# Patent

## Title
Vapor-permeable, substantially water-impermeable multilayer article

## Abstract

This disclosure relates to an article that includes a nonwoven substrate and a film supported by the nonwoven substrate. The film can include a first polymer and a polymer that is immiscible with the first polymer. The first polymer can include a polyolefin and the second polymer can include a polycycloolefin, a polymethylpentene, or a copolymer thereof.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims priority to U.S. Provisional Patent Application No. 61/500,694 filed Jun. 24, 2011, which is incorporated herein by reference in its entirety.


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 a 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
This disclosure is based on the unexpected findings that a polyolefin and a relatively large amount of a polymer that is immiscible with the polyolefin (also referred to hereinafter as “immiscible polymer”) can be blended together to form a microporous breathable film with superior processability without using a compatibilizer. 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 film. The film includes first and second polymers. The first polymer includes a polyolefin. The second polymer is immiscible with the first polymer and includes a polycycloolefin, a polymethylpentene, or a copolymer thereof.
In another aspect, this disclosure features an article (e.g., a vapor-permeable, substantially water-impermeable multilayer article) that includes a nonwoven substrate and a film supported by the nonwoven substrate. The film includes first and second polymers. The first polymer includes a polyolefin. The second polymer is immiscible with the first polymer and includes a polycycloolefin, a polymethylpentene, or a copolymer thereof.
In another aspect, this disclosure features an article that includes a nonwoven substrate and a film supported by the nonwoven substrate. The film includes first and second polymers. The first polymer includes a polyolefin. The second polymer includes a polycycloolefin, a polymethylpentene, or a copolymer thereof.
In another aspect, this disclosure features a construction material that includes an article described above.
In still another aspect, this disclosure features a method of making an article. The method includes forming a nonwoven substrate and a film supported by the nonwoven substrate, and stretching the laminate to form the article. The film includes first and second polymers. The first polymer includes a polyolefin. The second polymer is immiscible with the first polymer and includes a polycycloolefin, a polymethylpentene, or a copolymer thereof.
Embodiments can include one or more of the following optional features.
The second polymer can include a poly(cycloolefin-co-olefin), such as a poly(norbornene-co-ethylene) or a copolymer formed from ethylene and norbornene substituted with a substituent (e.g., a hydrocarbon moiety such as C1-C20 alkyl).
The film can include at least about 1% by weight of the second polymer.
The first polymer can include a polyethylene or a polypropylene. The polyethylene can be selected from the group consisting of low-density polyethylene, linear low-density polyethylene, high-density polyethylene, and copolymers thereof.
The film can further include an elastomer or a nanoclay.
The film can further include a pore-forming filler (e.g., calcium carbonate). For example, the film can include from about 30% by weight to about 70% by weight of calcium carbonate.
The film can be substantially uniform in the absence of a compatibilizer.
The nonwoven substrate can include randomly disposed polymeric fibers, at least a portion of the fibers being bonded to one another.
The article can be embossed.
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% relative humidity (RH %).
The construction material can be a housewrap or a roofwrap.
Forming the laminate can include extruding the film 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 one or more of the following advantages.
Without wishing to be bound by theory, it is believed that, as the immiscible polymer has a polymer backbone similar to that of the polyolefin polymer in the breathable film, a relatively large amount (e.g., at least about 30% by weight) of the immiscible polymer can be blended with the polyolefin polymer to form a microporous breathable film that is substantially uniform and has superior processability without using a compatibilizer, thereby significantly reducing the cost for manufacturing the film. By contrast, when a conventional immiscible polymer (e.g., a polystyrene) is blended with the polyolefin polymer at the same concentration level, a uniform film is generally not formed even in the presence of a compatibilizer.
Other features and advantages 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 example, an article (e.g., a vapor-permeable, substantially water-impermeable multilayer article) containing a nonwoven substrate and a microporous breathable film supported by the nonwoven substrate. The microporous breathable film can include a first polymer (e.g., a polyolefin) and a second polymer that is immiscible with the first polymer (e.g., a polycycloolefin, a polymethylpentene, or a copolymer thereof). 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 microporous breathable film 12 and a nonwoven substrate 14.
Microporous Breathable Film
Microporous breathable film 12 can include a first polymer and a second polymer immiscible with the first polymer.
In some embodiments, the first polymer includes a polyolefin. As used herein, 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 12 include polyethylene, polypropylene, polybutene, polypentene, and polymethylpentene. In some embodiments, film 12 can include two or more (e.g., three, four, or five) different polyolefins.
Exemplary polyethylene suitable for film 12 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 12 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 12 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.
The amount of the first polymer in film 12 can vary depending on the desired applications. For example, the first polymer can be at least about 40% (e.g., at least about 45%, at least about 50%, at least about 55%, at least about 60%, at least about 65%, at least about 70%, or at least about 80%) and/or at most about 99% (e.g., at most about 95%, 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 12.
The second polymer can be immiscible with the first polymer. For example, the second polymer can form phase separation when blended with the first polymer. Without wishing to be bound by theory, it is believed that using two immiscible polymers in film 12 can form pores upon stretching, which impart breathability to film 12 (i.e., allowing passage of moisture, but not water, through film 12). As such, the second polymer can serve as an organic pore-forming agent. In some embodiments, film 12 can include three or more (e.g., four or five) immiscible polymers.
Examples of suitable second polymers include a polycycloolefin, a polymethylpentene, or a copolymer thereof. The monomers that can be used to prepare polycycloolefin include non-aromatic cyclic hydrocarbons containing one or more (e.g., two or three) ring double bonds. Examples of suitable monomers include dipentene, dicyclopentadiene, alpha-terpinene, gamma-terpinene, limonene, alpha-pinene, 3-carene, norbornene, and norbornadiene. Examples of suitable polycycloolefins include poly(cycloolefin-co-olefin), such as poly(norbornene-co-ethylene) or a copolymer formed from ethylene and substituted norbornene. A commercial example of a polycycloolefin suitable for use in film 12 is APEL available from Mitsui Chemicals America, Inc. (Rye Brook, N.Y.). A commercial example of a polymethylpentene suitable for use in film 12 is TPX MX0002 available from Mitsui Chemicals America, Inc. The substituted norbornene can include those substituted with C1-C20 alkyl, C3-C20 cycloalkyl, or aryl.
The amount of the second polymer in film 12 can vary depending on the first polymer used or the intended applications. For example, the second polymer can be at least about 1% (e.g., at least about 5%, 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 50%, at most about 45%, at most about 40%, at most about 35%, at most about 30%, at most about 25%, or at most about 20%) of the total weight of film 12.
Without wishing to be bound by theory, it is believed that, as the second polymer has a polymer backbone similar to that of the first polymer, a relatively large amount (e.g., at least about 5% by weight or at least about 30% by weight) of the second polymer can be blended with the first polymer to form microporous breathable film 12 that is substantially uniform and has superior processability even without using a compatibilizer, thereby significantly reducing the cost for manufacturing the film. By contrast, when a conventional immiscible polymer (e.g., a polystyrene) is blended with the first polymer (e.g., a polyolefin) at the same concentration level, a uniform film is generally not formed even in the presence of a compatibilizer.
In some embodiments, film 12 can further include a pore-forming filler (e.g., an inorganic pore-forming filler) to facilitate generation of pores upon stretching (e.g., by using a ring-rolling process during the manufacture of multilayer article 10).
The pore-forming filler can have a low affinity to and a lower elasticity than the polyolefin polymer in film 12. In some embodiments, 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 12 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 12 while allowing the filler to be pulled away from the polyolefin when film 12 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.
The amount of the pore-forming filler in film 12 can vary as desired. For example, film 12 can include from at least about 5% (e.g., at least about 10%, at least about 15%, or at least about 20%) to at most about 30% (e.g., at most about 25%, at most about 20%, or at most about 15%) by weight of the pore-forming filler (e.g., calcium carbonate).
In some embodiments, film 12 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 12 and/or to improve adhesion between film 12 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 12.
Optionally, film 12 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 anyhydride (EMA) copolymers, ethylene-acrylic acid (EEA) copolymers, and butyl rubber. A commercial example of such an elastomer is VERSIFY (i.e., an ethylene-propylene copolymer) available from Dow (Midland, Mich.). Film 12 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 12 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 12 can optionally include a nanoclay (e.g., montmorillonite nanoclay). Examples of nanoclays have been described in, e.g., Provisional Application No. 61/498,328, entitled “Vapor-permeable, Substantially Water-impermeable Multilayer 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 12. 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 12. 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 12 can have a chemical structure similar to or the same as the chemical structure of a polyolefin in film 12. Both examples described above can result in a multilayer article with improved adhesion between film 12 and nonwoven substrate 14.
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 fiber.
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., a nSMS, 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 and about 40 percent (e.g., between about 8 and about 30 percent or between about 22 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 film 12 onto nonwoven substrate 14 to form a laminate. Film 12 can be applied onto nonwoven substrate 14 by extruding (e.g., cast extrusion) a suitable composition for film 12 (e.g., a composition containing the first and second polymers described above) at an elevated temperature to form a film onto nonwoven substrate 14. In some embodiments, the just-mentioned composition can be 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 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 one of the films is film 12 described above. The additional films can be made by one or more of the materials used to prepare film 12 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. As shown in FIG. 2, a suitable composition (e.g., a composition containing the first and second polymers described above) 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 28 to a flat film die 38. Extrusion melt 40 discharging from flat film die 38 can be coated on nonwoven substrate 14 from roll 30. The coated substrate can then enter a nip formed between rolls 34 and 36, 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 34 and 36 can quench extrusion melt 40 while at the same time compressing extrusion melt 40 so that it contacts nonwoven substrate 14. In some embodiments, roll 34 can be a smooth rubber roller with a low-stick surface coating while roll 36 can be a metal roll. A textured embossing roll can be used to replace metal roll 36 if a multilayer article with a textured film layer is desired. When extrusion melt 40 is cooled, it forms film 12 laminated onto nonwoven substrate 14. The laminate thus formed can then be collected on a collection roll 44. In some embodiments, the surface of nonwoven substrate 14 can be corona or plasma treated before it is coated with extrusion melt 40 to improve the adhesion between nonwoven substrate 14 and film 12.
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 between the first and second polymers in film 12 that allow air or moisture to pass through. 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 Patent 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 film 12 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, 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.
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
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 %. For instance, the 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 (osy), 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 breaking 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 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 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 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 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 or nonwoven substrate 14.
In some embodiments, the surface of film 12 or nonwoven substrate 14 can be at least partially treated to promote adhesion. For example, the surface of film 12 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 example is 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 microporous breathable film containing 60 wt % polypropylene, 20 wt % KRATON (i.e., a styrenic block copolymer serving as a compatibilizer) available from Kraton Polymers U.S. LLC (Houston, Tex.), and 20 wt % styrene (i.e., a conventional immiscible polymer), and (2) a multilayer article similar to multilayer article (1) except that it contained a microporous breathable film that included 65 wt % polypropylene, 30 wt % APEL (i.e., an exemplary polycycloolefin copolymer disclosed herein), and 5 wt % low-density polyethylene. Both multilayer articles were formed by extruding the microporous breathable film onto TYPAR at 480° F. and had total film unit weights of 22 gsm.
Multilayer article (1) and (2) were evaluated for their MVTR and their capability of forming uniform breathable films. The MVTR was measured by using ASTM E96-A. The test results are summarized in Table 1 below.









TABLE 1





Sample
Uniformity Observation
MVTR (Perm)







(1)
Holes in the film
N/A


(2)
Uniform film
11.1 after ring rolling









The results showed that, when using a conventional immiscible polymer, the microporous breathable film in multilayer article (1) exhibited poor uniformity (i.e., poor processability) even though it contained as much as 20 wt % of a compatibilizer. Unexpectedly, when using as much as 30 wt % of an exemplary immiscible polymer (i.e., APEL) described in this disclosure, multilayer article (2) exhibited superior uniformity in the microporous breathable film even though no compatibilizer was used in the film.
Other embodiments are in the claims.

## Claims

1. An article, comprising:
a nonwoven substrate; and
a microporous breathable film supported by the nonwoven substrate, the microporous breathable film comprising a first polymer comprising at most about 99% of a total weight of the microporous breathable film and an amount of a second polymer comprising at least about 1% of the total weight of the microporous breathable film, the second polymer being immiscible with the first polymer,
wherein the second polymer has a polymer backbone similar to that of the first polymer such that at least about 5% by weight of the amount of the second polymer is blended with the first polymer, and
wherein the microporous breathable film is devoid of a pore-forming filler.

2. The article of claim 1, wherein the first polymer comprises a polyolefin and the second polymer comprises a polycycloolefin, a polymethylpentene, or a copolymer thereof.

3. The article of claim 2, wherein the second polymer comprises a poly(cycloolefin-co-olefin).

4. The article of claim 2, wherein the second polymer comprises a poly(norbornene-co-ethylene) or a copolymer formed from ethylene and norbornene substituted with a substituent.

5. The article of claim 2, wherein the first polymer comprises a polyethylene or a polypropylene.

6. The article of claim 5, wherein the first polymer comprises a polyethylene selected from the group consisting of low-density polyethylene, linear low-density polyethylene, high-density polyethylene, and copolymers thereof.

7. The article of claim 5, wherein the film further comprises an elastomer.

8. The article of claim 1, wherein the microporous breathable film is substantially uniform in the absence of a compatibilizer.

9. The article of claim 1, wherein the nonwoven substrate comprises randomly disposed polymeric fibers, at least a portion of the fibers being bonded to one another.

10. The article of claim 1, wherein the article is embossed.

11. The article of claim 2, wherein the article has a moisture vapor transmission rate of at least about 35 g/m2/day when measured at 23° C. and 50 RH %.

12. A construction material, comprising the article of claim 1.

13. The construction material of claim 12, wherein the construction material is a housewrap or a roofwrap.

14. The article of claim 2, wherein:
the first polymer comprises a polyethylene or a polypropylene; and the second polymer comprises a poly(cycloolefin-co-olefin).

15. The article of claim 14, wherein the film further comprises an elastomer.

16. The article of claim 15, wherein the microporous breathable film is supported by a nonwoven substrate comprising randomly disposed polymeric fibers, at least some of the fibers being bonded to one another.

17. The article of claim 16, wherein:
the article has a moisture vapor transmission rate of at least about 35 g/m2/day when measured at 23° C. and 50 RH %;
the article has a unit weight of 1.25 osy;
the article has a tensile strength of at least about 35 pounds in at least one of the machine direction or the cross-machine direction as measured according to ASTM D5034; and
the article has a hydrostatic head of at least about 55 cm.

18. The article of claim 1, wherein at least about 30% by weight of the amount of the second polymer is blended with the first polymer.

19. The article of claim 1, wherein 5-30% by weight of the amount of the second polymer is blended with the first polymer.