Polyethylene film

Abstract

To provide a new film.SOLUTION: There is disclosed a new film containing a porous polyethylene membrane into which a hydrophilic polymer is adsorbed in order to form a film having excellent durability. The film is useful for producing a textile laminate capable of forming an article, especially waterproof and air-permeable apparel.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to waterproof, breathable polyethylene film composites useful for a variety of applications. The films can be used alone or laminated to other layers to form multi-layer laminates. [Background technology]

[0002] Clothing and other types of apparel, such as shoes, gloves, hats, etc., often incorporate a waterproof, breathable layer to keep the wearer dry in wet conditions. These clothing items may be formed using a laminate of a breathable waterproof layer with one or more textiles. Waterproof, breathable films made using porous PTFE membranes and hydrophilic polyurethanes are currently used in the manufacture of GORE-TEX® textile laminates. PTFE membranes are microporous and generally hydrophobic, with the membrane pore sizes being larger than water molecules, but the pores are much smaller than individual water droplets. Water vapor can pass through the material, while water droplets are prevented from passing from one side of the membrane to the other.

[0003] Although PTFE membranes work well, porous polyurethane membranes have also been developed for use in apparel, but these membranes can lack durability and in some instances can be dissolved by certain commonly used products such as nail polish or insect repellent sprays. These membranes can also have the limitation that they are stiff and noisy when the wearer moves. There continues to be a need to produce membranes that have excellent waterproofing and breathability, and that have a pleasant feel and low noise when articles such as clothing that contain the membrane are moved or bent. Summary of the Invention

[0004] In a first embodiment, the present disclosure provides a method for producing a porous polyethylene having a porous structure comprising the steps of: A) mixing the porous polyethylene with a porous material having a porous structure of 0.5×10 6a) a porous polyethylene membrane having a weight average molecular weight of more than 2500 g / mole, b) a porosity of 40% or more, and c) a Gurley number of less than 200 seconds; and B) a hydrophilic polymer filling at least a portion of the pores of the porous polyethylene, the film comprising: i) a hydrophilic polymer having an MVTR of 2500 g / m 2 / day or more, and ii) the mass is 30 grams / meter 2 and optionally, iii) a Gurley number of 1000 seconds or greater.

[0005] In a second embodiment, the present disclosure relates to the film of embodiment 1, wherein the ratio of matrix tensile strengths in two orthogonal directions of the film is in the range of 0.5 to 2.0.

[0006] In a third embodiment, the present disclosure relates to the film of embodiment 1 or 2, wherein substantially all of the pores in the porous polyethylene membrane are filled with the hydrophilic polymer.

[0007] In a fourth embodiment, the present disclosure relates to the film of any one of the first to third embodiments, wherein the hydrophilic polymer is a polyurethane, a polyamide, a polyester, an ionomer or a copolymer, or a copolymer or combination thereof.

[0008] In a fifth embodiment, the present disclosure provides a porous polyethylene membrane having a pore size of 10 grams per meter. 2 The film of any one of embodiments 1 to 4, having a mass of less than

[0009] In a sixth embodiment, the present disclosure relates to the film of any one of the first to fifth embodiments, wherein the porous polyethylene membrane has a porosity of 60% or more.

[0010] In a seventh embodiment, the present disclosure relates to the film of any one of the first to sixth embodiments, wherein the porous polyethylene membrane has a Gurley number of 60 seconds or less.

[0011] In an eighth embodiment, the present disclosure relates to the film according to any one of the first to seventh embodiments, wherein the ratio of matrix tensile strengths in two orthogonal directions of the film is in the range of 0.7 to 1.4.

[0012] In a ninth embodiment, the present disclosure relates to a film according to any one of embodiments 1 to 8, wherein the polyethylene membrane has a first side and a second side, and the hydrophilic polymer is applied to the first side of the polyethylene membrane, thereby filling at least a portion of the pores and forming a hydrophilic polymer cap on the first side of the polyethylene membrane.

[0013] In a tenth embodiment, the present disclosure relates to the film according to any one of the first to ninth embodiments, wherein the mass ratio of the porous polyethylene to the hydrophilic polymer is in the range of 30 to 0.5.

[0014] The present disclosure also relates to an article comprising the film according to any one of the first to tenth embodiments.

[0015] In a twelfth embodiment, the present disclosure relates to the article of embodiment 11, wherein the article is a multi-layer laminate comprising at least one other layer laminated to the film.

[0016] In a thirteenth embodiment, the present disclosure relates to the article of any one of embodiments 11 or 12, wherein the at least one other layer is a textile layer, a polymeric film layer, a natural leather layer, a synthetic leather layer, a fleece layer, or a combination thereof.

[0017] In a fourteenth embodiment, the present disclosure relates to the article of any one of embodiments 11 to 13, wherein the at least one other layer is a textile layer.

[0018] In a fifteenth embodiment, the present disclosure relates to the article of any one of embodiments 11 to 14, wherein the layers of the laminate are adhered to one another using a continuous or discontinuous adhesive.

[0019] In a sixteenth embodiment, the present disclosure relates to the article of any one of embodiments 11 to 15, wherein the adhesive is a thermoplastic or crosslinkable adhesive.

[0020] In a seventeenth embodiment, the present disclosure relates to the article of any one of embodiments 11 to 16, wherein the article is an article of clothing.

[0021] In an eighteenth embodiment, the present disclosure relates to the article of embodiment 17, wherein the article of clothing is a jacket, a coat, a shirt, pants, gloves, a hat, shoes, coveralls, or at least a portion thereof.

[0022] In a nineteenth embodiment, the present disclosure relates to the article of any one of embodiments 17 or 18, wherein the film is on the outside of the garment or the film is not on the outside of the garment.

[0023] In a twentieth embodiment, the present disclosure relates to the article of any one of embodiments 17-19, wherein the article of clothing is waterproof.

[0024] The present disclosure also relates to articles that include the films. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0025] The disclosures of all cited patent and non-patent publications are incorporated herein by reference in their entirety.

[0026] As used herein, the terms "embodiment" or "disclosure" are not meant to be limiting and generally apply to any of the embodiments defined in the claims or described herein. These terms are used interchangeably herein.

[0027] Unless otherwise disclosed, the terms "a" and "an" as used herein are intended to include one or more (i.e., at least one) of the referenced feature.

[0028] The features and advantages of the present disclosure will be more readily understood by those skilled in the art upon reading the following detailed description. It should be understood that certain features of the present disclosure that are described above and below in the context of separate embodiments for clarity may also be provided in combination in a single embodiment. Conversely, various features of the present disclosure that are described for brevity as a combination in the context of a single embodiment may also be provided separately or in any subcombination. Furthermore, references to the singular may include the plural (e.g., "a" and "an" may refer to one or more) unless the context clearly dictates otherwise.

[0029] The use of numerical values ​​in the various ranges specified in this application, unless otherwise indicated, is indicated as an approximation, as if both the minimum and maximum values ​​in the stated range were preceded by the word "about." In this manner, small variations above and below the stated ranges can be used to achieve substantially the same results as the values ​​within the range. Also, the disclosure of these ranges is intended as a continuous range including any and all values ​​between the minimum and maximum values.

[0030] As used herein, the term "membrane" refers to a polymer in the form of an essentially two-dimensional sheet, with both the length and width being much greater than the thickness, e.g., both the length and width being 100 times or more greater than the thickness. In some embodiments, the membrane is a microporous membrane, for example, having a structure that allows water vapor to pass through the thickness of the membrane without allowing liquid water to permeate from one side of the membrane to the other. On average, the pore size is on the order of a few nanometers to about 1 micrometer.

[0031] The term "film" refers to a membrane whose pores are at least partially filled with a polymer such that gas or liquid flow does not occur through the open pore channels of the membrane. In some embodiments, the polymer that at least partially fills the pores can be a hydrophilic polymer.

[0032] The term "hydrophilic polymer" refers to a polymer that is capable of transporting substantial amounts of water through a film by absorbing water on one side of the film where the water concentration is higher and desorbing or evaporating water on the opposite side of the film where the water vapor concentration is lower. In some embodiments, a layer of hydrophilic polymer that is 10 micrometers thick has a water vapor content of 5,000 g / m 2 / day or more, or 10,000g / meter 2 / day or more.

[0033] The terms "porous polyethylene membrane" and "polyethylene membrane" are used interchangeably throughout this specification. Unless otherwise specified, both terms refer to a) 0.5×10 6 By porous polyethylene membrane is meant a) a porous polyethylene membrane having a weight average molecular weight of more than 30% by weight of porous polyethylene having a weight average molecular weight of more than g / mol, b) a porosity of more than 40%, and c) a Gurley number of less than 200 seconds or less than 100 seconds. Under magnification, the porous polyethylene membrane exhibits a fibrillated structure of polyethylene fibrils, where at sufficient magnification one or more polyethylene fibrils can be seen, and in some cases three or more fibrils can be interconnected by one or more crossing points of three or more fibrils.

[0034] As used herein, the term "polyethylene" refers to a polyethylene polymer having less than 5 weight percent of one or more comonomers. In some embodiments, the polyethylene does not contain a fluorine-containing comonomer, and in yet other embodiments, the polyethylene is a polyethylene homopolymer.

[0035] The present disclosure relates to a film comprising A) a porous polyethylene membrane and B) a hydrophilic polymer, said hydrophilic polymer filling at least a portion of the pores of said porous polyethylene membrane. The film is leak-proof due to contamination with oil, detergent or other contact angle reducing materials and is itself waterproof. Furthermore, articles containing the film are more durable in the field and during washing than other non-air permeable hydrophilic films that do not include a porous polyethylene membrane as a structural support. The porous polyethylene is a material in which 30% or more by weight of polyethylene is at least 0.5×10 6 In some embodiments, the porous polyethylene has a weight average molecular weight of greater than 0.75×10 6 In yet another embodiment, the porous polyethylene comprises 30% by weight or more of polyethylene having a weight average molecular weight of greater than 1.0×10 g / mol. 6 In yet another embodiment, the polyethylene comprises 30% by weight or more of a polyethylene having a weight average molecular weight of more than 0.5×10 g / mol. 6 Weight average molecular weight in grams per mole (g / mol) or more than 50% by weight of polyethylene is less than 0.5 × 10 6 The porous polyethylene has a weight average molecular weight greater than grams per mole (g / mol). All weight percentages are based on the total weight of the porous polyethylene membrane. In some embodiments, the porous polyethylene has a weight average molecular weight greater than 750,000 g / mol. In yet other embodiments, the porous polyethylene has a weight average molecular weight greater than 1,000,000 g / mol. In yet other embodiments, the polyethylene has a weight average molecular weight greater than 1,500,000 g / mol, or greater than 1,750,000 g / mol. In yet other embodiments, the polyethylene has a weight average molecular weight greater than 2,000,000 g / mol, 3,000,000 g / mol, 4,000,000 g / mol, 5,000,000 g / mol, or 8,000,000 g / mol.

[0036] The polyethylene membrane is a porous polyethylene membrane, where the membrane has a porosity of at least 40%. In some embodiments, the porosity of the porous polyethylene membrane can be at least 50%, or at least 60%, or at least 70%, or at least 80%. The porosity φ of the membrane is determined by measuring the mass per unit area of ​​the membrane, MPA, and the thickness of the membrane, t, where φ=(1-MPA / (t * ρ)) * 100 relationship, where ρ is the density of the membrane polymer. The porous polyethylene membranes can also have a Gurley number of less than 200 seconds, or less than 100 seconds, or 90 seconds or less, or 80 seconds or less, or 70 seconds or less, or 60 seconds or less, or 50 seconds or less, or 40 seconds or less, or less than 10 seconds.

[0037] Porous polyethylene membranes can be relatively lightweight, e.g., 10 grams per meter 2 In other embodiments, the porous polyethylene membrane can have a mass of 9 gsm or less, or 8 gsm or less, or 7 gsm or less, or 6 gsm or less, or 5 gsm or less, or 4 gsm or less, or 3 gsm or less, or 2 gsm or less.

[0038] The porous polyethylene film may be colored or uncolored. The use of the porous polyethylene film can provide valuable aesthetic qualities to the film and articles containing the film, especially when the porous polyethylene film is visible in the article. Any of the known coloring methods can be used. For example, the porous polyethylene film can be colored throughout the bulk of the film by adding a pigment or dye during the film formation process. In other embodiments, the porous polyethylene film can be colored after formation via known printing and dyeing processes. In yet another embodiment, the porous polyethylene film can be free or essentially free of added color, and color can be added at one or more steps during the film formation process described herein.

[0039] The film also includes B) a hydrophilic polymer that fills at least a portion of the pores of the porous polyethylene membrane. The phrase "fills at least a portion of the pores" means that the hydrophilic polymer is absorbed into the pores of the polyethylene membrane and fills the pores to the point where airflow through the area of ​​the film containing the hydrophilic polymer is not measurable (Gurley number of 1000 seconds or more). In other words, the hydrophilic polymer is not merely a coating on the walls that define the pores of the polyethylene membrane. Although some voids may be present, it is believed that the hydrophilic polymer forms a continuous layer in the area of ​​the porous polyethylene membrane where the hydrophilic polymer is applied. In other embodiments, the hydrophilic polymer forms a continuous layer that is void-free or essentially void-free in the area of ​​the porous polyethylene membrane where the hydrophilic polymer is applied. In yet another embodiment, substantially all of the pores of the porous polyethylene membrane are filled with the hydrophilic polymer.

[0040] The polyethylene membrane has a first surface and a second surface. A hydrophilic polymer can be applied to the first surface of the porous polyethylene membrane, and the hydrophilic polymer can penetrate at least some of the pores to form a film, thereby filling at least some of the pores of the polyethylene membrane. The first surface of the polyethylene membrane can include a cap layer of hydrophilic polymer on the outside of the membrane. There is essentially no upper limit to the cap layer or amount of hydrophilic polymer on the first surface of the porous polyethylene membrane. However, if the cap layer is too thick, the beneficial properties of the porous polyethylene membrane cannot be realized, so the upper capping limit is about 50 micrometers. In some embodiments, the cap layer of hydrophilic copolymer can be up to 40 micrometers, or up to 30 micrometers, or up to 20 micrometers, or up to 15 micrometers thick on the first surface of the polyethylene membrane. In some embodiments, the cap layer of hydrophilic polymer can be up to about 10 micrometers thick on the first surface of the polyethylene membrane. In other embodiments, the cap layer on the first side of the polyethylene film is 10 micrometers or less, or 8 micrometers or less, or 6 micrometers or less, or 4 micrometers or less, or 2 micrometers or less. In yet another embodiment, the cap layer of hydrophilic polymer is not present on the first side of the polyethylene film. The second side of the polyethylene film may be essentially free of hydrophilic polymer on the surface, e.g., no more than 1 micrometer of hydrophilic polymer is present from the surface of the polyethylene film. In some embodiments, less than the entire thickness of the porous polyethylene film is filled with hydrophilic polymer, e.g., no more than 90% of the thickness of the polyethylene film may be filled with hydrophilic polymer, provided that sufficient hydrophilic polymer is absorbed to provide the porous polyethylene film with a Gurley number of 1000 seconds or more. In other embodiments, essentially the entire thickness of the porous polyethylene film is filled with hydrophilic polymer. As used herein, the phrase "essentially the entire thickness" means that at least 90% of the thickness of the porous polyethylene film is filled with hydrophilic polymer.In another embodiment, the hydrophilic polymer may be applied to the second side of the polyethylene membrane in the same manner as the first side. The hydrophilic polymer applied to the second side may be the same or different from the hydrophilic polymer applied to the first side. In yet another embodiment, the film may be a composite film, where a sufficient amount of hydrophilic polymer is applied to the first side of a first porous polyethylene membrane to form a cap layer, and then a second porous polyethylene membrane, which may be the same or different from the first porous polyethylene membrane, may be bonded to the laminate via the cap layer of hydrophilic polymer. This results in a three-layer structure with two porous polyethylene membranes bonded together with a hydrophilic polymer as the layer between the two porous polyethylene membranes. Optionally, one or more additional hydrophilic polymer layers may be applied to one or both of the outer surfaces of the composite film.

[0041] In some embodiments, the hydrophilic polymer can be applied to the porous polyethylene membrane in a continuous manner, such that essentially 100 percent of the surface area of ​​the porous polyethylene membrane comprises the hydrophilic polymer. As used in this context, the term "continuous" means that the entire width or nearly the entire width of the porous polyethylene membrane is coated with the hydrophilic polymer. It should be noted that in many coating processes, the edges of the roll of material may not be coated due to frames or dams at the edges that do not allow the entire width of the membrane to be coated. In other embodiments, the hydrophilic polymer can be applied to the porous polyethylene membrane in a discontinuous manner. As used in this context, the term "discontinuous" means that less than 100 percent of the surface area of ​​the porous polyethylene membrane is coated with the hydrophilic polymer, and portions of the non-edge regions of the porous polyethylene membrane do not comprise the hydrophilic polymer. For example, a hydrophilic polymer applied to a porous polyethylene membrane as a series of dots or a grid of orthogonal lines should be considered a discontinuous coating. The percent area of ​​the porous polyethylene film filled with the hydrophilic polymer can range from 20 percent to 100 percent, or from 30 percent to less than 100 percent, or from 40 percent to less than 100 percent, or from 50 percent to less than 100 percent, or from 60 percent to less than 100 percent, or from 70 percent to less than 100 percent, or from 80 percent to less than 100 percent, or from 90 percent to less than 100 percent. In other embodiments, the application of the hydrophilic polymer can be done in a manner that produces a random or non-random pattern of dots, polygons, parallel lines, intersecting lines, straight lines, curved lines, or any combination thereof to provide the desired percent by area coverage. If oleophobicity is desired in such films, in certain embodiments, it may be desirable to include an oleophobic coating, as described herein.

[0042] In terms of mass ratio, the film can have a ratio of the mass of hydrophilic polymer to the mass of the porous polyethylene membrane in the range of 30.0 to 0.5, in other embodiments, the mass ratio of hydrophilic polymer to the polyethylene membrane can be 20.0, 15.0, 10.0, 9.0, 8.0, 7.0, 6.0, 5.0, 4.0, 3.0, 2.0, 1.0, 0.9, 0.8, 0.7, 0.6, 0.5, or any mass ratio therebetween.

[0043] Suitable hydrophilic polymers may include, for example, polyurethanes, polyamides, polyesters, ionomers, or copolymers or combinations thereof. In other embodiments, nearly any suitable hydrophilic polymer may be used, provided that the hydrophilic polymer has a viscosity of 5000 grams per meter or more. 2 / day or more or 10,000 grams / meter 2 The hydrophilic polymer may have a water vapor transmission rate of 100 / day or more. The hydrophilic polymer may be a thermoplastic or crosslinkable polymer. In some embodiments, the hydrophilic polymer is a polyurethane, and in further embodiments, the polyurethane is a crosslinked polyurethane. Suitable polyurethane polymers may be, for example, polyester urethane, polyether urethane, or polyether-polyester urethane.

[0044] In some embodiments where coloration is desired, color can be added using, for example, a colored hydrophilic polymer, where a pigment or dye is added to the hydrophilic polymer resulting in a film with the desired color. In other embodiments, the porous polyethylene film can be colored during the formation of the porous polyethylene membrane according to known methods, for example, masterbatch processing. Thus, one or both of the porous polyethylene membrane and the hydrophilic membrane can be colored or not colored. If both the porous polyethylene and the hydrophilic polymer are colored, they can be colored with the same or similar shades, or the colors can be selected independently of each other. Any known pigment or dye can be used, including organic pigments and dyes, inorganic pigments or dyes, metals, metal oxides, carbon black, titanium dioxide, or combinations thereof.

[0045] In yet another embodiment, the porous polyethylene membrane can be treated with both an oleophobic polymer and a hydrophilic polymer. For example, in a first step, the first surface of the porous polyethylene membrane can be treated with an oleophobic polymer that can coat the walls that define the pores of the porous polyethylene membrane without filling the pores, where the oleophobic polymer is provided such that a thickness less than the entire thickness of the porous polyethylene membrane is treated with the oleophobic polymer. After an optional step of drying and curing the oleophobic polymer, the second surface of the porous polyethylene membrane can be treated with a hydrophilic polymer to fill at least a part of the remaining thickness of the porous polyethylene membrane, followed by an optional step of heating and curing the hydrophilic and oleophobic polymers. In these embodiments, the hydrophilic polymer fills only the parts of the porous polyethylene membrane that do not have the oleophobic treatment because the hydrophilic polymer cannot wet the oleophobically treated parts of the porous polyethylene membrane.

[0046] In some embodiments, the porous polyethylene membrane can be treated with an oleophobic polymer over 5 percent or more of the thickness of the porous polyethylene membrane. In other embodiments, the porous polyethylene membrane can include an oleophobic treatment over 95 percent or less of its thickness. In yet other embodiments, the oleophobic treatment can be present in the range of 10-90 percent, or 10-80 percent, or 10-70 percent, or 10-60 percent, or 10-50 percent, or 10-40 percent, or 10-30 percent, or 10-20 percent of the thickness of the porous polyethylene membrane. After treatment of the first surface of the porous polyethylene membrane, the second surface of the porous polyethylene membrane can be treated with a hydrophilic polymer that can fill the remaining thickness of the porous polyethylene membrane, in some embodiments, forming a cap layer of hydrophilic polymer.

[0047] The resulting film, comprising a porous polyethylene membrane and a hydrophilic polymer, had a viscosity of 2500 g / m 2 / day(g / m 2 / day) or more Moisture Vapor Transmission Rate (MVTR) of 30 grams / meter 2 In order to be breathable, i.e., to allow water vapor to be transported from one side of the film to the other without liquid water migrating through the film, the MVTR must be 2500 g / m 2 / day or more. In another embodiment, the film has a coating strength of 3000 g / m 2 / day or more, 3500g / m 2 / day or more, 4000g / m 2 / day or more, 4500g / m 2 / day or more, 5000g / m 2 / day or more, 5500g / m 2 / day or more, 6000g / m 2 / day or more, 6500g / m 2 / day or more, 7000g / m 2 / day or more, 7500g / m 2 / day or more, 8000g / m 2 / day or more, 8500g / m 2 / day or more, 9000g / m 2 / day or more, 9500g / m 2 / day or more or 10,000g / m 2 / day or more MVTR.

[0048] The film may also have a ratio of matrix tensile strengths in two orthogonal directions in the range of 0.5 to 2.0. In other embodiments, the ratio of tensile strengths in two orthogonal directions may range from 0.7 to 1.4. In yet other embodiments, the ratio of tensile strengths may be 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, or any value between these two numbers. The difference in tensile strengths in the two orthogonal directions is related to the difference in the total strain applied in the two directions during the membrane manufacturing process.

[0049] The film can also be stain-resistant due to the presence of a hydrophilic polymer filling the voids in at least a portion of the thickness of the membrane, thereby forming a continuous layer without voids in that portion of the porous polyethylene membrane. Stain-resistant, as used herein, means that the film does not become stained with sweat, sebum or oil, thereby reducing its waterproofness over time. If at least a portion of the pores of the porous polyethylene membrane are left unfilled, an oleophobic coating on the walls of the unfilled pores can provide stain resistance to the unfilled pores.

[0050] The present disclosure also provides a method for producing a film comprising a porous polyethylene membrane and a hydrophilic polymer, comprising: 1) 30% or more of the total mass of porous polyethylene is 0.5 × 10 6 providing a porous polyethylene membrane comprising porous polyethylene having a weight average molecular weight of greater than 1 g / mol, a porosity of 40% or greater, and a Gurley number of less than 200 seconds; 2) coating at least a portion of the porous polyethylene membrane with a hydrophilic polymer; and 3) Optionally, crosslinking the hydrophilic polymer. The present invention relates to a method comprising the steps of:

[0051] In another embodiment, the film comprises: 1) 30% or more of the total mass of porous polyethylene is 0.5 × 10 6 providing a porous polyethylene membrane comprising porous polyethylene having a weight average molecular weight of greater than 1 g / mol, a porosity of 40% or greater, and a Gurley number of less than 200 seconds; 2) coating a first surface of the porous polyethylene membrane with an oleophobic polymer to coat the walls defining the pores of the porous polyethylene membrane; 3) coating a second surface of the porous polyethylene membrane with a hydrophilic polymer to form the film; and 4) Optionally, crosslinking the hydrophilic polymer. It can be produced according to the following procedure.

[0052] The film can also be stain-resistant due to the presence of a hydrophilic polymer filling the voids in at least a portion of the thickness of the membrane, thereby forming a continuous layer without voids in that portion of the porous polyethylene membrane. Stain-resistant, as used herein, means that the film does not become stained with sweat, sebum or oil, thereby reducing its waterproofness over time. If at least a portion of the pores of the porous polyethylene membrane remain unfilled, an oleophobic coating on the walls of the unfilled pores can provide stain resistance to the unfilled pores.

[0053] The present disclosure also relates to an article comprising the film. One advantage of the article of the present disclosure is that the article is wash-durable. As used herein, the term "wash-durable" means that a laminate comprising the disclosed film can be washed for at least 15 hours according to the wash-durability test procedure disclosed herein, and the laminate is waterproof as determined according to the Suter test described herein. In other embodiments, the laminate maintains its wash-durability after being washed for at least 50 hours or at least 100 hours. In some embodiments, the laminate did not leak after more than 200 hours of wash testing. The article can also be waterproof and breathable.

[0054] In some embodiments, the article comprises: 1) 30% or more of the total mass of porous polyethylene is 0.5 × 10 6 providing a porous polyethylene membrane comprising porous polyethylene having a weight average molecular weight of greater than 1 g / mol, a porosity of 40% or greater, and a Gurley number of less than 200 seconds; 2) coating at least a portion of the porous polyethylene membrane with a hydrophilic polymer; 3) laminating the film to at least one other layer; and 4) Optionally, crosslinking the hydrophilic polymer. It can be produced according to the following procedure.

[0055] In another embodiment, the article comprises: 1) 30% or more of the total mass of porous polyethylene is 0.5 × 10 6 providing a porous polyethylene membrane comprising porous polyethylene having a weight average molecular weight of greater than 1 g / mol, a porosity of 40% or greater, and a Gurley number of less than 200 seconds; 2) laminating at least one other layer to the first surface of the porous polyethylene membrane; 3) coating at least a portion of the second surface of the porous polyethylene membrane with a hydrophilic polymer; and 4) Optionally, crosslinking the hydrophilic polymer. It can be produced according to the following procedure.

[0056] The article can be a multi-layer laminate, for example, one or more layers of a film can be superimposed with one or more other layers to form a laminate. The other one or more layers can be a textile layer, a polymeric film layer, a natural leather layer, a synthetic leather layer, a fleece layer, or a combination thereof. The one or more layers can be a textile layer, a film layer, or a combination thereof. In some embodiments, the article can be a two-layer laminate including a textile layer adhered to a first side or a second side of the film. In some embodiments, the article can be a three-layer laminate including a first textile layer adhered to a first side of the film and a second textile layer adhered to a second side of the film. In yet other embodiments, additional layers can be applied to produce a multi-layer laminate having four, five, six or more layers. Suitable textile layers can include any woven, knitted or nonwoven fabric. The textiles can be natural and / or synthetic, such as cotton, wool, silk, jute, polyamide, polyester, acrylic, aramid, viscose, rayon, carbon fiber, or combinations thereof. Suitable polymeric films can include, for example, polyolefins, polyesters, polyamides, polyurethanes, polyvinyl alcohols, polyvinyl acetates, fluoropolymers, polyvinyl halides, polyvinyl chlorides, epoxy resins, silicone polymers, or combinations thereof. Laminates can also be made that include one or more layers of the disclosed films, one or more textile layers, and / or one or more polymeric film layers.

[0057] Due to the high strength of the disclosed films, laminates can be made using any of the relatively low mass textiles or materials listed above. In some embodiments, the laminates have a mass of less than 5 grams per meter. 2 ~30 grams / meter 2The textile may include relatively low mass textiles having a basis weight in the range of 1000 gsm (gsm). In other embodiments, the textile may have a weight of 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 gsm or any value between two of these values. Although relatively low mass textiles can be used, textiles having a weight of 30 gsm or more can also be used. For example, relatively high mass textiles having a weight of as much as 500 gsm can be used.

[0058] Lamination techniques are well known in the art and may include, for example, adhesive lamination, thermal bonding, and stitching. If a waterproof laminate is required, stitch bonding may not be desirable unless care is taken to make the stitch holes impermeable to liquid water, for example by sealing the stitch holes using seam tape. In some embodiments, lamination is accomplished by adhesive lamination, where an adhesive is applied to one or more layers to be joined together, which are then optionally placed together with heat and / or pressure, for example, via nip rollers. The adhesive may be applied to the film layer, the textile layer, or both the film layer and the textile layer. The adhesive may be applied in a discontinuous manner, for example, in a series of adhesive dots, shapes, lines, or combinations thereof. In other embodiments, the adhesive may be applied as a continuous layer of adhesive. The adhesive composition may be a thermoplastic or crosslinkable adhesive in certain embodiments. In yet another embodiment, a hydrophilic polymer may be used as the adhesive to form the laminate. For example, after application of the hydrophilic polymer to one side of a porous polyethylene film with the formation of a cap layer of the hydrophilic polymer, a textile can be applied to the hydrophilic polymer, and heat and / or pressure can be applied to the laminate to ensure that the hydrophilic polymer is in sufficient contact with and adheres to the textile. If a hydrophilic polymer is used as the adhesive of the laminate, the curing step of the hydrophilic polymer can be performed after the textile or other material is placed on the side of the film containing the hydrophilic polymer cap layer. In some embodiments, a heat press can be used to provide sufficient pressure to allow the hydrophilic polymer to flow into the spaces between the textile fibers, and the heat from the heat press can perform the desired curing and heat treatment steps to create the laminate. In other embodiments, one or more rollers can provide the pressure and / or heat required to accomplish the same task, for example, continuously.

[0059] Laminates with stretch and recovery properties can be made according to known methods, such as those taught in U.S. Pat. No. 4,443,511, U.S. Pat. No. 9,950,504, U.S. Pat. No. 9,126,390, U.S. Pat. No. 9,233,520, U.S. Pat. No. 9,238,344, and WO2018 / 67529, all of which are incorporated herein by reference in their entirety, teach how to impart stretch to conventional membrane and laminate structures, and these teachings can be adapted to provide stretch to laminates that include the films of the present disclosure.

[0060] The article can be, for example, clothing, enclosures, protective enclosures, tents, sleeping bags, bivy bags, backpacks, packs, covers, and other similar forms that benefit from the properties of the disclosed films. The clothing can be a jacket, coat, shirt, pants, gloves, hat, shoes, coveralls, or at least a portion thereof. Many articles are manufactured from multiple panels that are sewn or otherwise glued together to form a finished product. Thus, "at least a portion" of an article means that at least one panel or a portion of a panel includes the disclosed film. The articles and clothing can be manufactured such that the film is on the outside of the clothing, or on the inside of the clothing, or the film is at least one of the middle layers of the clothing, for example, the middle layer of a three-layer laminate. One advantage of the articles and clothing that include the disclosed films is their wash durability. Another advantage of the clothing is that the clothing is waterproof and breathable.

[0061] In embodiments where the film is on the outside of the garment, i.e., it is the outermost part of the garment, the film can be colored, uncolored, textured, embossed, or any combination thereof to create the desired appearance. Methods for coloring the film are described herein. To emboss the film, the film can be selectively compressed in a random or non-random manner, for example, patterns, letters, words, pictures, sports team logos, business logos, or combinations thereof can be embossed into the membrane or film before or after treatment with the hydrophilic polymer, or both. Selective compression can result in areas of different translucency of the film, which can also vary the breathability of the film, with the embossed areas having relatively lower breathability than the non-embossed areas. Suitable methods of embossing can be found in US20080143012, the entirety of which is incorporated herein by reference.

[0062] In embodiments where the film is on the outside of the article of clothing, i.e., it is the outermost portion of the article of clothing, at least a portion of the film can be textured. The film can be textured by treating the film with a random or non-random pattern of an abrasion-resistant polymer. The abrasion-resistant polymer can be applied as a series of dots, lines, or other shapes to provide a desired appearance and improved abrasion resistance to the outermost portion of the article of clothing. Suitable abrasion-resistant polymers and methods for applying them can be found in US2010 / 0071115, which is incorporated herein by reference in its entirety. Another method for texturing the film can include applying flock to at least a portion of the film. Suitable methods for applying flock material can be found in WO99 / 39038, which is incorporated herein by reference in its entirety.

[0063] It has also been found that films and articles, such as laminates that include films, can be provided with essentially permanent wrinkles without the need for additional chemicals used today. This can be particularly useful in clothing articles that include a film and at least one textile layer, such as pants. It has been found that laminates that include a film and textile that have been placed in an embroidery hoop, heated, and then cooled, when removed from the embroidery hoop, exhibited wrinkles in the portions of the laminate that were secured to the embroidery hoop. The heating temperature should be 125°C or higher or 130°C or higher, and 180°C or lower. In embodiments where wrinkles are desired, such as in clothing, the wrinkles can be produced by folding the article and pressing it with heat. EXAMPLES

[0064] Test Method

[0065] molecular weight

[0066] Molecular weight determinations were performed according to the procedure given by Mead, DW, "Determination of Molecular Weight Distributions of Linear Flexible Polymers from Linear Viscoelastic Material Functions," Journal of Rheology 1994, 38(6):1797-1827.

[0067] porosity

[0068] Porosity, expressed as percent porosity, was determined by subtracting the quotient of the average density of the porous polyethylene membrane and the true density of the polymer from 1 and multiplying the result by 100. For the purposes of this calculation, the true density of polyethylene was taken as 0.94 grams per cubic centimeter. The density of the sample was calculated by dividing the mass / area of ​​the sample by its thickness.

[0069] Moisture Vapor Transmission Rate Test Protocol (MVTR)

[0070] MVTR is measured according to DIN EN ISO 15496 (2004). As this is a standard test used in the textile industry, please refer to the detailed description of the MVTR test disclosed in DIN EN ISO 15496 (2004). For a description of the MVTR test please also refer to WO 90 / 04175 A1.

[0071] The basic principle is summarized as follows: The sample to be tested is inserted into an annular sample support together with a highly water vapor permeable but waterproof microporous membrane. The support is then immersed in water (deionized water at 23 ° C) for 15 minutes so that the membrane is in contact with the water. The cup is filled with a saturated aqueous solution of potassium acetate to generate a relative humidity of 23% at the surface of the sample and is covered with a second piece of the same waterproof microporous membrane. The mass of the cup containing the potassium acetate solution and the second membrane is then weighed and placed on the sample support so that the second membrane is in contact with the sample. This allows water vapor to transfer from the water side through the sample to the cup containing potassium acetate. After 15 minutes, the cup containing potassium acetate is removed and its mass is measured. To determine the water vapor permeability of the test device without the sample, the same procedure is performed using the first and second membranes without the sample. The MVTR of the sample can then be determined from the difference of both measurements, taking into account also the influence of the two additional microporous membranes.

[0072] The moisture vapour transmission rate (MVTR) of the laminate according to the invention is measured according to EN ISO 15496 (2004) and is in g / m 2 / 24hr. To be considered water vapor permeable as used herein, a laminate generally has a surface area of ​​at least 3000 g / m 2 / 24hr, preferably at least 8000g / m 2 / 24hr, more preferably at least 12000g / m 2 It should have a water vapor permeability of 24hr / 20000g / m 2 Can go up to 24hr.

[0073] Gurley

[0074] The Gurley airflow test is performed at 100 cm 3 of air flows at 6.45cm under 12.4cm water pressure. 2 The time in seconds it takes for the solution to flow through the sample is measured. The samples were measured on a Gurley Densometer Model 4110 automated densitometer equipped with a Gurley Model 4320 automated digital timer. Reported results are the average of multiple measurements.

[0075] Matrix Tensile Strength (MTS)

[0076] To determine the MTS, the sample membranes were cut in the longitudinal and transverse directions using an ASTM D412-Dogbone Die Type F (DD412F). The tensile failure load was measured using an INSTRON® 5500R (Illinois Tool Works Inc., Norwood, MA) tensile tester equipped with flat-face grips and a "200 lb" (approximately 90.72 kg) load cell. The gauge length of the grips was set at 8.26 cm, and a strain rate of 0.847 cm / s or 14.3% / s was used. After placing the sample in the grips, the sample was retracted 1.27 cm to obtain a baseline, and tensile testing was performed at the aforementioned strain rate. Two samples of each condition were tested separately, and the average of the maximum load (i.e., peak force) measurements was used to calculate the MTS. The longitudinal and transverse MTS were calculated using the following equations:

[0077] MTS=(maximum load / cross-sectional area)*(true density of polymer / density of membrane).

[0078] Cleaning Test

[0079] A Kenmore Series 80 washing machine was modified to allow the timer to be set to run the washer for a specified period of time. Wash durability was performed by washing a sample of the laminate for the desired period of time in a modified Kenmore washing machine set on a large volume of cold water and heavy duty cycle without the use of laundry detergent. Once the sample had been washed for the desired period of time, it was removed from the washer and allowed to dry at ambient conditions.

[0080] Suter Examination

[0081] The Suter test method was used to determine whether the samples were liquid resistant, and is generally based on that described in ASTM D 751-00, Standard Test Method for Coated Fabrics (Hydrostatic Resistance Procedure B2).

[0082] The test sample was clamped and sealed between rubber gaskets in a fixture holding the sample so that water could be applied to a specific area. The circular area to which the water was applied was approximately 10.8 centimeters (4.25 inches) in diameter. Water was applied to one side of the sample at a pressure of 0.07 bar (1 psig). In testing of laminates with one textile layer, the pressurized water was incident on the film side.

[0083] The non-pressurized side of the sample was visually observed for signs of water appearing for a period of three minutes. If no water was observed, the sample was deemed to have passed the test and was considered liquid resistant. Values ​​reported were the average of three measurements.

[0084] Example 1

[0085] A polyethylene membrane comprised of polyethylene having a weight average molecular weight of 3,150,000 grams / mole (g / mole), where greater than 30% by weight of the porous polyethylene membrane has a weight average molecular weight greater than 500,000 g / mole, a porosity of 64.9%, and a Gurley number of 68.0 seconds, was laminated to a polyester fabric using a water-impermeable polyurethane adhesive that was applied in a discrete dot pattern using a gravure coating roll such that the polyurethane adhesive covered approximately 35% of the surface area of ​​the membrane.

[0086] The membrane in this two-layer (2L) laminate was gravure coated with a 17 gsm hydrophilic polyurethane prepolymer mixture containing a heat-activated curing agent and sent to an infrared oven for about 20 seconds to activate the curing agent and crosslink the polyurethane. The film was then wound into a roll. The polyurethane-coated 2L laminate was cooled to room temperature and cured.

[0087] A sample of this 2L laminate was then tested for durability in washing. In the first test, a sample of the 2L laminate was placed in a domestic washing machine filled with water only. The washing machine was turned on and allowed to run continuously for 24 hours. The sample was then removed and hung on a rack to dry for 24 hours. The sample was then tested for water leakage in three separate circular areas measuring 4 inches in diameter by applying 1 psi of water pressure to one side of the laminate for three minutes. No water leakage was observed in any of the three areas of the sample. The 2L laminate was returned to the wash and the test repeated until a total of 216 hours of washing was completed. No water leakage was observed in any of the three circular areas when 1 psi of water pressure was applied for three minutes. In the second test, a sample of the 2L laminate was washed in a domestic washing machine and then dried in a domestic dryer. This process was repeated for a total of five complete wash and dry cycles. The sample was then tested for leakage in three separate circular areas measuring 4 inches in diameter by applying 1 psi of water pressure to one side for three minutes. No water leakage was observed in any of the three circular areas. The sample was returned to the wash and the test repeated for an additional 10 wash and dry cycles. After applying 1 psi water pressure for 3 minutes, no water leakage was observed in any of the three circular areas of the sample.

[0088] Comparative example A

[0089] A 30 micron thick polyethylene film with a polyethylene weight average molecular weight of 769,000 g / mol (available from Gelon LIB Co., Ltd, China) was stretched in the machine direction (MD) at 2.25:1 and then in the transverse direction (TD) at 9:1. The resulting PE film had a mass per unit area of ​​2.1 grams / meter. 2(gsm), had a thickness of 10 microns, a Gurley time of 7.5 seconds, and a porosity of 78%. The stretched membrane was then laminated to a polyester fabric (available from Nanya, item number J47P) using a water-impermeable polyurethane adhesive that was applied in a discrete dot pattern using a gravure coating roll. The polyurethane adhesive covered approximately 35% of the membrane surface area. The two-layer (2L) laminate was then allowed to cure in roll form for two days.

[0090] The membrane in this 2L laminate was then gravure coated with a 17 gsm hydrophilic polyurethane prepolymer mixture containing a heat activated curative. The polyurethane coated laminate was then passed through an infrared oven for approximately 20 seconds to activate the curative and crosslink the polyurethane to produce a tack-free surface. The film was then wound into a roll. The roll of polyurethane coated laminate was left in roll form for 2 days to fully cure.

[0091] A sample of this 2L laminate was then tested for durability in washing. In the first test, a sample of the 2L laminate was placed in a domestic washing machine filled with water only. The washing machine was turned on and allowed to run continuously for 24 hours. The sample was then removed and hung on a rack to dry for 24 hours. The sample was then tested for water leakage in three separate circular areas measuring 4 inches in diameter by applying 1 psi water pressure to one side of the laminate for three minutes. Water leakage was observed in all three areas of the sample. In a second test, a sample of the 2L laminate was washed and dried following the procedure described above. This process was repeated for a total of five complete wash and dry cycles. The sample was then tested for leakage in three separate circular areas measuring 4 inches in diameter by applying 1 psi water pressure to one side for three minutes. Water leakage was observed in two of the three circular areas.

[0092] Example 2

[0093] A polyethylene resin having a weight average molecular weight of about 7,000,000 g / mol was obtained from Mitsui Chemicals, Inc., manufactured according to WO2012 / 053261, and made into a membrane according to the process described in U.S. Pat. No. 9,926,416. The resulting membrane had a molecular weight of 2.4 g / m 2 The composite had a mass of 5.1 g / m2 and a porosity of 62.5%. 2 A composite film was produced by coating the membrane with a hydrophilic polyurethane prepolymer mixture of 1000 g / m2 and then heating the film in an infrared oven set at a temperature of 130° C. to activate the curing agent and crosslink the polyurethane. The film was then laminated to a polyester fabric using a water-impermeable polyurethane adhesive to form a two-layer (2L) laminate. The water-impermeable polyurethane adhesive was applied in a discrete dot pattern using a gravure coating roll such that the polyurethane adhesive covered approximately 35% of the membrane surface area.

[0094] A sample of this 2L laminate was then tested according to the Wash Durability Test. The washing machine was turned on and run continuously for 68.5 hours. The sample was then removed and hung on a rack to dry for 24 hours. The sample was then tested for leaks in five separate 4 inch diameter circular areas using the Sooter Test. No leaks were observed in any of the five circular areas. The laminate was placed back in the washing machine and the washing machine was run continuously for 54.75 hours. The laminate was again tested for leaks and no leaks were observed in any of the five circular areas. The laminate was placed back in the washing machine and the washing machine was run continuously for 113.5 hours. The laminate was again tested for leaks and no leaks were observed in any of the five circular areas. The total wash test time was 236.75 hours.

[0095] Comparative example B

[0096] A Columbia Omni-Dry Peak 2 Peak Waterproof Jacket (Columbia Sportswear Company) was purchased. The garment was a 3L laminate, containing an outer textile and an inner textile laminated to a polyethylene membrane. The back of this jacket was cut out to test the wash durability of the laminate by running the washing machine continuously for 15.25 hours. Three separate 4 inch diameter circular areas of the laminate were tested according to the Suter test. These circular areas did not contain any seams. All three circular areas showed multiple water leaks.

Claims

[Claim 1] An article comprising a film, the film comprising: A) a porous polyethylene membrane having a first surface and a second surface, the porous polyethylene membrane comprising: a) 30% by mass or more of the total mass of the porous polyethylene is 0.5 × 10 6 a porous polyethylene having a weight average molecular weight of greater than 100 g / mol; b) the porosity is 40% or more, and c) The Gurley number is less than 200 seconds a porous polyethylene film; B) a hydrophilic polymer that fills at least a portion of the pores of the porous polyethylene; C) a cap layer of the hydrophilic polymer having a thickness of 50 micrometers or less on at least one of the first and second surfaces of the porous polyethylene membrane; An article comprising: