first polymer and a pore-forming filler. The difference between a surface energy of the first film and a surface energy of the nonwoven substrate being at most about 10 mN/m. The second film includes a second polymer selected from the group consisting of maleic anhydride block copolymers, glycidyl methacrylate block copolymers, polyether block copolymers, polyurethanes, polyethylene-containing ionomers, and mixtures thereof.


In another aspect, this disclosure features an article that includes a nonwoven substrate, a first film supported by the nonwoven substrate, and a second film. The first film is between the nonwoven substrate and the second film, and includes a first polymer and a pore-forming filler. The first polymer includes a polyolefin or a polyester. The second film includes a second polymer selected from the group consisting of maleic anhydride block copolymers, glycidyl methacrylate block copolymers, polyether block copolymers, polyurethanes, polyethylene-containing ionomers, and mixtures thereof.


In another aspect, this disclosure features a constructive material (e.g., a housewrap or a roofwrap) that includes at least one of the articles described above.


In still another aspect, this disclosure features a method of making the article described above. The method includes (1) applying a first film and a second film onto a nonwoven substrate to form a laminate such that the first film is between the nonwoven substrate and the second film; and (2) stretching the laminate to form the article. The first film includes a first polymer and a pore-forming filler. The difference between a surface energy of the first film and a surface energy of the nonwoven substrate is at most about 10 mN/m. The second film includes a second polymer capable of absorbing and desorbing moisture and providing a barrier to aqueous fluids.


Embodiments can include one or more of the following optional features.


The second polymer is selected from the group consisting of maleic anhydride block copolymers (e.g., poly(olefin-co-acrylate-co-maleic anhydride) such as poly(ethylene-co-acrylate-co-maleic anhydride)), glycidyl methacryalte block copolymers (e.g., poly(olefin-co-acrylate-co-glycidyl methacrylate) such as poly(ethylene-co-acrylate-co-glycidyl methacrylate)), polyether block copolymers (e.g., polyether ester block copolymers, polyether amide block copolymers, or poly(ether ester amide) block copolymers), polyurethanes, polyethylene-containing ionomers, and mixtures thereof.


The second film can further include a polyolefin, such as a polyethylene or a polypropylene. Examples of polyethylene polymers include those selected from the group consisting of low-density polyethylene, linear low-density polyethylene, high-density polyethylene, and copolymers thereof.


The second film can further include a vinyl polymer. The vinyl polymer can include a copolymer formed between a first comonomer and a second comonomer, in which the first comonomer can include ethylene, and the second commoner can include alkyl methacrylate, alkyl acrylate, or vinyl acetate. Exemplary vinyl polymers include poly(ethylene-co-methyl acrylate), poly(ethylene-co-vinyl acetate), poly(ethylene-co-ethyl acrylate), and poly(ethylene-co-butyl acrylate).


The second film can further include a compatibilizer, such as polypropylene grafted with maleic anhydride (PP-g-MAH) or a polymer formed by reacting PP-g-MAH with a polyetheramine.


The second film can include at least about 20% by weight of the second polymer; at least about 10% by weight of the vinyl polymer; at least about 5% by weight of the polyolefin; and at least about 0.1% by weight of the compatibilizer, based on the weight of the second film.


The second film can further include a polyester, such as a polybutylene terephthalate, a polyethylene terephthalate, or a polytrimethylene terephthalate.


The first polymer can include a polyolefin (e.g., a polyethylene or a polypropylene) or a polyester (e.g., a polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, polyglycolide, polylactide, polycaprolactone, polyethylene adipate, polyhydroxyalkanoate, or a copolymer thereof).


The pore-forming filler can include calcium carbonate. For example, the first film can include from about 30% by weight to about 70% by weight of the calcium carbonate.


The first film can further include a nanoclay, such as a montmorillonite clay.


The first film can further include an elastomer, such as a propylene-ethylene copolymer.


The first film can be from about 2% to about 98% of the total weight of the first and second films.


The nonwoven substrate can include randomly disposed polymeric fibers, at least some of the fibers being bonded to one another.


The article can have a moisture vapor transmission rate (MVTR) of at least about 35 g/m2/day when measured at 23° C. and 50 RH %.


The article can have a tensile strength of at least about 40 pounds in the machine direction and/or a tensile strength of at least about 35 pounds in the cross-machine direction as measured according to ASTM D5034.


The article can have a hydrostatic head of at least about 55 cm.


The article can be embossed.


The first and second films can be co-extruded onto the nonwoven substrate.


The laminate can be stretched at an elevated temperature (e.g., at least about 30° C.).


The laminate can be stretched in the machine direction or in the cross-machine direction.


The laminate can be stretched by a method selected from the group consisting of ring rolling, tentering, embossing, creping, and button-breaking.


The method can further include embossing the laminate prior to or after stretching the laminate.


The method can further include bonding randomly disposed polymeric fibers to produce the nonwoven substrate prior to forming the laminate.


Embodiments can provide the following advantage.


Without wishing to be bound by theory, it is believed that a vapor-permeable, substantially water-impermeable multilayer article containing a microporous breathable film (e.g., a film containing the same type of polymer used in the nonwoven substrate) between a monolithic breathable film and a nonwoven substrate can improve the adhesion of the monolithic breathable film to the nonwoven substrate while maintaining the MVTR of the entire article.


Other features and advantages of the invention will be apparent from the description, drawings, and claims.





DESCRIPTION OF DRAWINGS


FIG. 1 is a cross-sectional view of a vapor permeable, substantially water impermeable multilayer article.



FIG. 2 is a scheme illustrating an exemplary extruding process.



FIG. 3 is a scheme illustrating an exemplary ring-rolling apparatus.





Like reference symbols in the various drawings indicate like elements.


DETAILED DESCRIPTION

This disclosure relates to, for instance, an article (e.g., a vapor-permeable, substantially water-impermeable multilayer article) containing a microporous breathable film between a monolithic breathable film and a nonwoven substrate. The microporous breathable film can include a polymer and a pore-forming filler. The monolithic breathable film can include a polymer capable of absorbing and desorbing moisture and providing a barrier to aqueous fluids. The nonwoven substrate can be formed from polymeric fibers (e.g., fibers made from polyolefins).



FIG. 1 is a cross-sectional view of a vapor permeable, substantially water impermeable multilayer article 10 containing a monolithic breathable film 12, a microporous breathable film 16, and a nonwoven substrate 14.


Microporous Breathable Film


Microporous breathable film 16 can include a polymer and a pore-forming filler.


The polymer used to form film 16 and the polymer forming the surface of nonwoven substrate 14 can be selected in such a manner that the difference between the surface energy of film 16 and that of nonwoven substrate 14 is at most about 10 mN/m (e.g., at most about 8 mN/m, at most about 6 mN/m, at most about 4 mN/m, at most about 2 mN/m, at most about 1 mN/m, or at most about 0.5 mN/m). In some embodiments, the surface energy of film 16 is substantially the same as that of nonwoven substrate 14. Without wishing to be bound by theory, it is believed that when the difference between the surface energy of film 16 and that of nonwoven substrate 14 is relatively small, the adhesion between the film 16 and nonwoven substrate can be significantly improved.


In some embodiments, film 16 can be made from a polyolefin or a polyester. In some embodiments, film 16 can include at least two (e.g., three, four, or five) polymers. In such embodiments, the difference between the surface energy of film 16 and that of that of nonwoven substrate 14 can be at most about 10 mN/m. As an example, when the polymer on the surface of nonwoven substrate 14 is a polyolefin (e.g., a polyethylene or polypropylene), the polymer used to form film 16 can also be a polyolefin (e.g., a polyethylene or polypropylene). As used here, the term “polyolefin” refers to a homopolymer or a copolymer made from a linear or branched, cyclic or acyclic alkene. Examples of polyolefins that can be used in film 16 include polyethylene, polypropylene, polybutene, polypentene, and polymethylpentene.


Polyethylene has been reported to have a surface energy of from about 35.3 mN/m to about 35.7 mN/m at 20° C. and polypropylene has been reported to have a surface energy of about 30 mN/m at 20° C. Thus, when both film 16 and nonwoven substrate 14 are made primarily from a polyethylene or polypropylene, the difference between the surface energy of film 16 and that of substrate 14 can range from about 0.5 mN/m to about 0 mN/m. When one of film 16 and substrate 14 is made primarily from a polyethylene and the other is made primarily from a polypropylene, the difference between the surface energy of film 16 and that of substrate 14 can range from about 5 mN/m to about 6 mN/m.


Exemplary polyethylene include low-density polyethylene (e.g., having a density from 0.910 g/cm2 to 0.925 g/cm2), linear low-density polyethylene (e.g., having a density from 0.910 g/cm2 to 0.935 g/cm2), and high-density polyethylene (e.g., having a density from 0.935 g/cm2 to 0.970 g/cm2). High-density polyethylene can be produced by copolymerizing ethylene with one or more C4 to C20 α-olefin co-monomers. Examples of suitable α-olefin co-monomers include 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, and combinations thereof. The high-density polyethylene can include up to 20 mole percent of the above-mentioned α-olefin co-monomers. In some embodiments, the polyethylene suitable for use in film 16 can have a melt index in the range of from about 0.1 g/10 min to about 10 g/10 min (e.g., from about 0.5 g/10 min to 5 g/10 min).


Polypropylene can be used in film 16 by itself or in combination with one or more of the polyethylene polymers described above. In the latter case, polypropylene can be either copolymerized or blended with one or more polyethylene polymers. Both polyethylene and polypropylene are available from commercial sources or can be readily prepared by methods known in the art.


In some embodiments, when the polymer forming the surface of nonwoven substrate 14 is a polyester (e.g., a polyethylene terephthalate), the polymer used to form film 16 can also be a polyester (e.g., a polyethylene terephthalate or a polybutylene terephthalate). Examples of polyesters that can be used in film 16 include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), polyglycolide or polyglycolic acid (PGA), polylactide or polylactic acid (PLA), polycaprolactone (PCL), polyethylene adipate (PEA), polyhydroxyalkanoate (PHA), and copolymers thereof. As an example, polyethylene terephthalate has been reported to have a surface energy of about 44.6 mN/m at 20° C.


The amount of the polymer in film 16 can vary depending on the desired applications. For example, the polymer can be at least about 30% (e.g., at least about 35%, at least about 40%, at least about 45%, at least about 50%, or at least about 60%) and/or at most about 95% (e.g., at most about 90%, at most about 85%, at most about 80%, at most about 75%, or at most about 70%) of the total weight of film 16.


The pore-forming filler in film 16 can generate pores upon stretching (e.g., by using a ring-rolling process during the manufacture of multilayer article 10) to impart breathability to film 16 (i.e., to allow passage of vapor through film 16).


The pore-forming filler generally has a low affinity to and a lower elasticity than the polyolefin component or the other optional components. The pore-forming filler can be a rigid material. It can have a non-smooth surface, or have a surface treated to become hydrophobic.


In some embodiments, the pore-forming filler is in the form of particles. In such embodiments, the average value of the maximum linear dimension of the filler particles can be at least about 0.5 micron (at least about 1 micron or at least about 2 microns) and/or at most about 7 microns (e.g., at most about 5 microns or at most about 3.5 microns). Without wishing to be bound by theory, it is believed that filler particles with a relatively small average value of the maximum linear dimension (e.g., from about 0.75 microns to 2 microns) can provide a better balance of compoundability and breathability than filler particles with a relatively large average value of the maximum linear dimension.


The pore-forming filler in film 16 can be any suitable inorganic or organic material, or combinations thereof. Examples of the inorganic fillers include calcium carbonate, talc, clay, kaolin, silica diatomaceous earth, magnesium carbonate, barium carbonate, magnesium sulfate, barium sulfate, calcium sulfate, aluminum hydroxide, zinc oxide, magnesium oxide, calcium oxide, magnesium oxide, titanium oxide, alumina, mica, glass powder, glass beads (hollow or non-hollow), glass fibers, zeolite, silica clay, and combinations thereof. In some embodiments, the pore forming filler in film 16 includes calcium carbonate. In some embodiments, the inorganic pore-forming filler can be surface treated to be hydrophobic so that the filler can repel water to reduce agglomeration of the filler. In addition, the pore-forming filler can include a coating on the surface to improve binding of the filler to the polyolefin in film 16 while allowing the filler to be pulled away from the polyolefin when film 16 is stretched or oriented (e.g., during a ring-rolling process). Exemplary coating materials include stearates, such as calcium stearate. Examples of organic fillers that can be used in film 16 include wood powder, pulp powder, and other cellulose type powders. Polymer powders such as TEFLON powder and KEVLAR powder can also be included as an organic pore forming filler. The pore forming fillers described above are either available from commercial sources or can be readily prepared by methods known in the art.


Film 16 can include a relatively high level of the pore-forming filler as long as the level of the filler does not undesirably affect the formation of film 16. For example, film 16 can include from at least about 5% (e.g., at least about 10%, at least about 20%, or at least about 30%) to at most about 70% (e.g., at most about 60%, at most about 50%, or at most about 40%) by weight of the pore-forming filler (e.g., calcium carbonate). In some embodiments, film 16 can include about 50% by weight of the pore-forming filler. Without wishing to be bound by theory, it is believed that, if film 16 does not include a sufficient amount (e.g., at least about 30% by weight) of the pore-forming filler, the film may not have an adequate moisture vapor transmission rate (MVTR) (e.g., at least about 35 g/m2/day when measured at 23° C. and 50 RH %). Further, without wishing to be bound by theory, it is believed that, if film 16 includes too much (e.g., more than about 70%) of the pore-forming filler, film 16 may not be uniform or may have a low tensile strength.


In some embodiments, film 16 can further include a functionalized polyolefin (e.g., functionalized polyethylene or polypropylene), such as a polyolefin graft copolymer. Examples of such polyolefin graft copolymers include polypropylene-g-maleic anhydride and polymers formed by reacting PP-g-MAH with a polyetheramine. In some embodiments, such a functionalized polyolefin can be used a compatibilizer to minimize the phase separation between the components in film 16 and/or to improve adhesion between film 16 and nonwoven substrate 14. The compatibilizer can be at least about 0.1% (e.g., at least about 0.2%, at least about 0.4%, at least about 0.5%, at least about 1%, or at least about 1.5%) and/or at most about 30% (e.g., at most about 25%, at most about 20%, at most about 15%, at most about 10%, at most about 5%, at most about 4%, at most about 3%, or at most about 2%) of the total weight of film 16.


Optionally, film 16 can include an elastomer (e.g., a thermoplastic olefin elastomer) to improve the elasticity of the film. Examples of suitable elastomers include vulcanized natural rubber, ethylene alpha olefin rubber (EPM), ethylene alpha olefin diene monomer rubber (EPDM), styrene-isoprene-styrene (SIS) copolymers, styrene-butadiene-styrene (SBS) copolymers, styrene-ethylene-butylene-styrene (SEBS) copolymers, ethylene-propylene (EP) copolymers, ethylene-vinyl acetate (EVA) copolymers, ethylene-maleic anhydride (EMA) copolymers, ethylene-acrylic acid (EEA) copolymers, and butyl rubber. Commercial examples of such an elastomer include VERSIFY (i.e., an ethylene-propylene copolymer) available from Dow (Midland, Mich.) and LOTRYL (i.e., an ethylene-maleic anhydride copolymer) available from Arkema (Philadelphia, Pa.). Film 16 can include from about 5% (e.g., at least about 6% or at least about 7%) to at most about 30% (e.g., at most about 25%, at most about 20%, or at most about 15%) by weight of the elastomer. Without wishing to be bound by theory, it is believed that one advantage of using an elastomer in film 16 is that multilayer article 10 containing such a film can have both improved tensile strength (e.g., by at least about 5% or at least about 10%) and improved elongation (e.g., by at least about 20% or at least about 50%).


Further, film 16 can optionally include a nanoclay (e.g., montmorillonite nanoclay). Examples of nanoclays have been described in, e.g., U.S. Provisional Patent Application No. 61/498,328, entitled “Vapor Permeable, Substantially Water Impermeable Multilayer Article.”


Monolithic Breathable Film


Film 12 can include a breathable polymer capable of absorbing and desorbing moisture and providing a barrier to aqueous fluids (e.g., water). For example, the breathable polymer can absorb moisture from one side of film 12 and release it to the other side of film 12. As the breathable polymer imparts breathability to film 12, film 12 does not need to include pores. As such, film 12 can be monolithic and not porous. In addition, as film 12 can be co-extruded with film 16 onto nonwoven substrate 14, the extruded films thus obtained can have excellent adhesion between each other. Thus, film 12 does not need to have a surface energy similar to that of film 16 and can have any suitable surface energy.


In some embodiments, the breathable polymer in film 12 can include maleic anhydride block copolymers, glycidyl methacrylate block copolymers, polyether block copolymers, polyurethanes, polyethylene-containing ionomers, and mixtures thereof. Examples of maleic anhydride block copolymers include poly(olefin-co-acrylate-co-maleic anhydride), such as poly(ethylene-co-acrylate-co-maleic anhydride). Commercial examples of maleic anhydride block copolymers include LOTADER MAH available from Arkema and BYNEL available from E.I. du Pont de Nemours and Company, Inc. (Wilmington, Del.). Examples of glycidyl methacrylate block copolymers include poly(olefin-co-acrylate-co-glycidyl methacrylate), such as poly(ethylene-co-acrylate-co-glycidyl methacrylate). A commercial example of a glycidyl methacrylate block copolymer is LOTADER GMA available from Arkema.


Examples of polyether block copolymers include polyether ester block copolymers, polyether amide block copolymers, and poly(ether ester amide) block copolymers. Commercial examples of polyether ester block copolymers include ARNITEL available from DSM Engineering Plastics (Evansville, Ind.), HYTREL available from E.I. du Pont de Nemours and Company, Inc., and NEOSTAR available from Eastman Chemical Company (Kingsport, Tenn.). A commercial example of a polyether amide block copolymer is PEBAX available from Arkema.


A polyethylene-containing ionomer can include an ethylene copolymer moiety and an acid copolymer moiety. The ethylene copolymer moiety can be formed by copolymerizing ethylene and a monomer selected from the group consisting of vinyl acetate, alkyl acrylate, and alkyl methacrylate. The acid copolymer moiety can be formed by copolymerizing ethylene and a monomer selected from the group consisting of acrylic acid and methacrylic acid. The acidic groups in the polyethylene-containing ionomer can be partially or fully converted to salts that include suitable cations, such as Li+, Na+, K+, Mg2+, and Zn2+. Examples of polyethylene-containing ionomers include those described in U.S. Patent Application Publication Nos. 2009/0142530 and 2009/0123689. Commercial examples of polyethylene-containing ionomers include ENTIRA and DPO AD 1099 available from E.I. du Pont de Nemours and Company, Inc. (Wilmington, Del.).


Other suitable breathable polymers have been described in, for example, U.S. Pat. Nos. 5,800,928 and 5,869,414.


The amount of the breathable polymer in film 12 can vary depending on the desired applications. Film 12 can include an amount of the breathable polymer that is large enough to impart desired breathability to film 12 but small enough to minimize manufacturing costs. For example, the breathable polymer can be at least about 20% (e.g., at least about 25%, at least about 30%, at least about 35%, at least about 40%, or at least about 45%) and/or at most about 100% (e.g., at most about 90%, at most about 80%, at most about 70%, at most about 60%, or at most about 50%) of the total weight of film 12.


As breathable polymers can be expensive to manufacture, film 12 can optionally include a vinyl polymer to reduce costs while maintaining the properties of this film. The vinyl polymer can include a copolymer formed between a first comonomer and a second comonomer different from the first comonomer. Examples of the first comonomer can be olefins (such as ethylene or propylene). Examples of the second commoner can include alkyl methacrylate (e.g., methyl methacrylate), alkyl acrylate (e.g., methyl acrylate, ethyl acrylate, or butyl acrylate), and vinyl acetate. Examples of suitable vinyl polymers include poly(ethylene-co-methyl acrylate), poly(ethylene-co-vinyl acetate), poly(ethylene-co-ethyl acrylate), and poly(ethylene-co-butyl acrylate).


In some embodiments, film 12 can include at least about 10% (e.g., at least about 15%, at least about 20%, at least about 25%, at least about 30%, or at least about 40%) and/or at most about 70% (e.g., at most about 65%, at most about 60%, at most about 55%, at most about 50%, or at most about 45%) by weight of the vinyl polymer.


In some embodiments, when film 16 is made from a polyolefin, film 12 can optionally include a suitable amount of a polyolefin that is either the same as or similar to that in film 16 to improve adhesion between these two films. For example, the polyolefin in film 12 can be a polyethylene (e.g., a low-density polyethylene, a linear low-density polyethylene, a high density polyethylene, and a copolymer thereof), a polypropylene, or a mixture thereof. The amount of the polyolefin in film 12 can be at least about 5% (e.g., at least about 10%, at least about 15%, at least about 20%, at least about 25%, or at least about 30%) and/or at most about 60% (e.g., at most about 55%, at most about 50%, at most about 45%, at most about 40%, or at most about 35%) of the total weight of film 12. Similarly, when film 16 is made from a polyester or a mixture of polymers, film 12 can optionally include a suitable amount of a polyester (e.g., a polybutylene terephthalate, a polyethylene terephthalate, or a polytrimethylene terephthalate) or a mixture of polymers that are either the same as or similar to those in film 16.


When film 12 includes at least two polymers, it can optionally include a compatibilizer to improve the compatibility of the polymers (e.g., by reducing phase separation). The compatibilizer can be a functionalized polyolefin (e.g., functionalized polyethylene or polypropylene), such as a polyolefin graft copolymer. Examples of such polyolefin graft copolymers include polypropylene-g-maleic anhydride and a polymer formed by reacting PP-g-MAH with a polyetheramine. The compatibilizer can be at least about 0.1% (e.g., at least about 0.2%, at least about 0.4%, at least about 0.5%, at least about 1%, or at least about 1.5%) and/or at most about 5% (e.g., at most about 4.5%, at most about 4%, at most about 3.5%, at most about 3%, or at most about 2.5%) of the total weight of film 12.


The weight ratio between films 12 and 16 can vary depending on, e.g., the compositions of the films or the intended applications. In some embodiments, film 12 is from about 2% to about 98% (e.g., from about 5% to about 95%, from about 10% to about 90%, from about 20% to about 80%, or from about 40% to about 60%) of the total weight of films 12 and 16.


Without wishing to be bound by theory, it is believed that a vapor-permeable, substantially water-impermeable multilayer article containing microporous breathable film 16 (e.g., containing the same type of polymer used in the nonwoven substrate) between monolithic breathable film 12 and nonwoven substrate 14 can improve the adhesion of film 12 to nonwoven substrate 14 while maintaining the MVTR of the entire article.


Nonwoven Substrate


Nonwoven substrate 14 can include randomly disposed polymeric fibers, at least some of the fibers being bonded to one another. As used herein, the term “nonwoven substrate” refers to a substrate containing one or more layers of fibers that are bonded together, but not in an identifiable manner as in a knitted or woven material.


Nonwoven substrate 14 can be formed from any suitable polymers. Exemplary polymers that can be used to form nonwoven substrate 14 include polyolefins and polyesters. Examples of suitable polyolefins include polyethylene, polypropylene, and copolymers thereof, such as those in film 12 described above. Examples of suitable polyesters include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), polyglycolide or polyglycolic acid (PGA), polylactide or polylactic acid (PLA), polycaprolactone (PCL), polyethylene adipate (PEA), polyhydroxyalkanoate (PHA), and copolymers thereof.


Nonwoven substrate 14 can be formed from single component fibers, i.e., fibers containing a polymer having a single chemical structure (e.g., a polymer described in the preceding paragraph such as a polyethylene, a polypropylene, or a polyethylene terephthalate). In some embodiments, nonwoven substrate 14 can include single component fibers made from polymers having the same chemical structure but different characteristics (e.g., molecular weights, molecular weight distributions, density, or intrinsic viscosities). For example, substrate 14 can include a mixture of a low density polyethylene and a high density polyethylene. Such fibers are still referred to as single component fibers in this disclosure.


Nonwoven substrate 14 can also be formed from multicomponent fibers, i.e., fibers containing polymers with different chemical structures (such as two different polymers described above). For example, substrate 14 can be formed from a mixture of a polypropylene and a polyethylene terephthalate. In some embodiments, a multicomponent fiber can have a sheath-core configuration (e.g., having a polyethylene terephthalate as the core and a polypropylene as the sheath). In some embodiments, a multicomponent fiber can include two or more polymer domains in a different configuration (e.g., a side-by-side configuration, a pie configuration, or an “islands-in-the-sea” configuration).


In some embodiments, the surface of nonwoven substrate 14 can be formed of a polymer having a chemical structure similar to (e.g., the same type as) or the same as the chemical structure of a polymer in the surface of film 16. As an example, a polyolefin (e.g., a polyethylene or propylene) is of the same type as and similar to a different polyolefin (e.g., a polyethylene or propylene). Without wishing to be bound by theory, it is believed that such two layers can have improved adhesion. For example, when nonwoven substrate 14 is formed from single component fibers, the fibers can be made from a polyolefin, which has a chemical structure similar to or the same as a polyolefin that is used to make film 16. When nonwoven substrate 14 is formed of multicomponent fibers (e.g., having a sheath-core configuration), the polymer (e.g., a polyolefin in the sheath) in the fibers that contacts film 16 can have a chemical structure similar to or the same as the chemical structure of a polyolefin in film 16. Both examples described above can result in a multilayer article with improved adhesion between the film and the nonwoven substrate.


Nonwoven substrate 14 can be made by methods well known in the art, such as a spunlacing, spunbonding, meltblowing, carding, air-through bonding, or calendar bonding process.


In some embodiments, nonwoven substrate 14 can be a spunbonded nonwoven substrate. In such embodiments, nonwoven substrate 14 can include a plurality of random continuous fibers, at least some (e.g., all) of which are bonded (e.g., area bonded or point bonded) with each other through a plurality of intermittent bonds. The term “continuous fiber” mentioned herein refers to a fiber formed in a continuous process and is not shortened before it is incorporated into a nonwoven substrate containing the continuous fibers.


As an example, nonwoven substrate 14 containing single component fibers can be made by using a spunbonding process as follows.


After the polymer for making single component fibers is melted, the molten polymer can be extruded from an extruding device. The molten polymer can then be directed into a spinneret with composite spinning orifices and spun through this spinneret to form continuous fibers. The fibers can subsequently be quenched (e.g., by cool air), attenuated mechanically or pneumatically (e.g., by a high-velocity fluid), and collected in a random arrangement on a surface of a collector (e.g., a moving substrate such as a moving wire or belt) to form a nonwoven web. In some embodiments, a plurality of spinnerets with different quenching and attenuating capability can be used to place one or more (e.g., two, three, four, or five) layers of fibers on a collector to form a substrate containing one or more layers of spunbonded fibers (e.g., an S, SS, or SSS type of substrate). In some embodiments, one or more layers of meltblown fibers can be inserted between the layers of the above-described spunbonded fibers to form a substrate containing both spunbonded and meltblown fibers (e.g., an SMS, SMMS, or SSMMS type of substrate).


A plurality of intermittent bonds can subsequently be formed between at least some of the fibers (e.g., all of the fibers) randomly disposed on the collector to form a unitary, coherent, nonwoven substrate. Intermittent bonds can be formed by a suitable method such as mechanical needling, thermal bonding, ultrasonic bonding, or chemical bonding. Bonds can be covalent bonds (e.g., formed by chemical bonding) or physical attachments (e.g., formed by thermal bonding). In some embodiments, intermittent bonds are formed by thermal bonding. For example, bonds can be formed by known thermal bonding techniques, such as point bonding (e.g., using calender rolls with a point bonding pattern) or area bonding (e.g., using smooth calender rolls without any pattern). Bonds can cover between about 6 percent and about 40 percent (e.g., between about 8 percent and about 30 percent or between about 22 percent and about 28 percent) of the total area of nonwoven substrate 14. Without wishing to be bound by theory, it is believed that forming bonds in substrate 14 within these percentage ranges allows elongation throughout the entire area of substrate 14 upon stretching while maintaining the strength and integrity of the substrate.


Optionally, the fibers in nonwoven substrate 14 can be treated with a surface-modifying composition after intermittent bonds are formed. Methods of applying a surface-modifying composition to the fibers have been described, for example, in U.S. Provisional Patent Application No. 61/294,328.


The nonwoven substrate thus formed can then be used to form multilayer article 10 described above. A nonwoven substrate containing multicomponent fibers can be made in a manner similar to that described above. Other examples of methods of making a nonwoven substrate containing multicomponent fibers have been described in, for example, U.S. Provisional Patent Application No. 61/294,328.


Method of Making Multilayer Article


Multilayer article 10 can be made by the methods known in the art or the methods described herein. For example, multilayer article 10 can be made by first applying films 12 and 16 onto nonwoven substrate 14 to form a laminate. Films 12 and 16 can be applied onto nonwoven substrate 14 by co-extruding (e.g., cast extrusion) a suitable composition for film 12 (e.g., a composition containing a breathable polymer) and a suitable composition for film 16 (e.g., a composition containing a polyolefin and a pore forming filler) at an elevated temperature to form two layers of films onto nonwoven substrate 14. In some embodiments, the just-mentioned compositions can be co-extruded (e.g., by tubular extrusion or cast extrusion) to form a web, which can be cooled (e.g., by passing through a pair of rollers) to form a precursor two-layer film. A laminate can then be formed by attaching the precursor film to nonwoven substrate 14 by using, for example, an adhesive (e.g., a spray adhesive, a hot melt adhesive, or a latex based adhesive), thermal bonding, ultra-sonic bonding, or needle punching.


In some embodiments, multilayer article 10 can include multiple (e.g., two, three, four, or five) films supported by nonwoven substrate 14, wherein at least two of the films are films 12 and 16 described above. The additional films can be made by one or more of the materials used to prepare film 12 or 16 described above or other materials known in the art. In some embodiments, nonwoven substrate 14 can be disposed between two of the multiple films. In some embodiments, all of the films can be disposed on one side of nonwoven substrate 14.



FIG. 2 is a scheme illustrating an exemplary process for making a laminate described above. As shown in FIG. 2, a suitable composition for film 16 (e.g., a composition containing a polyolefin and a pore-forming filler) can be fed into an inlet 26 of an extruder hopper 24. The composition can then be melted and mixed in a screw extruder 20. The molten mixture can be discharged from extruder 20 under pressure through a heated line 22 to a flat film die 38. A suitable composition for film 12 (e.g., a composition containing a breathable polymer) can be fed into an inlet 36 of an extruder hopper 34. The composition can then be melted and mixed in a screw extruder 30. The molten mixture can be discharged from extruder 30 under pressure through a heated line 32 to flat film die 38 to be co-extruded with the molten mixture for film 16. Co-extruded melt 40 discharging from flat film die 38 can be coated on nonwoven substrate 14 from roll 50 such that film 16 is between nonwoven substrate 14 and film 12. The coated substrate can then enter a nip formed between rolls 52 and 56, which can be maintained at a suitable temperature (e.g., between about 10-120° C.). Passing the coated substrate through the nip formed between cooled rolls 52 and 56 can quench co-extrusion melt 40 while at the same time compressing co-extrusion melt 40 so that it forms a contact on nonwoven substrate 14. In some embodiments, roll 52 can be a smooth rubber roller with a low-stick surface coating while roll 56 can be a metal roll. A textured embossing roll can be used to replace metal roll 56 if a multilayer article with a textured film layer is desired. When co-extrusion melt 40 is cooled, it forms films 16 and 12 laminated onto nonwoven substrate 14. The laminate thus formed can then be collected on a collection roll 54. In some embodiments, the surface of nonwoven substrate 14 can be corona or plasma treated before it is coated with co-extrusion melt 40 to improve the adhesion between nonwoven substrate 14 and film 16.


The laminate formed above can then be stretched (e.g., incrementally stretched or locally stretched) to form a vapor-permeable, substantially water-impermeable multilayer article 10. Without wishing to be bound by theory, it is believed that stretching the laminate generates pores around the pore-forming filler in film 16 that render this film breathable (i.e., allowing air and/or water vapor to pass through), but does not generate pores in film 12. The laminate can be stretched (e.g., incrementally stretched) in the machine direction (MD) or the cross-machine direction (CD) or both (biaxially) either simultaneously or sequentially. As used herein, “machine direction” refers to the direction of movement of a nonwoven material during its production or processing. For example, the length of a nonwoven material can be the dimension in the machine direction. As used herein, “cross-machine direction” refers to the direction that is essentially perpendicular to the machine direction defined above. For example, the width of a nonwoven material can be the dimension in the cross-machine direction. Examples of incremental-stretching methods have been described in, e.g., U.S. Pat. Nos. 4,116,892 and 6,013,151.


Exemplary stretching methods include ring rolling (in the machine direction and/or the cross-machine direction), tentering, embossing, creping, and button-breaking. These methods are known in the art, such as those described in U.S. Pat. No. 6,258,308 and U.S. Provisional Application No. 61/294,328.


In some embodiments, the laminate described above can be stretched (e.g., incrementally stretched) at an elevated temperature as long as the polymers in the laminate maintain a sufficient mechanical strength at that temperature. The elevated temperature can be at least about 30° C. (e.g., at least about 40° C., at least about 50° C., or at least about 60° C.) and/or at most about 100° C. (e.g., at least about 90° C., at least about 80° C., or at least about 70° C.). Without wishing to be bound by theory, it is believed that stretching the laminate described above at an elevated temperature can soften the polymers in films 12 and 16 and nonwoven substrate 14, and therefore allow these polymers to be stretched easily. In addition, without wishing to be bound by theory, it is believed that stretching the laminate described above at an elevated temperature can increase the MVTR by increasing the number of the pores in film 16, rather than the size of the pores (which can reduce the hydrostatic head (i.e., resistance of water) of the multilayer article). As a result, it is believed that stretching the laminate described above at an elevated temperature can unexpectedly improve the MVTR of the resultant multilayer article while still maintaining an appropriate hydrostatic head of the multilayer article. In certain embodiments, the laminate described above can be stretched (e.g., incrementally stretched) at an ambient temperature (e.g., at about 25° C.).



FIG. 3 illustrates an exemplary ring-rolling apparatus 320 used to incrementally stretch the laminate described above in the cross-machine direction. Apparatus 320 includes a pair of grooved rolls 322, each including a plurality of grooves 324. The grooves 324 stretch the laminate described above to form multilayer article 10. In some embodiments, one or both of rolls 322 can be heated to an elevated temperature (e.g., between about 30° C. and about 100° C.) by passing a hot liquid through roll 322. The laminate described above can also be incrementally stretched in the machine direction in a similar manner. It is contemplated that the laminate can also be incrementally stretched using variations of the ring-rolling apparatus 320 and/or one or more other stretching apparatus known in the art.


In some embodiments, the laminate described above can be embossed prior to or after being stretched (e.g., by using a calendering process). For example, the laminate can be embossed by passing through a pair of calender rolls in which one roll has an embossed surface and the other roll has a smooth surface. Without wishing to be bound by theory, it is believed that an embossed multilayer article can have a large surface area, which can facilitate vapor transmission through the multilayer article. In some embodiments, at least one (e.g., both) of the calender rolls is heated, e.g., by circulating a hot oil through the roll.


Properties of Multilayer Article


Without wishing to be bound by theory, it is believed that the adhesion between film 16 and nonwoven substrate 14 is significantly higher than that between film 12 and nonwoven substrate. For example, the adhesion between film 16 and nonwoven substrate 14 can be at least about 200 gram-force/in (e.g., at least about 300 gram-force/in, at least about 500 gram-force/in, at least about 1,000 gram-force/in, or at least about 1,500 gram-force/in). By contrast, the adhesion between film 12 and nonwoven substrate 14 can be at most about 200 gram-force/in (e.g., at most about 150 gram-force/in, at most about 100 gram-force/in, at most about 50 gram-force/in, or at most about 10 gram-force/in).


In some embodiments, multilayer article 10 can have a suitable MVTR based on its intended uses. As used herein, the MVTR values are measured according to ASTM E96-A. For example, multilayer article 10 can have a MVTR of at least about 35 g/m2/day (e.g., at least about 50 g/m2/day, at least about 75 g/m2/day, or at least about 100 g/m2/day) and/or at most about 140 g/m2/day (e.g., at most about 130 g/m2/day, at most about 120 g/m2/day, or at most about 110 g/m2/day) when measured at 23° C. and 50 RH %. Multilayer article 10 can have a MVTR of between 70 g/m2/day and 140 g/m2/day.


In some embodiments, multilayer article 10 can have a sufficient tensile strength in the machine direction and/or the cross-machine direction. The tensile strength is determined by measuring the tensile force required to rupture a sample of a sheet material. The tensile strength mentioned herein is measured according to ASTM D5034 and is reported in pounds. In some embodiments, multilayer article 10 can have a tensile strength of at least about 40 pounds (e.g., at least about 50 pounds, at least about 60 pounds, at least about 70 pounds, or at least about 80 pounds) and/or at most about 160 pounds (e.g., at most about 150 pounds, at most about 140 pounds, at most about 130 pounds, or at most about 120 pounds) in the machine direction. In some embodiments, multilayer article 10 can have a tensile strength of at least about 35 pounds (e.g., at least about 40 pounds, at least about 50 pounds, at least about 60 pounds, or at least about 70 pounds) and/or at most about 140 pounds (e.g., at most about 130 pounds, at most about 120 pounds, at most about 110 pounds, or at most about 100 pounds) in the cross-machine direction.


As a specific example, when multilayer article 10 has a unit weight of 1.25 ounce per square yard, it can have a tensile strength of at least about 40 pounds (e.g., at least about 45 pounds, at least about 50 pounds, at least about 55 pounds, or at least about 60 pounds) and/or at most about 100 pounds (e.g., at most about 95 pounds, at most about 90 pounds, at most about 85 pounds, or at most about 80 pounds) in the machine direction, and at least about 35 pounds (e.g., at least about 40 pounds, at least about 45 pounds, at least about 50 pounds, or at least about 55 pounds) and/or at most about 95 pounds (e.g., at most about 90 pounds, at most about 85 pounds, at most about 80 pounds, or at most about 75 pounds) in the cross-machine direction.


In some embodiments, multilayer article 10 can have a sufficient elongation in the machine direction and/or the cross-machine direction. Elongation is a measure of the amount that a sample of a sheet material will stretch under tension before the sheet breaks. The term “elongation” used herein refers to the difference between the length just prior to break and the original sample length, and is expressed as a percentage of the original sample length. The elongation values mentioned herein are measured according to ASTM D5034. For example, multilayer article 10 can have an elongation of at least about 5% (e.g., at least about 10%, at least about 20%, at least about 30%, at least about 35%, or at least about 40%) and/or at most about 100% (e.g., at most 90%, at most about 80%, or at most about 70%) in the machine direction. As another example, multilayer article 10 can have an elongation of at least about 5% (e.g., at least about 10%, at least about 20%, at least about 30%, at least about 35%, or at least about 40%) and/or at most about 100% (e.g., at most about 90%, at most about 80%, or at most about 70%) in the cross-machine direction.


In some embodiments, multilayer article 10 can have a sufficient hydrostatic head value so as to maintain sufficient water impermeability. As used herein, the term “hydrostatic head” refers to the pressure of a column of water as measured by its height that is required to penetrate a given material and is determined according to AATCC 127. For example, multilayer article 10 can have a hydrostatic head of at least about 55 cm (e.g., at least about 60 cm, at least about 70 cm, at least about 80 cm, at least about 90 cm, or at least about 100 cm) and/or at most about 900 cm (e.g., at most about 800 cm, at most about 600 cm, at most about 400 cm, or at most about 200 cm).


Multilayer article 10 can be used in a consumer product with or without further modifications. Examples of such consumer products include construction materials, such as a housewrap or a roofwrap. Other examples include diapers, adult incontinence devices, feminine hygiene products, medical and surgical gowns, medical drapes, and industrial apparels.


While certain embodiments have been disclosed, other embodiments are also possible.


In some embodiments, an effective amount of various additives can be incorporated in film 12, film 16, or nonwoven substrate 14. Suitable additives include pigments, antistatic agents, antioxidants, ultraviolet light stabilizers, antiblocking agents, lubricants, processing aids, waxes, coupling agents for fillers, softening agents, thermal stabilizers, tackifiers, polymeric modifiers, hydrophobic compounds, hydrophilic compounds, anticorrosive agents, and mixtures thereof. In certain embodiments, additives such as polysiloxane fluids and fatty acid amides can be included to improve processability characteristics.


Pigments of various colors can be added to provide the resultant multilayer article 10 that is substantially opaque and exhibits uniform color. For example, multilayer article 10 can have a sufficient amount of pigments to produce an opacity of at least about 85% (e.g., at least about 90%, at least about 95%, at least about 98%, or at least about 99%). Suitable pigments include, but are not limited to, antimony trioxide, azurite, barium borate, barium sulfate, cadmium pigments (e.g., cadmium sulfide), calcium chromate, calcium carbonate, carbon black, chromium(III) oxide, cobalt pigments (e.g., cobalt(II) aluminate), lead tetroxide, lead(II) chromate, lithopone, orpiment, titanium dioxide, zinc oxide and zinc phosphate. Preferably, the pigment is titanium dioxide, carbon black, or calcium carbonate. The pigment can be about 1 percent to about 20 percent (e.g., about 3 percent to about 10 percent) of the total weight of film 12, film 16, or nonwoven substrate 14. Alternatively, the pigment can be omitted to provide a substantially transparent multilayer article.


In some embodiments, certain additives can be used to facilitate manufacture of multilayer article 10. For example, antistatic agents can be incorporated into film 12, film 16, or nonwoven substrate 14 to facilitate processing of these materials. In addition, certain additives can be incorporated in multilayer article 10 for specific end applications. For example, anticorrosive additives can be added if multilayer article 10 is to be used to package items that are subject to oxidation or corrosion. As another example, metal powders can be added to provide static or electrical discharge for sensitive electronic components such as printed circuit boards.


Each of film 12, film 16, and nonwoven substrate 14 can also include a filler. The term “filler” can include non-reinforcing fillers, reinforcing fillers, organic fillers, and inorganic fillers. For example, the filler can be an inorganic filler such as talc, silica, clays, solid flame retardants, Kaolin, diatomaceous earth, magnesium carbonate, barium carbonate, magnesium sulfate, calcium sulfate, aluminum hydroxide, zinc oxide, magnesium hydroxide, calcium oxide, magnesium oxide, alumina, mica, glass powder, ferrous hydroxide, zeolite, barium sulfate, or other mineral fillers or mixtures thereof. Other fillers can include acetyl salicylic acid, ion exchange resins, wood pulp, pulp powder, borox, alkaline earth metals, or mixtures thereof. The filler can be added in an amount of up to about 60 weight percent (e.g., from about 2 weight percent to about 50 weight percent) of film 12, film 16, or nonwoven substrate 14.


In some embodiments, the surface of film 12, film 16, or nonwoven substrate 14 can be at least partially treated to promote adhesion. For example, the surface of film 12, film 16, or nonwoven substrate 14 can be corona charged or flame treated to partially oxidize the surface and enhance surface adhesion. Without wishing to be bound by theory, it is believed that multilayer article 10 having enhanced surface adhesion can enable printing on its surface using conventional inks. Ink-jet receptive coating can also be added to the surface of multilayer article 10 to allow printing by home or commercial ink-jet printers using water based or solvent based inks.


The following examples are illustrative and not intended to be limiting.


Example 1

The following two multilayer articles were prepared: (1) TYPAR (i.e., a polypropylene spunbonded nonwoven substrate available from Fiberweb, Inc.) having a unit weight of 1.9 ounce per square inch and coated with a monolithic breathable film containing 40 wt % LOTADER, 56 wt % ethyl methacrylate, 2 wt % TiO2, and 2 wt % UV stabilizer, and (2) a multilayer article similar to multilayer article (1) except that it contained a microporous breathable film between the TYPAR and the monolithic breathable film, where the microporous breathable film included 50 wt % calcium carbonate (i.e., a pore-forming filler), 41 wt % polypropylene, 5 wt % low-density polyethylene, 2 wt % TiO2, and 2 wt % UV stabilizer. Multilayer article (1) was formed by extruding the monolithic breathable film onto TYPAR at 480° F. Multilayer article (2) was formed by co-extruding the microporous breathable film and the monolithic breathable film onto TYPAR at the same temperature. Multilayer articles (1) and (2) had total film unit weights of 22 gsm and 27 gsm, respectively.


Multilayer article (1) and (2) were evaluated for their MVTR and the adhesion between the nonwoven substrate and the film(s). The MVTR was measured by using ASTM E96-A. The adhesion was measured as follows: 9-inch long samples were prepared by adhering a 2-inch wide housewrap tape over the coating (folding over one end of the tape onto itself to provide a tab for gripping) to prevent elongation of the coating. The peel adhesion of the samples was then measured by using an Instron or IMASS peel tester with a 5-pound load cell. A 180 degree peel angel was used with a rate of separation of 12 in/minute. The test results are summarized in Table 1 below.











TABLE 1





Sample
Adhesion (gram-force/in)
MVTR (Perm)

















(1)
19.4
7.3


(2)
>200
6.5-8.9









The results showed that, although multilayer article (1) had an adequate MVTR, it exhibited poor adhesion between the nonwoven substrate and the monolithic breathable film. Unexpectedly, multilayer article (2) exhibited superior adhesion between the microporous breathable film and the nonwoven substrate while maintaining the MVTR of the multilayer article.


Example 2

Multilayer articles (3) and (4) were prepared in the same manner as described in Example 1. Multilayer article (3) was similar to multilayer article (1) except that it included a monolithic breathable film containing 45 wt % PEBAX MV3000, 50 wt % LOTRYL 20MA08, and 5 wt % BYNEL 22E757. Multilayer article (4) was similar to multilayer article (2) except that it included a monolithic breathable film containing 45 wt % PEBAX MV3000 and 55 wt % LOTRYL 20MA08.


Multilayer article (3) and (4) were evaluated for their MVTR and the adhesion between the nonwoven substrate and the film(s) using the same methods described in Example 1. The results are summarized in Table 2 below.











TABLE 2





Sample
Adhesion (gram-force/in)
MVTR (Perm)

















(3)
53
13


(4)
286
7.2









The results showed that, although multilayer article (3) had an adequate MVTR, it exhibited poor adhesion between the nonwoven substrate and the monolithic breathable film. Unexpectedly, multilayer article (4) exhibited superior adhesion between the microporous breathable film and the nonwoven substrate while maintaining the MVTR of the multilayer article.


Other embodiments are in the claims.

Claims
  • 1. An article, comprising: a nonwoven substrate;a microporous film supported by the nonwoven substrate, the microporous film comprising a first polymer and a pore-forming filler, the difference between a surface energy of the microporous and a surface energy of the nonwoven substrate being at most about 10 mN/m; anda monolithic film comprising a second polymer capable of absorbing and desorbing moisture and providing a barrier to aqueous fluids, the microporous film being between the nonwoven substrate and the monolithic filmwherein the article has the combination of (i) a maximum percent elongation determined by a difference between an elongated length of the article at break and an original length of the article of less than 70% according to ASTM D5034, and (ii) a moisture vapor transmission rate of at least 35 g/m2/day and at most 140 g/m2/day when measured at 23° C. and 50 RH %.
  • 2. The article of claim 1, wherein the second polymer is selected from the group consisting of maleic anhydride block copolymers, glycidyl methacrylate block copolymers, polyether block copolymers, polyurethanes, polyethylene-containing ionomers, and mixtures thereof.
  • 3. The article of claim 1, wherein the second polymer is selected from the group consisting of poly(olefin-co-acrylate-co-maleic anhydride), poly(olefin-co-acrylate-co-glycidyl methacrylate), polyether ester block copolymers, polyether amide block copolymers, poly(ether ester amide) block copolymers, and polyurethanes.
  • 4. The article of claim 1, wherein the second polymer is selected from the group consisting of poly(ethylene-co-acrylate-co-maleic anhydride) and poly(ethylene-co-acrylate-co-glycidyl methacrylate).
  • 5. The article of claim 2, wherein the monolithic film further comprises a polyolefin.
  • 6. The article of claim 5, wherein the polyolefin comprises a polyethylene or a polypropylene.
  • 7. The article of claim 2, wherein the monolithic film further comprises a vinyl polymer.
  • 8. The article of claim 7, wherein the vinyl polymer comprises a poly(ethylene-co-methyl acrylate), a poly(ethylene-co-vinyl acetate), a poly(ethylene-co-ethyl acrylate), or a poly(ethylene-co-butyl acrylate).
  • 9. The article of claim 2, wherein the monolithic film further comprises a compatibilizer; the compatibilizer comprises a polypropylene grafted with maleic anhydride (PP-g-MAH) or a polymer formed by reacting PP-g-MAH with a polyetheramine.
  • 10. The article of claim 1, wherein the monolithic film comprises at least about 20% by weight of the second polymer; at least about 10% by weight of a vinyl polymer; at least about 5% by weight of a polyolefin; and at least about 0.1% by weight of a compatibilizer, based on the weight of the monolithic film.
  • 11. The article of claim 2, wherein the monolithic film further comprises a polyester.
  • 12. The article of claim 1, wherein the first polymer comprises a polyolefin or a polyester.
  • 13. The article of claim 1, wherein the pore-forming filler comprises calcium carbonate.
  • 14. The article of claim 13, wherein the microporous film comprises from about 30% by weight to about 70% by weight of the calcium carbonate.
  • 15. The article of claim 1, wherein the microporous film further comprises a nanoclay.
  • 16. The article of claim 1, wherein the microporous film further comprises an elastomer.
  • 17. The article of claim 16, wherein the elastomer is a propylene-ethylene copolymer.
  • 18. The article of claim 1, wherein the article has a hydrostatic head of at least about 55 cm.
  • 19. The article of claim 1, wherein the article has a tensile strength of at least about 40 pounds in the machine direction as measured according to ASTM D5034, the article has a tensile strength of at least about 35 pounds in the cross-machine direction as measured according to ASTM D5034, or both.
  • 20. A construction material, comprising the article of claim 1; wherein the construction material is a housewrap or a roofwrap.
CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of U.S. patent application Ser. No. 15/794,110 filed Oct. 26, 2017, which is a divisional application of U.S. patent application Ser. No. 13/530,425 filed on Jun. 22, 2012, and which claims priority to U.S. Provisional Patent Application No. 61/500,476 filed on Jun. 23, 2011, and claims the benefit of the its earlier filing date under 35 U.S.C. 119(e); each of U.S. patent application Ser. No. 15/794,110, U.S. patent application Ser. No. 13/530,425 and U.S. Provisional Patent Application No. 61/500,476 are incorporated herein by reference in their entirety.

US Referenced Citations (898)
Number Name Date Kind
3257488 Rasmussen Jun 1966 A
3808639 Tautvaisas May 1974 A
4116892 Schwarz Sep 1978 A
4284671 Cancio et al. Aug 1981 A
4376147 Byrne et al. Mar 1983 A
4452845 Lloyd et al. Jun 1984 A
4472328 Sugimoto et al. Sep 1984 A
4517714 Sneed et al. May 1985 A
4522203 Mays Jun 1985 A
4582871 Noro et al. Apr 1986 A
4596738 Metcalfe et al. Jun 1986 A
4626574 Cancio et al. Dec 1986 A
4668463 Cancio et al. May 1987 A
4705813 Ito et al. Nov 1987 A
4725473 Van Gompel et al. Feb 1988 A
4753840 Van Gompel Jun 1988 A
4777073 Sheth Oct 1988 A
4814124 Aoyama et al. Mar 1989 A
4898761 Dunaway et al. Feb 1990 A
4921653 Aoyama et al. May 1990 A
4929303 Sheth May 1990 A
5143774 Cancio et al. Sep 1992 A
5147346 Cancio et al. Sep 1992 A
5196247 Wu et al. Mar 1993 A
5200247 Wu et al. Apr 1993 A
5202173 Wu et al. Apr 1993 A
5240216 Lin et al. Aug 1993 A
5254111 Cancio et al. Oct 1993 A
5296184 Wu et al. Mar 1994 A
5308693 Ryle et al. May 1994 A
5336457 Wu et al. Aug 1994 A
5375383 Lin et al. Dec 1994 A
5382461 Wu Jan 1995 A
5404927 Bailey Apr 1995 A
5407979 Wu et al. Apr 1995 A
5409761 Langley Apr 1995 A
5422172 Wu Jun 1995 A
5435108 Overholt et al. Jul 1995 A
5445874 Shehata Aug 1995 A
5532053 Mueller Jul 1996 A
5555923 Leist et al. Sep 1996 A
5577544 Carper et al. Nov 1996 A
5592690 Wu Jan 1997 A
5615723 Carper Apr 1997 A
5626176 Lewis, Jr. et al. May 1997 A
5626950 Shimano et al. May 1997 A
5632063 Carper et al. May 1997 A
5634216 Wu Jun 1997 A
5636678 Carper et al. Jun 1997 A
5662978 Brown et al. Sep 1997 A
5679422 Lind et al. Oct 1997 A
5691052 Jones Nov 1997 A
5695868 McCormack Dec 1997 A
5709259 Lewis et al. Jan 1998 A
5709921 Shawver Jan 1998 A
5728451 Langley et al. Mar 1998 A
5759926 Pike et al. Jun 1998 A
5800928 Fischer et al. Sep 1998 A
5851937 Wu et al. Dec 1998 A
5855999 McCormack Jan 1999 A
5861074 Wu Jan 1999 A
5865925 Lindsay Feb 1999 A
5869414 Fischer et al. Feb 1999 A
5882749 Jones et al. Mar 1999 A
5882789 Jones et al. Mar 1999 A
5885269 Boyer, III et al. Mar 1999 A
5910225 McAmish et al. Jun 1999 A
5914084 Benson et al. Jun 1999 A
5939181 Kumano et al. Aug 1999 A
5942080 Mortellite et al. Aug 1999 A
5959042 Bouilloux et al. Sep 1999 A
5964268 Carper et al. Oct 1999 A
5992497 Jaehnen et al. Nov 1999 A
6006817 Stone et al. Dec 1999 A
6013151 Wu et al. Jan 2000 A
6015764 McCormack et al. Jan 2000 A
6037281 Mathis et al. Mar 2000 A
6045900 Haffner et al. Apr 2000 A
6047761 Jaehnen et al. Apr 2000 A
6075179 McCormack et al. Jun 2000 A
6092761 Mushaben Jul 2000 A
6096014 Haffner et al. Aug 2000 A
6100208 Brown et al. Aug 2000 A
6110849 Tsai et al. Aug 2000 A
6123134 Thomas et al. Sep 2000 A
6133168 Doyle et al. Oct 2000 A
6179939 Jones, Jr. et al. Jan 2001 B1
6187696 Lim et al. Feb 2001 B1
6191055 Boyer, III et al. Feb 2001 B1
6191221 McAmish et al. Feb 2001 B1
6214147 Mortellite et al. Apr 2001 B1
6235658 Panzer et al. May 2001 B1
6248258 Tomita et al. Jun 2001 B1
6258308 Brady et al. Jul 2001 B1
6260601 Thomas Jul 2001 B1
6261674 Branham et al. Jul 2001 B1
6264864 Mackay Jul 2001 B1
6265045 Mushaben Jul 2001 B1
6309736 McCormack et al. Oct 2001 B1
H2000 Middlesworth et al. Nov 2001 H
6348258 Topolkaraev et al. Feb 2002 B1
6352948 Pike et al. Mar 2002 B1
6368444 Jameson et al. Apr 2002 B1
6369292 Strack et al. Apr 2002 B1
6383431 Dobrin et al. May 2002 B1
6437064 Eckstein et al. Aug 2002 B1
6444302 Srinivas et al. Sep 2002 B1
6475591 Mushaben Nov 2002 B2
6479154 Walton et al. Nov 2002 B1
6497690 Haarer Dec 2002 B2
6497691 Bevins et al. Dec 2002 B1
6506695 Gardner et al. Jan 2003 B2
6511568 Eckstein et al. Jan 2003 B1
6521552 Honna et al. Feb 2003 B1
6541072 Doyle et al. Apr 2003 B1
6605172 Anderson et al. Aug 2003 B1
6610163 Mathis Aug 2003 B1
6620490 Malchow et al. Sep 2003 B1
6623586 Mortellite et al. Sep 2003 B2
6623837 Morman et al. Sep 2003 B2
6638636 Tucker Oct 2003 B2
6645641 Eckstein et al. Nov 2003 B2
6649548 Shawver et al. Nov 2003 B1
6653523 McCormack et al. Nov 2003 B1
6656581 Wu et al. Dec 2003 B2
6673297 Mushaben Jan 2004 B2
6677258 Carroll et al. Jan 2004 B2
6682803 McCormack et al. Jan 2004 B2
6698492 Lewis, Jr. et al. Mar 2004 B2
6712922 Sorenson et al. Mar 2004 B2
6713159 Blenke et al. Mar 2004 B1
6740184 Mortellite et al. May 2004 B2
6764566 Griesbach, III et al. Jul 2004 B1
6772814 Leist et al. Aug 2004 B2
6776947 Brady et al. Aug 2004 B2
6811643 McAmish et al. Nov 2004 B2
6811865 Morman et al. Nov 2004 B2
6818083 McAmish et al. Nov 2004 B2
6821915 Morman et al. Nov 2004 B2
6840300 Lewis, Jr. Jan 2005 B2
6843949 Brady et al. Jan 2005 B2
6849324 Meece et al. Feb 2005 B2
6861132 Ikeda et al. Mar 2005 B2
6909028 Shawver et al. Jun 2005 B1
6946182 Allgeuer et al. Sep 2005 B1
6951591 Mortellite et al. Oct 2005 B2
6953610 Heckmeier et al. Oct 2005 B2
6982231 Uitenbroek et al. Jan 2006 B1
7059379 Lewis, Jr. et al. Jun 2006 B2
7201207 Colston et al. Apr 2007 B2
7270723 McCormack et al. Sep 2007 B2
7270889 Campbell et al. Sep 2007 B2
7307031 Carroll et al. Dec 2007 B2
7378565 Anderson et al. May 2008 B2
7381666 Little et al. Jun 2008 B2
7393799 Porter Jul 2008 B2
7405009 Ahmed et al. Jul 2008 B2
7442332 Cancio et al. Oct 2008 B2
7481321 Ismert Jan 2009 B2
7501357 Carroll et al. Mar 2009 B2
7510758 Thomas et al. Mar 2009 B2
7517579 Campbell et al. Apr 2009 B2
7584699 Ford Sep 2009 B2
7625363 Yoshimasa et al. Dec 2009 B2
7625620 Kose Dec 2009 B2
7625829 Cree et al. Dec 2009 B1
7628829 Woo et al. Dec 2009 B2
7629000 Sabesan Dec 2009 B2
7629042 Jones et al. Dec 2009 B2
7629406 Kanz et al. Dec 2009 B2
7629416 Li et al. Dec 2009 B2
7631760 Guelzow et al. Dec 2009 B2
7632766 Erb, Jr. et al. Dec 2009 B2
7637898 Kuen et al. Dec 2009 B2
7640637 Efremova et al. Jan 2010 B2
7641952 O'Rourke et al. Jan 2010 B2
7642398 Järpenberg et al. Jan 2010 B2
7647667 Benjamin et al. Jan 2010 B2
7648607 Morin Jan 2010 B2
7648752 Hoying et al. Jan 2010 B2
7648771 Day et al. Jan 2010 B2
7650716 Schemeley Jan 2010 B1
7651653 Morman et al. Jan 2010 B2
7652095 Filiatrault et al. Jan 2010 B2
7655360 Hennige et al. Feb 2010 B2
7660040 Starry et al. Feb 2010 B2
7662137 Sayama et al. Feb 2010 B2
7662473 Aoki Feb 2010 B2
7662885 Coffey et al. Feb 2010 B2
7666343 Johnson et al. Feb 2010 B2
7670665 Hoying et al. Mar 2010 B2
7674522 Pohlmann Mar 2010 B2
7674722 Nishita et al. Mar 2010 B2
7674734 Suzuki et al. Mar 2010 B2
7674949 Wahlstrom et al. Mar 2010 B2
7675004 Nakajima et al. Mar 2010 B2
7678221 Takahaski et al. Mar 2010 B2
7678719 Ogle et al. Mar 2010 B2
7682686 Curro et al. Mar 2010 B2
7686903 Muncaster et al. Mar 2010 B2
7687139 Chan et al. Mar 2010 B2
7690069 Chen et al. Apr 2010 B2
7695583 Schneider et al. Apr 2010 B2
7695660 Berrigan et al. Apr 2010 B2
7695799 Cree Apr 2010 B2
7695812 Peng et al. Apr 2010 B2
7699826 Werenicz et al. Apr 2010 B2
7699827 Sandin et al. Apr 2010 B2
7700504 Tsujiyama et al. Apr 2010 B2
7704374 Sommer et al. Apr 2010 B2
7713894 Tsai et al. May 2010 B2
7714535 Yamazaki et al. May 2010 B2
7721887 Hancock-Cooke et al. May 2010 B2
7722591 Báck May 2010 B2
7722743 Best et al. May 2010 B2
7722943 Baldauf et al. May 2010 B2
7723246 Baldauf et al. May 2010 B2
7727211 LaVon et al. Jun 2010 B2
7727217 Hancock-Cooke Jun 2010 B2
7727297 Dauber et al. Jun 2010 B2
7727353 Nair et al. Jun 2010 B2
7727915 Skirius et al. Jun 2010 B2
7730928 Stone et al. Jun 2010 B2
7735149 Jarvis Jun 2010 B2
7736688 Oetjen et al. Jun 2010 B2
7737061 Chang et al. Jun 2010 B2
7737215 Chang et al. Jun 2010 B2
7737324 LaVon et al. Jun 2010 B2
7740469 Cancio et al. Jun 2010 B2
7740786 Gerndt et al. Jun 2010 B2
7744577 Otsubo et al. Jun 2010 B2
7744807 Berrigan et al. Jun 2010 B2
7754257 Matsumoto et al. Jul 2010 B2
7754939 Yoshida et al. Jul 2010 B2
7757809 Pfaffelhuber et al. Jul 2010 B2
7758947 Maschino et al. Jul 2010 B2
7759788 Aoki et al. Jul 2010 B2
7763002 Otsubo Jul 2010 B2
7763004 Beck et al. Jul 2010 B2
7763061 Schorr et al. Jul 2010 B2
7772136 Arthurs et al. Aug 2010 B2
7772137 Jones Aug 2010 B2
7775170 Zafiroglu Aug 2010 B2
7776020 Kaufman et al. Aug 2010 B2
7776416 Kinard et al. Aug 2010 B2
7777156 Rock et al. Aug 2010 B2
7781046 Kalkanoglu et al. Aug 2010 B2
7781051 Burr et al. Aug 2010 B2
7781069 Ahmed et al. Aug 2010 B2
7781353 Snowden et al. Aug 2010 B2
7785106 Takahashi Aug 2010 B2
7785307 Wennerback Aug 2010 B2
7786032 Zhou et al. Aug 2010 B2
7786034 Armantrout et al. Aug 2010 B2
7786208 Kondou Aug 2010 B2
7786340 Gagliardi et al. Aug 2010 B2
7786341 Schneider et al. Aug 2010 B2
7789482 Ishihara Sep 2010 B2
7790641 Baker, Jr. et al. Sep 2010 B2
7794486 Quincy, III Sep 2010 B2
7794737 Fish et al. Sep 2010 B2
7794819 Black et al. Sep 2010 B2
7795366 Yang et al. Sep 2010 B2
7799174 Bartelmuss et al. Sep 2010 B2
7799431 Corzani et al. Sep 2010 B2
7803244 Siqueira et al. Sep 2010 B2
7803446 Martz Sep 2010 B2
7803728 Poon et al. Sep 2010 B2
7805907 Bletsos et al. Oct 2010 B2
7806883 Fossum et al. Oct 2010 B2
7807593 Patel et al. Oct 2010 B2
7811949 Snowden et al. Oct 2010 B2
7811950 Greiser et al. Oct 2010 B2
7812214 Koele et al. Oct 2010 B2
7813108 Liu et al. Oct 2010 B2
7816285 MacDonald et al. Oct 2010 B2
7819852 Feller et al. Oct 2010 B2
7819853 Desai et al. Oct 2010 B2
7820562 Flat et al. Oct 2010 B2
7820574 Ashida et al. Oct 2010 B2
7823355 Hohmann, Jr. Nov 2010 B1
7824762 Ziegler Nov 2010 B2
7825045 Wagner et al. Nov 2010 B1
7825050 Wilfong et al. Nov 2010 B2
7826198 Jiang et al. Nov 2010 B2
7826199 Liu et al. Nov 2010 B2
7828922 Kronzer Nov 2010 B2
7829099 Woeller et al. Nov 2010 B2
7829484 Sharma et al. Nov 2010 B2
7829485 Mikura Nov 2010 B2
7829486 Nobuto et al. Nov 2010 B2
7833211 Mansfield Nov 2010 B2
7837009 Gross et al. Nov 2010 B2
7838099 Curro et al. Nov 2010 B2
7838104 Chen et al. Nov 2010 B2
7838123 Chen et al. Nov 2010 B2
7842630 Morton et al. Nov 2010 B2
7846282 Nishio et al. Dec 2010 B2
7850809 Schneider et al. Dec 2010 B2
7854817 Thompson Dec 2010 B2
7857801 Hamall et al. Dec 2010 B2
7858706 Arriola et al. Dec 2010 B2
7861763 Leist et al. Jan 2011 B2
7862549 Desai et al. Jan 2011 B2
7867208 Samuelsson et al. Jan 2011 B2
7870651 Middlesworth et al. Jan 2011 B2
7872575 Tabe Jan 2011 B2
7875012 Arco et al. Jan 2011 B2
7875334 Zafiroglu et al. Jan 2011 B2
7879452 Muslet Feb 2011 B2
7879747 Conrad et al. Feb 2011 B2
7886668 Hugus et al. Feb 2011 B2
7887900 DiPede Feb 2011 B2
7887916 Kaneko Feb 2011 B2
7888545 Fabo Feb 2011 B2
7896858 Trennepohl et al. Mar 2011 B2
7897078 Petersen et al. Mar 2011 B2
7900267 Chiou Mar 2011 B2
7901390 Ashton et al. Mar 2011 B1
7901392 Kline et al. Mar 2011 B2
7901756 Burr et al. Mar 2011 B2
7901759 Burmeister et al. Mar 2011 B2
7902095 Hassonjee et al. Mar 2011 B2
7905871 Mueller et al. Mar 2011 B2
7905872 McKiernan et al. Mar 2011 B2
7910794 Quinn et al. Mar 2011 B2
7910795 Thomas et al. Mar 2011 B2
7914537 Boyd et al. Mar 2011 B2
7914634 Moll Mar 2011 B2
7914723 Kim et al. Mar 2011 B2
7915184 Ellis et al. Mar 2011 B2
7915477 Shimada et al. Mar 2011 B2
7917985 Dorsey et al. Apr 2011 B2
7918313 Gross et al. Apr 2011 B2
7918838 Minato et al. Apr 2011 B2
7919420 Bornemann et al. Apr 2011 B2
7919480 Liu et al. Apr 2011 B2
7923035 Ii et al. Apr 2011 B2
7923391 Thomas Apr 2011 B2
7923392 Thomas Apr 2011 B2
7927323 Mizutani et al. Apr 2011 B2
7928282 Dibb et al. Apr 2011 B2
7931944 Snowden et al. Apr 2011 B2
7932196 McCormack et al. Apr 2011 B2
7934521 Busse et al. May 2011 B1
7935099 Sue et al. May 2011 B2
7935207 Zhao et al. May 2011 B2
7935234 Mett May 2011 B2
7935540 Kalgutkar et al. May 2011 B2
7935647 Howard, Jr. et al. May 2011 B2
7935859 Roe et al. May 2011 B2
7935861 Suzuki May 2011 B2
7937777 Sakaguchi et al. May 2011 B2
7938921 Ng et al. May 2011 B2
7943051 Dieziger May 2011 B2
7943537 Vincent et al. May 2011 B2
7947027 VanDenBogart et al. May 2011 B2
7947147 Bormann et al. May 2011 B2
7947358 Kling May 2011 B2
7947367 Poon et al. May 2011 B2
7950382 Maeda May 2011 B2
7951313 Matsubayashi et al. May 2011 B2
7951732 Dharmarajan et al. May 2011 B2
7955457 Middlesworth et al. Jun 2011 B2
7956754 Long Jun 2011 B2
7959618 Hermansson et al. Jun 2011 B2
7959619 Cartier et al. Jun 2011 B2
7959624 Riesinger Jun 2011 B2
7959751 Hanson et al. Jun 2011 B2
7963363 Niwa et al. Jun 2011 B2
7964161 Kadel et al. Jun 2011 B2
7967804 Ishikawa Jun 2011 B2
7968025 Pedoja Jun 2011 B2
7968479 Welch et al. Jun 2011 B2
7968656 Andjelic et al. Jun 2011 B2
7971526 Blenke et al. Jul 2011 B2
7972692 Chakravarty et al. Jul 2011 B2
7972981 Anderson et al. Jul 2011 B2
7975650 Vicari et al. Jul 2011 B2
7976523 Suzuki et al. Jul 2011 B2
7976662 Thomas et al. Jul 2011 B2
7976764 Schlemmer et al. Jul 2011 B2
7977608 Diemer et al. Jul 2011 B2
7979946 Kister et al. Jul 2011 B2
7981177 Ogale Jul 2011 B2
7981226 Pourdeyhimi et al. Jul 2011 B2
7981231 Schneider et al. Jul 2011 B2
7981336 Pourdeyhimi Jul 2011 B2
7982090 Snauwaert et al. Jul 2011 B2
7982355 Takizawa et al. Jul 2011 B2
7984591 Cashin et al. Jul 2011 B2
7985210 Ashton et al. Jul 2011 B2
7988824 Shannon et al. Aug 2011 B2
7989062 Chakravarty et al. Aug 2011 B2
20010011666 Lori et al. Aug 2001 A1
20020004350 Morman et al. Jan 2002 A1
20020019187 Carroll et al. Feb 2002 A1
20020066522 Nickel et al. Jun 2002 A1
20020074691 Mortellite et al. Jun 2002 A1
20020089087 Mushaben Jul 2002 A1
20020094742 Jones et al. Jul 2002 A1
20020105110 Dobrin et al. Aug 2002 A1
20020106959 Huffines et al. Aug 2002 A1
20020112809 Mortellite et al. Aug 2002 A1
20020132547 Grondin et al. Sep 2002 A1
20020143306 Tucker et al. Oct 2002 A1
20020150704 Baer et al. Oct 2002 A1
20020179255 Leist et al. Dec 2002 A1
20030047271 Wu et al. Mar 2003 A1
20030106560 Griesbach, III et al. Jun 2003 A1
20030153226 Jones et al. Aug 2003 A1
20030175504 Mientus et al. Sep 2003 A1
20040016502 Jones Jan 2004 A1
20040023585 Carroll et al. Feb 2004 A1
20040029467 Lacroix Feb 2004 A1
20040029469 Anderson et al. Feb 2004 A1
20040087235 Morman et al. May 2004 A1
20040115458 Kong Jun 2004 A1
20040142621 Carroll et al. Jul 2004 A1
20040224596 Mathis et al. Nov 2004 A1
20040253892 Baker et al. Dec 2004 A1
20050054779 Zhou Mar 2005 A1
20050054780 Zhou et al. Mar 2005 A1
20050089682 Su et al. Apr 2005 A1
20050175805 Hild et al. Aug 2005 A1
20050176331 Martin et al. Aug 2005 A1
20050227086 Murphy Oct 2005 A1
20060008643 Lin et al. Jan 2006 A1
20060102295 Leist et al. May 2006 A1
20060147716 Braverman et al. Jul 2006 A1
20060160453 Suh Jul 2006 A1
20060162875 Magill et al. Jul 2006 A1
20060257652 Su Nov 2006 A1
20070178784 Jones et al. Aug 2007 A1
20070275618 Lorentz et al. Nov 2007 A1
20080131676 Becke et al. Jun 2008 A1
20080155913 Magill Jul 2008 A1
20080166533 Jones et al. Jul 2008 A1
20080177242 Chang et al. Jul 2008 A1
20080227353 Klingelhage et al. Sep 2008 A1
20080228159 Anderson et al. Sep 2008 A1
20080276495 Jones Nov 2008 A1
20090042471 Cashin et al. Feb 2009 A1
20090092816 Flat et al. Apr 2009 A1
20090107047 Magill et al. Apr 2009 A1
20090157021 Sullivan et al. Jun 2009 A1
20090191780 Aldrey et al. Jul 2009 A1
20090193716 Magill et al. Aug 2009 A1
20090258210 Iyad et al. Oct 2009 A1
20090286023 Dobreski et al. Nov 2009 A1
20090293404 Belt et al. Dec 2009 A1
20090294034 Thompson Dec 2009 A1
20090295014 Matsubayashi et al. Dec 2009 A1
20090297815 Higuchi et al. Dec 2009 A1
20090298372 Chou et al. Dec 2009 A1
20090298374 Delmas Dec 2009 A1
20090299314 Middlesworth et al. Dec 2009 A1
20090299316 Seyler Dec 2009 A1
20090300832 Howard, Jr. Dec 2009 A1
20090301022 Rockwell et al. Dec 2009 A1
20090304225 Kamimura et al. Dec 2009 A1
20090304759 Howard, Jr. Dec 2009 A1
20090305035 Kaneko Dec 2009 A1
20090305038 Duran et al. Dec 2009 A1
20090305592 Shi et al. Dec 2009 A1
20090306616 Wennerbäck Dec 2009 A1
20090308524 Gunji et al. Dec 2009 A1
20090312507 Standaert et al. Dec 2009 A1
20090312731 Steindl et al. Dec 2009 A1
20090312734 LaVon et al. Dec 2009 A1
20090312738 LaVon et al. Dec 2009 A1
20090315389 Seradarian et al. Dec 2009 A1
20090317611 Mueller et al. Dec 2009 A1
20090318843 Van Holten et al. Dec 2009 A1
20090320718 Hierse et al. Dec 2009 A1
20090323300 Fujimoto et al. Dec 2009 A1
20090324893 Söder et al. Dec 2009 A1
20090324905 Welch et al. Dec 2009 A1
20090325440 Thomas et al. Dec 2009 A1
20090325447 Austin et al. Dec 2009 A1
20090325448 Welch et al. Dec 2009 A1
20090326429 Siniaguine Dec 2009 A1
20090326499 Veith et al. Dec 2009 A1
20090326503 Lakso et al. Dec 2009 A1
20100000170 Parks Jan 2010 A1
20100000599 Greulich-Weber et al. Jan 2010 A1
20100003882 Sumi et al. Jan 2010 A1
20100004613 Cohen Jan 2010 A1
20100004615 Boissier Jan 2010 A1
20100010462 Kurata Jan 2010 A1
20100010598 Igaki et al. Jan 2010 A1
20100012214 Kamiyama et al. Jan 2010 A1
20100014164 O'Brien Jan 2010 A1
20100019416 Pfaffelhuber et al. Jan 2010 A1
20100023099 Hidaka et al. Jan 2010 A1
20100024136 Takenoir et al. Feb 2010 A1
20100024329 Gray et al. Feb 2010 A1
20100025888 Bader et al. Feb 2010 A1
20100028595 Backer et al. Feb 2010 A1
20100029158 Kamiyama et al. Feb 2010 A1
20100029161 Pourdeyhimi Feb 2010 A1
20100029455 Skopek et al. Feb 2010 A1
20100029871 Crowther et al. Feb 2010 A1
20100030176 Beckert et al. Feb 2010 A1
20100032089 Spies et al. Feb 2010 A1
20100032234 Niwa et al. Feb 2010 A1
20100035014 Hammons et al. Feb 2010 A1
20100035498 Lundmark et al. Feb 2010 A1
20100036339 Hammons et al. Feb 2010 A1
20100036347 Hammons et al. Feb 2010 A1
20100036349 Hammons et al. Feb 2010 A1
20100040659 Fahland et al. Feb 2010 A1
20100040826 Autran et al. Feb 2010 A1
20100041293 Anderson et al. Feb 2010 A1
20100041295 Malz et al. Feb 2010 A1
20100042062 Fernkvist et al. Feb 2010 A1
20100044075 Weiss et al. Feb 2010 A1
20100047326 Castel et al. Feb 2010 A1
20100047518 Husemann et al. Feb 2010 A1
20100047533 Almansa et al. Feb 2010 A1
20100049148 Siniaguine Feb 2010 A1
20100051495 Guelzow et al. Mar 2010 A1
20100055273 Chen Mar 2010 A1
20100055276 Chen Mar 2010 A1
20100056896 Park Mar 2010 A1
20100057028 Catalan Mar 2010 A1
20100057032 Hardegree Mar 2010 A1
20100057034 Dennis et al. Mar 2010 A1
20100062231 Abed et al. Mar 2010 A1
20100063468 Lehto et al. Mar 2010 A1
20100064491 Dumas et al. Mar 2010 A1
20100066121 Gross Mar 2010 A1
20100068426 Kuboyama et al. Mar 2010 A1
20100068484 Kaufman Mar 2010 A1
20100069864 Berland et al. Mar 2010 A1
20100069870 Cohen Mar 2010 A1
20100069873 Elfsberg et al. Mar 2010 A1
20100071356 Tabata Mar 2010 A1
20100075103 Miyamoto Mar 2010 A1
20100075561 Burrow et al. Mar 2010 A1
20100076390 Norrby et al. Mar 2010 A1
20100080968 Mizuno et al. Apr 2010 A1
20100086719 Deiss Apr 2010 A1
20100089264 Warner Apr 2010 A1
20100089899 Döhring et al. Apr 2010 A1
20100092726 Schuette et al. Apr 2010 A1
20100093596 Tadrowski Apr 2010 A1
20100094240 Desai et al. Apr 2010 A9
20100095846 Skirius et al. Apr 2010 A1
20100096074 Schoenbeck et al. Apr 2010 A1
20100098919 Hartgrove et al. Apr 2010 A1
20100100068 Rodriguez et al. Apr 2010 A1
20100104830 Jaeger et al. Apr 2010 A1
20100105274 Haubruge et al. Apr 2010 A1
20100105833 Keller et al. Apr 2010 A1
20100106121 Holm Apr 2010 A1
20100107452 Baychar May 2010 A1
20100108287 Ota et al. May 2010 A1
20100109193 Tsai et al. May 2010 A1
20100111335 Lee et al. May 2010 A1
20100111889 Marsh et al. May 2010 A1
20100112199 McClure et al. May 2010 A1
20100112273 Pedoja May 2010 A1
20100112301 Powers May 2010 A1
20100119564 Kasuga et al. May 2010 A1
20100119788 Wachs et al. May 2010 A1
20100119988 Fukuhara May 2010 A1
20100120313 Bohme et al. May 2010 A1
20100120315 Imashiro et al. May 2010 A1
20100129426 Tanaka et al. May 2010 A1
20100129576 Zhang et al. May 2010 A1
20100130086 Dorsey et al. May 2010 A1
20100130907 Linkel May 2010 A1
20100130951 Pierson et al. May 2010 A1
20100130952 Murai May 2010 A1
20100130956 Wennerbäck May 2010 A1
20100136077 Bukshpan et al. Jun 2010 A1
20100136703 Purkayastha Jun 2010 A1
20100136865 Bletsos Jun 2010 A1
20100137141 Lipinsky et al. Jun 2010 A1
20100137902 Lee et al. Jun 2010 A1
20100137903 Lee et al. Jun 2010 A1
20100139195 Tinianov et al. Jun 2010 A1
20100139877 Black et al. Jun 2010 A1
20100143670 Baldauf et al. Jun 2010 A1
20100143684 Geel et al. Jun 2010 A1
20100146679 Heil Jun 2010 A1
20100146851 Schemeley Jun 2010 A1
20100147621 Gillette Jun 2010 A1
20100148183 Ward et al. Jun 2010 A1
20100150479 Smith Jun 2010 A1
20100151352 Haring et al. Jun 2010 A1
20100152692 Ong et al. Jun 2010 A1
20100155284 Gerstle et al. Jun 2010 A1
20100159050 Huang et al. Jun 2010 A1
20100159197 Ferguson et al. Jun 2010 A1
20100159203 Shi et al. Jun 2010 A1
20100159207 Schmidt Jun 2010 A1
20100159611 Song et al. Jun 2010 A1
20100159769 MacDonald et al. Jun 2010 A1
20100159772 Ashida et al. Jun 2010 A1
20100159776 Jones et al. Jun 2010 A1
20100159777 Wang et al. Jun 2010 A1
20100160885 Cohen Jun 2010 A1
20100163161 Gilgenbach et al. Jul 2010 A1
20100163162 Schneider et al. Jul 2010 A1
20100168704 Thomas et al. Jul 2010 A1
20100168705 Stabelfeldt et al. Jul 2010 A1
20100168706 Vasic Jul 2010 A1
20100172946 Song et al. Jul 2010 A1
20100173993 Sawyer et al. Jul 2010 A1
20100175354 Mizukami et al. Jul 2010 A1
20100178268 Bukshpan et al. Jul 2010 A1
20100178478 Bae et al. Jul 2010 A1
20100178822 Ketzer et al. Jul 2010 A1
20100179469 Hammond et al. Jul 2010 A1
20100180558 Ito et al. Jul 2010 A1
20100183883 Schaefer et al. Jul 2010 A1
20100184348 McAmish et al. Jul 2010 A1
20100189540 Hancock-Cooke et al. Jul 2010 A1
20100190405 Takebe Jul 2010 A1
20100191198 Heagle Jul 2010 A1
20100191213 O'Connell Jul 2010 A1
20100120314 Johnson et al. Aug 2010 A1
20100196653 Curro et al. Aug 2010 A1
20100197027 Zhang et al. Aug 2010 A1
20100198172 Wada et al. Aug 2010 A1
20100198177 Yahiaoui et al. Aug 2010 A1
20100199552 Weder Aug 2010 A1
20100201024 Gibson et al. Aug 2010 A1
20100202143 Ruehlemann et al. Aug 2010 A1
20100203638 Adachi et al. Aug 2010 A1
20100204411 Erneta et al. Aug 2010 A1
20100204786 Foulkes Aug 2010 A1
20100206763 Adeline et al. Aug 2010 A1
20100206817 Dieziger Aug 2010 A1
20100209650 Schlueter Aug 2010 A1
20100209667 Mitsuno et al. Aug 2010 A1
20100209679 Tompkins Aug 2010 A1
20100209687 Zhu Aug 2010 A1
20100209784 Yamazaki et al. Aug 2010 A1
20100211034 Fish et al. Aug 2010 A1
20100211036 Otsubo Aug 2010 A1
20100215908 Kline et al. Aug 2010 A1
20100215913 Kline et al. Aug 2010 A1
20100215914 Kline et al. Aug 2010 A1
20100215923 Frost Aug 2010 A1
20100215924 Di Pede Aug 2010 A1
20100217216 Sue et al. Aug 2010 A1
20100217217 Kline et al. Aug 2010 A1
20100217218 Bäck et al. Aug 2010 A1
20100217219 Kline et al. Aug 2010 A1
20100217220 Kline et al. Aug 2010 A1
20100217221 Kline et al. Aug 2010 A1
20100217222 Kline et al. Aug 2010 A1
20100219138 Scheerlinck et al. Sep 2010 A1
20100219561 Pfaffelhuber et al. Sep 2010 A1
20100221496 de Jong Sep 2010 A1
20100221515 Schröer Sep 2010 A1
20100221522 Mrozinski Sep 2010 A1
20100221965 Katayama et al. Sep 2010 A1
20100222759 Hammons et al. Sep 2010 A1
20100222761 Westwood et al. Sep 2010 A1
20100223715 Lyons Sep 2010 A1
20100223716 Howard, Jr. Sep 2010 A1
20100224199 Smith et al. Sep 2010 A1
20100228204 Beatty et al. Sep 2010 A1
20100228212 Desai et al. Sep 2010 A1
20100228213 Berland et al. Sep 2010 A1
20100228214 Bornemann et al. Sep 2010 A1
20100233927 Standaert et al. Sep 2010 A1
20100234823 Morita et al. Sep 2010 A1
20100236492 Calabrese Sep 2010 A1
20100239814 Mourad et al. Sep 2010 A1
20100239844 Teather Sep 2010 A1
20100243151 Stokes Sep 2010 A1
20100243500 McConnell et al. Sep 2010 A1
20100247825 Wood et al. Sep 2010 A1
20100247826 Wood et al. Sep 2010 A1
20100247855 Bletsos et al. Sep 2010 A1
20100247882 Hill et al. Sep 2010 A1
20100251466 Langley et al. Oct 2010 A1
20100254636 Elkhouli Oct 2010 A1
20100255048 Schmidt Oct 2010 A1
20100261398 Dry et al. Oct 2010 A1
20100262102 Turner et al. Oct 2010 A1
20100262103 Turner et al. Oct 2010 A1
20100262105 Turner et al. Oct 2010 A1
20100262107 Turner et al. Oct 2010 A1
20100262109 Eriksson Oct 2010 A1
20100262110 Lakso Oct 2010 A1
20100263152 Wildeman Oct 2010 A1
20100263565 Hugus, IV et al. Oct 2010 A1
20100263740 Borgmeier et al. Oct 2010 A1
20100263820 Köckritz et al. Oct 2010 A1
20100266835 Conboy Oct 2010 A1
20100267299 Anderle et al. Oct 2010 A1
20100267301 Servante et al. Oct 2010 A1
20100268144 Lu et al. Oct 2010 A1
20100269236 Wagner et al. Oct 2010 A1
20100269241 Baychar Oct 2010 A1
20100272938 Mitchell et al. Oct 2010 A1
20100273375 Teschner et al. Oct 2010 A1
20100273380 Chen et al. Oct 2010 A1
20100273383 Barney et al. Oct 2010 A1
20100274211 Beck et al. Oct 2010 A1
20100279173 Hying et al. Nov 2010 A1
20100279571 Poon et al. Nov 2010 A1
20100280471 Shah Nov 2010 A1
20100280532 Gingras Nov 2010 A1
20100282682 Eaton et al. Nov 2010 A1
20100285101 Moore et al. Nov 2010 A1
20100285301 Dieudonné et al. Nov 2010 A1
20100285520 Halverson et al. Nov 2010 A1
20100285655 Sakai Nov 2010 A1
20100286644 Li et al. Nov 2010 A1
20100286645 MacDonald et al. Nov 2010 A1
20100288131 Kilber et al. Nov 2010 A1
20100290721 Marin Nov 2010 A1
20100291213 Berrigan et al. Nov 2010 A1
20100291828 Reches et al. Nov 2010 A1
20100292664 Marin Nov 2010 A1
20100293691 Chabba et al. Nov 2010 A1
20100293698 Burr et al. Nov 2010 A1
20100293851 Weder Nov 2010 A1
20100295881 Yao et al. Nov 2010 A1
20100297411 Tsai et al. Nov 2010 A1
20100298795 Schneider et al. Nov 2010 A1
20100298798 Lakso et al. Nov 2010 A1
20100300309 Schneider Dec 2010 A1
20100304072 Ind Dec 2010 A1
20100304080 Black et al. Dec 2010 A1
20100304108 Doshi et al. Dec 2010 A1
20100304111 Vulpitta et al. Dec 2010 A1
20100304630 Morikawa et al. Dec 2010 A1
20100305529 Ashton et al. Dec 2010 A1
20100310825 Kalkanoglu et al. Dec 2010 A1
20100312205 Martin et al. Dec 2010 A1
20100313340 Du et al. Dec 2010 A1
20100313753 Calis et al. Dec 2010 A1
20100313759 Bones Dec 2010 A1
20100314026 Donovan et al. Dec 2010 A1
20100314195 Bliton et al. Dec 2010 A1
20100316421 Komuro Dec 2010 A1
20100316846 DeJong et al. Dec 2010 A1
20100316864 Yoshida Dec 2010 A1
20100317020 Roscoe et al. Dec 2010 A1
20100318052 Ha et al. Dec 2010 A1
20100318054 Langdon et al. Dec 2010 A1
20100318055 Hornung et al. Dec 2010 A1
20100323575 He et al. Dec 2010 A1
20100324513 Wennerbäck Dec 2010 A1
20100324522 Carstens Dec 2010 A1
20100324525 Carstens Dec 2010 A1
20100325833 Sauer et al. Dec 2010 A1
20100326902 Midkiff et al. Dec 2010 A1
20100330288 Segars et al. Dec 2010 A1
20100330860 Puerkner et al. Dec 2010 A1
20110000521 Tachibana Jan 2011 A1
20110003092 Lovgren et al. Jan 2011 A1
20110003523 Herve et al. Jan 2011 A1
20110003524 Claasen et al. Jan 2011 A1
20110004139 Pigg Jan 2011 A1
20110004169 Smith et al. Jan 2011 A1
20110004172 Eckstein et al. Jan 2011 A1
20110004180 Fossum et al. Jan 2011 A1
20110009843 Krook Jan 2011 A1
20110010826 Kaskel Jan 2011 A1
20110011396 Fang Jan 2011 A1
20110012474 Levit et al. Jan 2011 A1
20110014459 Hansen et al. Jan 2011 A1
20110015295 Gardi et al. Jan 2011 A1
20110015605 Zhang et al. Jan 2011 A1
20110017278 Kalkanoglu et al. Jan 2011 A1
20110020573 Chou et al. Jan 2011 A1
20110020590 Yoneda et al. Jan 2011 A1
20110020619 Van Den Bossche et al. Jan 2011 A1
20110021102 Inoue et al. Jan 2011 A1
20110021103 Alper et al. Jan 2011 A1
20110024412 Su et al. Feb 2011 A1
20110024940 Qureshi et al. Feb 2011 A1
20110028062 Chester et al. Feb 2011 A1
20110029047 Maruyama et al. Feb 2011 A1
20110030883 Schneider et al. Feb 2011 A1
20110033532 Angel et al. Feb 2011 A1
20110033625 Weichmann Feb 2011 A1
20110033658 Boeykens et al. Feb 2011 A1
20110034645 Standaert et al. Feb 2011 A1
20110034649 Standaert et al. Feb 2011 A1
20110034787 Hagino et al. Feb 2011 A1
20110039468 Baldwin, Jr. et al. Feb 2011 A1
20110041274 Ogale Feb 2011 A1
20110041970 Chang Feb 2011 A1
20110045337 Lee et al. Feb 2011 A1
20110046591 Warner Feb 2011 A1
20110048636 Fukuhara Mar 2011 A1
20110050202 Virtanen et al. Mar 2011 A1
20110053450 Baqai et al. Mar 2011 A1
20110056609 Iwao et al. Mar 2011 A1
20110059037 Canova et al. Mar 2011 A1
20110059666 Azuma et al. Mar 2011 A1
20110059668 Bieser et al. Mar 2011 A1
20110059669 He et al. Mar 2011 A1
20110060413 Kasuga et al. Mar 2011 A1
20110062042 Boldra et al. Mar 2011 A1
20110065569 Matsui et al. Mar 2011 A1
20110065573 McEneany et al. Mar 2011 A1
20110066126 Mansfield Mar 2011 A1
20110067797 Schneider et al. Mar 2011 A1
20110070410 Huang et al. Mar 2011 A1
20110073239 Manning et al. Mar 2011 A1
20110076312 Pokropinski, Jr. et al. Mar 2011 A1
20110076905 Müssig et al. Mar 2011 A1
20110077610 Kikumoto et al. Mar 2011 A1
20110079525 Peck et al. Apr 2011 A1
20110081817 Bieser et al. Apr 2011 A1
20110081818 Bieser et al. Apr 2011 A1
20110084539 Hofmann et al. Apr 2011 A1
20110086564 Chou et al. Apr 2011 A1
20110086568 Standaert et al. Apr 2011 A1
20110091682 Holland et al. Apr 2011 A1
20110091698 Zhou et al. Apr 2011 A1
20110092120 Todt et al. Apr 2011 A1
20110092124 Brendel et al. Apr 2011 A1
20110092606 Zhou Apr 2011 A1
20110092933 Canales Espinosa de los Monteros et al. Apr 2011 A1
20110092945 Carstens Apr 2011 A1
20110094661 Thorson Apr 2011 A1
20110098668 Thorson et al. Apr 2011 A1
20110100551 Müssig et al. May 2011 A1
20110100748 Nonogi et al. May 2011 A1
20110104461 Grubka May 2011 A1
20110104488 Müssig et al. May 2011 A1
20110109014 Rogers et al. May 2011 A1
20110111660 Morino et al. May 2011 A1
20110114414 Bliton et al. May 2011 A1
20110114675 Kelly et al. May 2011 A1
20110117176 Klun et al. May 2011 A1
20110117273 Mitsuishii et al. May 2011 A1
20110120620 Hiemeyer et al. May 2011 A1
20110123802 Chang et al. May 2011 A1
20110127188 Thompson et al. Jun 2011 A1
20110130062 Squires Jun 2011 A1
20110130063 Matsubayashi et al. Jun 2011 A1
20110130814 Nagano et al. Jun 2011 A1
20110131931 Weder Jun 2011 A1
20110135870 Gleich et al. Jun 2011 A1
20110137274 Klofta et al. Jun 2011 A1
20110139366 Belt et al. Jun 2011 A1
20110139658 Hird et al. Jun 2011 A1
20110143004 Wood et al. Jun 2011 A1
20110143620 Wu Jun 2011 A1
20110143621 MacDonald et al. Jun 2011 A1
20110143623 Abed et al. Jun 2011 A1
20110144603 Song Jun 2011 A1
20110144608 Kim et al. Jun 2011 A1
20110144609 Petersen et al. Jun 2011 A1
20110146039 Lin et al. Jun 2011 A1
20110147301 Johnson et al. Jun 2011 A1
20110147977 Sommer Jun 2011 A1
20110151060 Nakagiri Jun 2011 A1
20110151185 Cree Jun 2011 A1
20110151738 Moore et al. Jun 2011 A1
20110152641 Fernfors et al. Jun 2011 A1
20110152806 Zhou et al. Jun 2011 A1
20110155141 Sawyer et al. Jun 2011 A1
20110155301 Gilgenbach et al. Jun 2011 A1
20110156299 Chou et al. Jun 2011 A1
20110156303 Chou et al. Jun 2011 A1
20110159063 Ellis et al. Jun 2011 A1
20110159759 MacDonald et al. Jun 2011 A1
20110159764 Price et al. Jun 2011 A1
20110160526 Zunker et al. Jun 2011 A1
20110160687 Welch et al. Jun 2011 A1
20110160691 Ng et al. Jun 2011 A1
20110160692 Wilkes et al. Jun 2011 A1
20110165810 Mori et al. Jul 2011 A1
20110170938 Littig et al. Jul 2011 A1
20110172623 Roe et al. Jul 2011 A1
20110173883 Weder Jul 2011 A1
20110174317 Martin Jul 2011 A1
20110174430 Zhao et al. Jul 2011 A1
20110177735 Tasi et al. Jul 2011 A1
20110179558 Lyons Jul 2011 A1
20110179677 Jessiman et al. Jul 2011 A1
20110179753 Toms et al. Jul 2011 A1
20110183103 Kranz et al. Jul 2011 A1
20110183109 Seyler et al. Jul 2011 A1
20110183568 Haubruge et al. Jul 2011 A1
20110183712 Eckstein et al. Jul 2011 A1
20110184136 Haubruge et al. Jul 2011 A1
20110184367 Toms et al. Jul 2011 A1
20110188907 Seki Aug 2011 A1
20110189421 Sherman et al. Aug 2011 A1
20110189463 Moore et al. Aug 2011 A1
20110189916 Haubruge et al. Aug 2011 A1
20120157598 Song et al. Jun 2012 A1
20120168340 Liang et al. Jul 2012 A1
Foreign Referenced Citations (34)
Number Date Country
1263821 Aug 2000 CN
0893530 Jan 1999 EP
0979838 Feb 2000 EP
1022125 Jul 2000 EP
1148082 Oct 2001 EP
1970402 Sep 2008 EP
2001105520 Apr 2001 JP
2002205363 Jul 2002 JP
199103367 Mar 1991 WO
1991012125 Aug 1991 WO
1992000188 Jan 1992 WO
1993003098 Feb 1993 WO
1994020298 Sep 1994 WO
1995004654 Feb 1995 WO
1997029909 Aug 1997 WO
1998029481 Jul 1998 WO
1998040581 Sep 1998 WO
1998043810 Oct 1998 WO
1999014262 Mar 1999 WO
1999060050 Nov 1999 WO
2000023255 Apr 2000 WO
2001019592 Mar 2001 WO
2001066627 Sep 2001 WO
20030016042 Feb 2003 WO
20030050167 Jun 2003 WO
20040043693 May 2004 WO
20050017248 Feb 2005 WO
20050051635 Jun 2005 WO
20050110713 Nov 2005 WO
20070040609 Apr 2007 WO
20070081548 Jul 2007 WO
20070125506 Nov 2007 WO
20080045881 Apr 2008 WO
20100022066 Feb 2010 WO
Non-Patent Literature Citations (9)
Entry
Jones et al, Novel Microporous Films and Their Composites, Journal of Engineered Fibers and Fabrics, vol. 2, Issue 1 (Year: 2007).
Lotti et al., “Rheological, Mechanical and Transport Properties of Blown Films of High Density Polyethylene Nanocomposites”, European Polymer Journal 44 (2008), Feb. 2008, pp. 1346-1357, Brazil, all enclosed pages cited.
Dai et al., “Preparation and Properties of HDPE/CaCO3/OMMT Ternary Nanocomposite”, Polymer Engineering and Science, May 2010, pp. 894-899, People's Republic of China, all enclosed pages cited.
International Search Report and Written Opinion of corresponding International Application No. PCT/US2012/043752 dated Jan. 31, 2013, all enclosed pages cited.
International Preliminary Report on Patentability of corresponding International Application No. PCT/US2012/043752 dated Jan. 9, 2014, all enclosed pages cited.
Extended European Search Report of corresponding European Patent Application No. 12802064.1 dated Nov. 21, 2014, all enclosed pages cited.
Third Office Action of corresponding Chinese Application No. 201280039954.2 dated Jan. 29, 2016, all enclosed pages cited.
Fourth Office Action of corresponding Chinese Application No. 201280039954.2 dated Jun. 21, 2016, all enclosed pages cited.
Notification to Grant Patent Right of corresponding Chinese Application No. 201280039954.2 dated Dec. 15, 2016, all enclosed pages cited.
Related Publications (1)
Number Date Country
20210039374 A1 Feb 2021 US
Provisional Applications (1)
Number Date Country
61500476 Jun 2011 US
Divisions (1)
Number Date Country
Parent 13530425 Jun 2012 US
Child 15794110 US
Continuations (1)
Number Date Country
Parent 15794110 Oct 2017 US
Child 17077213 US