TITLE
REINFORCING SCAFFOLD WITH FLAME RETARDANT HYDROPHILIC COATING
TECHNICAL FIELD OF THE DISCLOSURE
[0001] The present disclosure relates to waterproof, breathable laminates comprising a film layer that are flame resistant and are useful in a variety of applications. The films can be used by themselves or can be laminated to other layers to form multilayer laminates.
BACKGROUND OF THE DISCLOSURE
[0002] Garments and other types of apparel, such as shoes, gloves, and hats often incorporate a waterproof breathable layer to keep a wearer dry in wet conditions. These garments can be formed using laminates of the breathable waterproof layer and one or more textiles. Waterproof breathable films made using expanded PTFE (ePTFE) membranes and hydrophilic polyurethane are currently being used to make GORETEX® textile laminates. The ePTFE membranes are microporous and generally hydrophobic wherein the pore size of the membrane is larger than molecules of water, but the pores are much smaller than individual drops of water. Water vapor is able to pass through the material while water droplets are prevented from passing from one side of the membrane to the other. Protective garments produced using ePTFE also have the advantage that the ePTFE layer is stable at very high temperatures (>300°C). [0003] While ePTFE membranes work well, porous polyurethane membranes have also been developed for use in apparel, but these can lack durability and, in some cases, can be dissolved or otherwise degraded by certain commonly used products, for example, nail polish or bug sprays. Polyurethane membranes can also have limitations in that they melt at relatively low temperatures (compared to ePTFE) and are flammable. Non-ePTFE membranes are often not durable enough for use in protective garments for structural fire-fighting applications. There is a continuing need to produce laminates that have excellent waterproofness and breathability as well as having good temperature stability and durability when an article, such as a garment comprising is using in challenging environments, such as fire-fighting.
SUMMARY OF THE DISCLOSURE
[0004] In a first embodiment, the present disclosure relates to a laminate including: a first textile layer and a film, wherein the film includes: a) a reinforcing scaffold; and b) at least one hydrophilic polymer; and wherein the hydrophilic layer is a polymeric layer and includes one or more flame retardant agents.
[0005] In a second embodiment, the disclosure relates to the laminate of the first embodiment, wherein the first textile layer is positioned on one side of the film.
[0006] In a third embodiment, the disclosure relates to the laminate of any one of the previous embodiments, wherein the reinforcing scaffold is a polymer that is meltable. [0007] In a fourth embodiment, the disclosure relates to the laminate of any one of the previous embodiments, wherein the reinforcing scaffold is a polymer that is flammable.
[0008] In a fifth embodiment, the disclosure relates to the laminate of any one of the previous embodiments, wherein the reinforcing scaffold is a porous polymer, and the porous polymer is polyester, polyamide, polyurethane, polyether, polyolefin, polyether sulfone, polyether ether ketone (PEEK), polyimide, ultrahigh molecular weight polyethylene, or a copolymer or a blend thereof.
[0009] In a sixth embodiment, the disclosure relates to the laminate of any one of the previous embodiments, wherein the hydrophilic polymer is a polyester, a polyether, a polyurethane, ionomer, chitosan, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylic acid or a copolymer or a blend thereof.
[0010] In a seventh embodiment, the disclosure relates to the laminate of any one of the previous embodiments, wherein the hydrophilic polymer fills at least a portion of the pores of the porous polymer.
[0011] In an eighth embodiment, the disclosure relates to the laminate of any one of the previous embodiments, wherein substantially all of the pores in the porous polymer are filled with the hydrophilic polymer. [0012] In a ninth embodiment, the disclosure relates to the laminate of any one of the previous embodiments, wherein the film includes a cap layer of the at least one hydrophilic polymer on one side of the reinforcing scaffold.
[0013] In a tenth embodiment, the disclosure relates to the laminate of any one of the previous embodiments, wherein the weight ratio of the hydrophilic polymer to the reinforcing scaffold is in the range of from 30 to 0.5.
[0014] In a twelfth embodiment, the disclosure relates to the laminate of any one of the previous embodiments, wherein the first textile layer is adhered to one side of the film using one or more adhesives, stitches, welds, or a combination thereof.
[0015] In a thirteenth embodiment, the disclosure relates to the laminate of any one of the previous embodiments, wherein the flame retardant agents are liquid flame retardants, solid flame retardants or a combination thereof.
[0016] In a fourteenth embodiment, the disclosure relates to the laminate of any one of the previous embodiments, wherein the solid flame retardant agents are present only in the cap layer of the film.
[0017] In a fifteenth embodiment, the disclosure relates to the laminate of any one of the previous embodiments, wherein the laminate further includes a second textile layer [0018] In a sixteenth embodiment, the disclosure relates to the laminate of any one of the previous embodiments, wherein the second textile is adhered to the film on a side of the film opposite the first textile layer using one or more adhesives, stitches, welds, or a combination thereof.
[0019] In a seventeenth embodiment, the disclosure relates to the laminate of any one of the previous embodiments, wherein the second textile layer is adhered to the film on a side of the film opposite the first textile layer.
[0020] In an eighteenth embodiment, the disclosure relates to an article including any of the laminates in the previous embodiments.
[0021] The disclosure also relates to a garment including the laminate described herein.
[0022] In some embodiments, a laminate includes a first textile layer; and a film, wherein the film includes: a reinforcing scaffold; and at least one hydrophilic polymer; wherein the at least one hydrophilic polymer includes one or more flame retardant agents.
[0023] In some embodiments, the first textile layer is positioned on one side of the film.
[0024] In some embodiments, the reinforcing scaffold is meltable.
[0025] In some embodiments, the reinforcing scaffold is flammable.
[0026] In some embodiments, the reinforcing scaffold is a porous polymer, and the porous polymer is polyester, polyamide, polyurethane, polyether, polyolefin, polyether sulfone, polyether ether ketone (PEEK), polyimide, ultrahigh molecular weight polyethylene, or a copolymer or a blend thereof.
[0027] In some embodiments, the at least one hydrophilic polymer is a polyester, a polyether, a polyurethane, ionomer, chitosan, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylic acid or a copolymer or a blend thereof.
[0028] In some embodiments, the at least one hydrophilic polymer fills at least a portion of pores of the porous polymer. In some embodiments, substantially all of the pores in the porous polymer are filled with the at least one hydrophilic polymer.
[0029] In some embodiments, the film includes a cap layer of the at least one hydrophilic polymer on one side of the reinforcing scaffold.
[0030] In some embodiments, the one or more flame retardant agents are liquid flame retardants, solid flame retardants, or a combination thereof.
[0031] In some embodiments, the one or more flame retardant agents are a solid flame retardant agent. In some embodiments, the solid flame retardant agent is present only in the cap layer of the at least one hydrophilic polymer.
[0032] In some embodiments, a weight ratio of the at least one hydrophilic polymer to the reinforcing scaffold is in a range of from 30 to 0.5.
[0033] In some embodiments, the at least one hydrophilic polymer further includes an antistatic agent.
[0034] In some embodiments, a first textile layer of the at least one textile layer is adhered to one side of the film using one or more adhesives, stitches, welds, or a combination thereof. In some embodiments, the laminate further includes a second textile layer of the at least one textile layer. In some embodiments, the second textile layer is adhered to the film on a side of the film opposite the first textile layer, using one or more adhesives, stitches, welds, or a combination thereof.
[0035] In some embodiments, any of the laminates described herein is included in an article. In some embodiments, the article is a garment.
[0036] In some embodiments, a laminate includes a first textile layer; and a film, wherein the film includes: a reinforcing scaffold; and at least one hydrophilic polymer; wherein the at least one hydrophilic polymer includes a combination of a liquid flame retardant agent and a solid flame retardant agent.
[0037] In some embodiments, the first textile layer is positioned on one side of the film.
[0038] In some embodiments, the reinforcing scaffold is meltable.
[0039] In some embodiments, the reinforcing scaffold is flammable.
[0040] In some embodiments, the reinforcing scaffold is a porous polymer, and the porous polymer is polyester, polyamide, polyurethane, polyether, polyolefin, polyether sulfone, polyether ether ketone (PEEK), polyimide, ultrahigh molecular weight polyethylene, or a copolymer or a blend thereof.
[0041] In some embodiments, the at least one hydrophilic polymer is a polyester, a polyether, a polyurethane, ionomer, chitosan, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylic acid or a copolymer or a blend thereof.
[0042] In some embodiments, the at least one hydrophilic polymer fills at least a portion of pores of the porous polymer. In some embodiments, substantially all of the pores in the porous polymer are filled with the at least one hydrophilic polymer.
[0043] In some embodiments, the film includes a cap layer of the at least one hydrophilic polymer on one side of the reinforcing scaffold. In some embodiments, the solid flame retardant agent is present only in the cap layer of the at least one hydrophilic polymer.
[0044] In some embodiments, a weight ratio of the at least one hydrophilic polymer to the reinforcing scaffold is in a range of from 30 to 0.5.
[0045] In some embodiments, the at least one hydrophilic polymer further includes an antistatic agent.
[0046] In some embodiments, a first textile layer of the at least one textile layer is adhered to one side of the film using one or more adhesives, stitches, welds, or a combination thereof. In some embodiments, the laminate further includes a second textile layer of the at least one textile layer. In some embodiments, the second textile layer is adhered to the film on a side of the film opposite the first textile layer, using one or more adhesives, stitches, welds, or a combination thereof.
[0047] In some embodiments, a laminate includes a first textile layer; and a film, wherein the film includes: a. a reinforcing scaffold comprising ultrahigh molecular weight polyethylene; and b. at least one hydrophilic polymer, wherein the at least one hydrophilic polymer comprises a mixture of a phosphoric acid, triethyl ester polymer and melamine polyphosphate.
[0048] In some embodiments, any of the laminates described herein is included in an article. In some embodiments, the article is a garment.
BRIEF DESCRIPTION OF THE FIGURES
[0049] Figure 1 is a cross-sectional representation of an exemplary film of the disclosure.
DETAILED DESCRIPTION
[0050] The disclosures of all cited patent and non-patent literature are incorporated herein by reference in their entirety.
[0051] As used herein, the term "embodiment" or "disclosure" is not meant to be limiting, but applies generally to any of the embodiments defined in the claims or described herein. These terms are used interchangeably herein.
[0052] Unless otherwise disclosed, the terms "a" and "an" as used herein are intended to encompass one or more (i.e. , at least one) of a referenced feature.
[0053] The features and advantages of the present disclosure will be more readily understood by those of ordinary skill in the art from reading the following detailed description. It is to be appreciated that certain features of the disclosure, which are, for clarity, described above and below in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the disclosure that are, for brevity, described as a combination in the context of a single embodiment, may also be provided separately or in any sub-combination. In addition, references to the singular may also include the plural (for example, "a" and "an" may refer to one or more) unless the context specifically states otherwise.
[0054] The use of numerical values in the various ranges specified in this application, unless expressly indicated otherwise, are stated as approximations as though the minimum and maximum values within the stated ranges were both preceded by the word "about". In this manner, slight variations above and below the stated ranges can be used to achieve substantially the same results as values within the ranges. Also, the disclosure of these ranges is intended as a continuous range including each and every value between the minimum and maximum values.
[0055] As used herein, the term “reinforcing scaffold” or “membrane” means a meltable and/or flammable polymer in the form of an essentially two-dimensional sheet or membrane, wherein the length and the width are both much greater than the thickness, for example both the length and the width are at least 100 times the thickness. In some embodiments, the reinforcing scaffold is a porous polymer having a structure of pores that allows, for example, water vapor to pass through the thickness of the reinforcing scaffold without liquid water being able to penetrate from one side of the reinforcing scaffold to the other. On average, the pore size is on the order of several nanometers to approximately one micrometer.
[0056] The term “film” means a reinforcing scaffold wherein at least a portion of the pores have been filled with a polymer such that the flow of gases or liquids does not occur through open pore channels in the reinforcing scaffold. In some embodiments the pores of the reinforcing scaffold are substantially completely filled with a polymer. In some embodiments, the polymer at least partially filling the pores can be a hydrophilic polymer.
[0057] The term “hydrophilic polymer” refers to a polymer that can allow substantial amounts of water to be transferred through a film of the polymer by absorbing water on one side of the film where the water concentration is higher, and desorbing or evaporating it on the opposite side of the film where the water vapor concentration is lower. In some embodiments, a layer of the hydrophilic polymer that is 10 micrometers thick can have a moisture vapor transmission rate of greater than or equal to 2,500 g/meter2/day, or greater than or equal to 5,000 g/meter2/day, or greater than or equal to 10,000 g/meter2/day.
[0058] The term “meltable” means a polymer having a melting or softening point as determined by differential scanning calorimetry (DSC) of less than 300°C or in other embodiments less than 280°C. The term “flammable” means a material that meets the definition of flammable when tested according to the ASTM D6413 Vertical Flame test. [0059] The phrases "porous polyethylene membrane” and “polyethylene membrane” are used interchangeably throughout the specification. Unless specifically stated otherwise, both phrases mean a reinforcing scaffold comprising or consisting essentially of porous polyethylene membrane having a) molecular weight distribution such that greater than or equal to 30% by weight of the porous polyethylene has a weight average molecular weight greater than 0.5x106 g/mol; b) a porosity of at least 40%; and c) a Gurley number of less than 200 seconds or less than 100 seconds. Under magnification, the porous polyethylene membrane shows a fibrillated structure of polyethylene fibrils, and with sufficient magnification it is possible to see one or more polyethylene fibrils, optionally three or more of the fibrils can be interconnected by one or more intersections of the three or more fibrils.
[0060] As used herein, the term “polyethylene” means a polyethylene polymer having less than 5 percent by weight of one or more comonomers. In some embodiments, the polyethylene is free from any fluorine containing comonomers, and, in still further embodiments, the polyethylene is polyethylene homopolymer.
[0061] The present disclosure relates to a laminate comprising a first textile layer and a film, wherein the film comprises a) a reinforcing scaffold; and b) a hydrophilic polymer wherein the hydrophilic layer is a polymeric layer and comprises one or more flame retardant agents. The film will not leak due to contamination by oils, detergents, or other contact angle reducing materials and as such it is waterproof. Furthermore, articles comprising the film have surprising flame resistance and greater durability in the field and in the wash than other non-air permeable hydrophilic films that do not include the reinforcing scaffold as a structural support. [0062] The reinforcing scaffold is a polymer that is flammable. In some embodiments, the reinforcing scaffold is a polymer that is meltable. In still further embodiments, the reinforcing scaffold is a polymer that is meltable and flammable. The reinforcing scaffold is a polymer, preferably a porous polymer, and the polymer is polyester, polyamide, polyurethane, polyether, polyolefin, polyether sulfone, polyether ether ketone (PEEK), polyimide, ultrahigh molecular weight polyethylene, or a copolymer or a blend thereof. Suitable polymers listed above typically have a melting point or a softening point below 300°C or below 280°C and/or are generally considered to be flammable according to the definitions provided above. The reinforcing scaffold can be a thermoplastic polymer having a melting point below 300°C or below 280°C or a crosslinked polymer having a softening point below 300°C or below 280°C. Due to their flammability or ability to sustain flames when ignited, meltable and/or flammable polymers are generally considered to be unsuitable for use in fire-fighting garments. [0063] In some embodiments, the reinforcing scaffold is a porous ultrahigh molecular weight polyethylene. As used herein, the phrase “ultrahigh molecular weight polyethylene” or “UHMWPE” means a porous polyethylene having a molecular weight distribution wherein greater than or equal to 30% by weight of the polyethylene has a weight average molecular weight of greater than 0.5x106 grams per mole (g/mol). In some embodiments, the porous polyethylene has a molecular weight distribution wherein greater than or equal to 30% by weight of the polyethylene having a weight average molecular weight of greater than 0.75x106 g/mol. In still further embodiments, the porous polyethylene has a molecular weight distribution wherein greater than or equal to 30% by weight of the polyethylene having a weight average molecular weight of greater than 1 .0x106 g/mol. In still further embodiments, greater than or equal to 40% by weight of the polyethylene has a weight average molecular weight of greater than 0.5x106 grams per mole (g/mol) or greater than or equal to 50% by weight of the polyethylene has a weight average molecular weight of greater than 0.5x106 grams per mole (g/mol). All of the percentages by weight are based on the total weight of the porous polyethylene membrane. In some embodiments, the porous polyethylene has a weight average molecular weight of greater than 750,000 g/mol. In still further embodiments, the porous polyethylene has a weight average molecular weight of greater than 1 ,000,000 g/mol. In still further embodiments, the polyethylene has a weight average molecular weight of greater than 1 ,500,000 grams per mole or greater than to 1 ,750,000 grams per mole. In still further embodiments, the polyethylene has a weight average molecular weight of greater than 2,000,000 grams per mole, 2,250,000 grams per mole, 2,500,000 grams per mole, 2,750,000 grams per mole, 3,000,000 grams per mole, 3,250,000 grams per mole, 3,500,000 grams per mole, 3,750,000 grams per mole, 4,000,000 grams per mole, 5,000,000 grams per mole or greater than
8,000,000 grams per mole. WO20/029328 and/or W020/029331 are herein incorporated by reference and describe embodiments of ultrahigh molecular weight polyethylene materials that can be used as the reinforcing scaffold.
[0064] The reinforcing scaffold has a porosity of at least 40%. In some embodiments, the porosity of the reinforcing scaffold can be at least 50% or at least 60% or at least 70% or at least 80%. The porosity, <|>, of the reinforcing scaffold can be calculated by measuring the mass per unit area of the membrane, MPA, and the thickness of the membrane, t, and using the relationship = (1- MPA/(t*p))*100, where p is the density of the polymer. The reinforcing scaffold can also have a Gurley of less than 200 seconds or less than 100 seconds or less than or equal to 90 seconds or less than or equal to 80 seconds or less than or equal to 70 seconds or less than or equal to 60 seconds or less than or equal to 50 seconds or less than or equal to 40 seconds or less than 10 seconds.
[0065] The reinforcing scaffold can have a relatively light weight, for example, less than or equal to 10 grams per square meter (gsm). In other embodiments, the reinforcing scaffold can have a weight of less than or equal to 9 gsm or less than or equal to 8 gsm or less than or equal to 7 gsm or less than or equal to 6 gsm or less than or equal to 5 gsm or less than or equal to 4 gsm or less than or equal to 3 gsm or less than or equal to 2 gsm.
[0066] In some embodiments, the reinforcing scaffold can be colored or uncolored. The use of a reinforcing scaffold can provide a valuable aesthetic quality to the film and articles comprising the film, especially when the reinforcing scaffold is visible in the article. Any of the known colorization methods can be used. For example, the reinforcing scaffold can be pigmented throughout its bulk via the addition of pigments or dyes during the formation process. In other embodiments, the reinforcing scaffold can be colorized after formation via known printing and dyeing processes or by adding pigments or dyes to the hydrophilic polymer. In still further embodiments, the reinforcing scaffold can be free from or essentially free from any added color and color can be added at one or more steps during the film formation processes described herein. [0067] The film also comprises b) at least one hydrophilic polymer. The hydrophilic polymer can fill at least a portion of the pores of the reinforcing scaffold. The phrase “fills at least a portion of the pores” means that the hydrophilic polymer is imbibed into the pores of the reinforcing scaffold and fills the pores to the point that no airflow can be determined through the area of the film containing the hydrophilic polymer, as evidenced by a Gurley number of greater than or equal to 1000 seconds. In other words, the hydrophilic polymer is not simply a coating on the walls of the reinforcing scaffold that define the pores. While some voids may be present, it is thought that the hydrophilic polymer forms a continuous layer within the area of the reinforcing scaffold to which the hydrophilic polymer is applied. In other embodiments, the hydrophilic polymer forms a continuous layer free from or essentially free from any voids within the area of the reinforcing scaffold to which the hydrophilic polymer is applied. In still further embodiments, substantially all of the pores of the reinforcing scaffold are filled with the hydrophilic polymer.
[0068] The reinforcing scaffold has a first side and a second side. The hydrophilic polymer can be applied to the first side of the reinforcing scaffold and the hydrophilic polymer can permeate at least a portion of the pores to form the film, resulting in filling at least a portion of the pores of the reinforcing scaffold. The first side of the reinforcing scaffold can also comprise a cap layer of the hydrophilic polymer on the exterior of the reinforcing scaffold. The cap layer is an amount of the hydrophilic polymer that is in excess of the amount of hydrophilic polymer needed to fill at least a portion of the pores of the reinforcing scaffold. Referring to Figure 1 , the film 10 is comprised of a reinforcing scaffold 20 and a hydrophilic polymer 30. The hydrophilic polymer 30 fills the pores of the reinforcing scaffold 20 and forms a cap layer 40 on one surface of the reinforcing scaffold 20. The thickness of the cap layer 40 on the first side of the reinforcing scaffold 20 has essentially no upper limit. However, if the cap layer 40 is too thick, then the beneficial properties of the reinforcing scaffold 20 cannot be realized. Therefore, the upper limit of the cap layer 40 is about 50 micrometers. In some embodiments, the cap layer 40 of the hydrophilic polymer 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 reinforcing scaffold 20. In some embodiments, the cap layer 40 of the hydrophilic polymer can be up to about 10 micrometers thick on the first surface of the reinforcing scaffold 20. In other embodiments, the cap layer 40 on the first side of the reinforcing scaffold 20 is less than or equal to 10 micrometers thick, or less than or equal to 8 micrometers or less than or equal to 6 micrometers or less than or equal to 4 micrometers or less than or equal to 2 micrometers. In still further embodiments, no cap layer 40 of the hydrophilic polymer is present on the first surface of the reinforcing scaffold 20. The second side of the reinforcing scaffold 20 can be essentially free from any of the hydrophilic polymer on the surface, for example, no hydrophilic polymer of a thickness more than 1 micrometer above the surface of the reinforcing scaffold 20 that is opposite the cap layer 40. In some embodiments, less than the entire thickness of the reinforcing scaffold 20 is filled with the hydrophilic polymer, for example, less than or equal to 90% of the thickness of the reinforcing scaffold 20 may be filled with the hydrophilic polymer, with the proviso that enough hydrophilic polymer is imbibed so as to provide the film with a Gurley number of greater than or equal to 1000 seconds. In other embodiments, essentially the entire thickness of the porous reinforcing scaffold 20 is filled with the hydrophilic polymer. As used herein, the phrase “essentially the entire thickness” means that at least 90% of the thickness of the reinforcing scaffold 20 is filled with the hydrophilic polymer.
[0069] In other embodiments, a hydrophilic polymer can be applied to the second side of the reinforcing scaffold as well as the first side (not shown). The hydrophilic polymer applied to the second side may be the same or different from the hydrophilic polymer applied to the first side. In still further embodiments, the film can be a composite film wherein a hydrophilic polymer is applied to a first side of a first reinforcing scaffold with a sufficient amount of the hydrophilic polymer applied to the first side of the reinforcing scaffold to form a cap layer and a second reinforcing scaffold that may be the same or different as the first reinforcing scaffold, is thereafter bonded to the film via the cap layer of the hydrophilic polymer. This can result in a 3-layer structure having 2 reinforcing scaffolds adhered to one another with the hydrophilic polymer as the layer in between the two reinforcing scaffolds. If desired, an additional layer or layers of hydrophilic polymer may be applied to one or both of the exterior sides of the film.
[0070] In some embodiments, the hydrophilic polymer may be applied to the reinforcing scaffold in a continuous manner, so that essentially 100 percent of the surface area of the reinforcing scaffold comprises the hydrophilic polymer. As used in this context, the term “continuous” means that the full width or nearly the full width of the reinforcing scaffold is coated with the hydrophilic polymer. It should be noted that in many coating processes, the edges of a roll of material may not be coated due to frames or dams at the edges not allowing the entire width of the membrane to be coated. In other embodiments, the hydrophilic polymer may be applied to the reinforcing scaffold in a discontinuous manner. As used in this context, the term “discontinuous” means that less than 100 percent of the surface area of the reinforcing scaffold is coated with the hydrophilic polymer and that portions of the non-edge areas of the reinforcing scaffold do not contain the hydrophilic polymer. For example, a hydrophilic polymer applied to the reinforcing scaffold as a series of dots or as a grid of intersecting lines are to be considered as discontinuous coatings. The area percent of the reinforcing scaffold that is filled with the hydrophilic polymer can be in the range of from greater than or equal to 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 to less than 100 percent or from 70 to less than 100 percent or from 80 to less than 100 percent or from 90 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 nonrandom pattern of dots, polygons, parallel lines, intersecting lines, straight lines, curved lines or any combination thereof in order to provide the desired percent by area coverage. If oleophobicity is desired in such films, it may be desirable in certain embodiments to include an oleophobic coating, as described otherwise herein.
[0071] As a weight ratio, the film can have a ratio of the weight of the hydrophilic polymer to the weight of the reinforcing scaffold in the range of from 30.0 to 0.5. In other embodiments, the weight ratio of the hydrophilic polymer to the reinforcing scaffold 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 weight ratio in between those numbers.
[0072] Suitable hydrophilic polymers can include, for example, polyester, polyurethane, polyether, ionomer, chitosan, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylic acid or a copolymer or a blend thereof. In other embodiments, nearly any suitable hydrophilic polymer could be used provided that the hydrophilic polymer is capable of having a moisture vapor transmission rate of greater than or equal to 2,500 grams/meter2/day, or greater than 5,000 grams/meter2/day or greater than or equal to 10,000 grams/meter2/day. The hydrophilic polymer can be a thermoplastic or a crosslinkable polymer. In some embodiments, the hydrophilic polymer is a polyurethane and in further embodiments, the polyurethane is a crosslinked polyurethane or copolymer. Suitable polyurethane copolymers can be, for example, polyesterurethanes, polyetherurethanes or polyether-polyesterurethanes.
[0073] In any of the embodiments above, the hydrophilic polymer comprises one or more flame retardant agents. The flame retardant agents can be liquid flame retardant agents, solid flame retardant agents, or a combination thereof. In some embodiments, the hydrophilic polymer comprises a liquid and a solid flame retardant agent. The flame retardant agent can be one or more of aluminum oxide, aluminum hydroxide (ATH), magnesium hydroxide (MDH), huntite, hydromagnesite, red phosphorus, boron borates, organochlorines, organobromines, antimony trioxide, antimony pentoxide, sodium antimonate, organophosphates, tris(2,3-dibromopropyl) phosphate, tetrabromobisphenol A (TBBPA), 2,2-bis(bromomethyl)-1 ,3-propanediol (BBMP), triphenylphosphate (TPP), tris(1,3-dichloro-2-propyl)phosphate (TDCPP), tris(2- chloroethyl)phosphate (TCEP), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (TBB), bis(2- ethylhexyl)3,4,5,6-tetrabromophthalate (TBPH), hexabromocyclododecane (HBCD), ammonium phosphate, ammonium sulfate, triisopropyl phosphate, diethyl ethyl phosphate, (tris-chloroethyl) phosphate, triphenyl phosphate, tris-(2-chloroethylhexyl) phosphate, tricresyl phosphate, mono-, bis- and tri-(isopropylphenyl) phosphate, triisopropylphenyl phosphate, resorcinol-bis-(diphenyl phosphate), bisphenol-A-bis- (diphenyl)phosphate, phosphoric acid, phosphorus oxide, melamine, melamine phosphate, melamine polyphosphate, melamine cyanurate, melamine poly-zinc, aluminum phosphate, melamine based hindered amine light stabilizers, ethylenediamine phosphate, cyclic phosphonates, aromatic phosphonates, aliphatic phosphate esters, chloroparafin, hexabromobenzol, tetrabromophthalic anhydride or a combination thereof. In some embodiments, the hydrophilic polymer comprises one or more flame retardant agents and an antistatic agent, for example, carbon black, metal fibers or a combination thereof.
[0074] The flame retardant agent(s) can be used in amounts ranging from 10 to 60 percent by weight, wherein the percentage by weight is based on the total weight of the hydrophilic polymer and the flame retardant agent. In other embodiments, the flame retardant agent can be present in amounts ranging from 15 to 55 percent by weight, or from 15 to 50 percent by weight, or from 15 to 45 percent by weight, or from 20 to 45 percent by weight, or from 25 to 45 percent by weight, wherein the percentage by weight are based on the total weight of the hydrophilic polymer and the flame retardant agent. In some embodiments, the FR agent is a mixture of a solid flame retardant agent and a liquid flame retardant agent, for example, a mixture of FYROL® PNX LE (phosphoric acid, triethyl ester polymer) and melamine polyphosphate.
[0075] The flame retardant agents can be added to the hydrophilic polymer prior to adding the hydrophilic polymer to the reinforcing scaffold. The hydrophilic polymer comprising the one or more flame retardant agents can then be imbibed within the pores of the reinforcing scaffold, as in the case of the flame retardant agent being a liquid or a solid particle small enough to penetrate the pores of the reinforcing scaffold. In other embodiments, wherein the flame retardant agent comprises solid particles that are relatively larger compared to the size of the pores of the reinforcing scaffold, any solid flame retardant particles are present in the cap layer on one surface of the reinforcing scaffold. In some embodiments, two flame retardant agents are used, the first being a liquid flame retardant agent and the second being a solid flame retardant agent. The liquid flame retardant agent is dispersed throughout the thickness of the hydrophilic polymer 30, including being dispersed within the pores of the reinforcing scaffold, and the solid flame retardant particles 50 are present only within the cap layer 40. This embodiment is represented by Figure 1 , where the film 10 is shown with at least one solid flame retardant particle 50, wherein the particles of the solid flame retardant agent 50 are larger than the pore size of the reinforcing scaffold 20 and therefore, are present only in the cap layer 40 of the hydrophilic polymer 30.
[0076] The resulting film comprising the reinforcing scaffold and the hydrophilic polymer can have a moisture vapor transmission rate (MVTR) of greater than or equal to 2500 grams/meter2/day (g/m2/day); a weight of less than 30 grams/meter2 and, optionally, a Gurley of greater than or equal to 1000 seconds. In order to be breathable, i.e. , moisture vapor is able to be transported from one side of the film to the other without liquid water moving through the film, the MVTR should be greater than or equal to 2500 g/m2/day. In other embodiments, the film can have an MVTR of greater than or equal to 3000 g/m2/day, greater than or equal to 3500 g/m2/day, greater than or equal to 4000 g/m2/day, greater than or equal to 4500 g/m2/day, greater than or equal to 5000 g/m2/day, greater than or equal to 5500 g/m2/day, greater than or equal to 6000 g/m2/day, greater than or equal to 6500 g/m2/day, greater than or equal to 7000 g/m2/day, greater than or equal to 7500 g/m2/day, greater than or equal to 8000 g/m2/day, greater than or equal to 8500 g/m2/day, greater than or equal to 9000 g/m2/day, greater than or equal to 9500 g/m2/day, or greater than or equal to 10,000 g/m2/day.
[0077] The film can also have a ratio of matrix tensile strengths in two orthogonal directions in the range of from 0.5 to 2.0. In other embodiments, the ratio of tensile strengths in two orthogonal directions can be in the range of from 0.7 to 1.4. In still further embodiments, the ratio of tensile strengths can 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 in between those two numbers. The difference in tensile strength in the two orthogonal directions relates to differences in the total strain applied in the two directions during the membrane manufacturing process.
[0078] The film can also be contamination resistant due to the presence of the hydrophilic polymer filling voids in at least a portion of the thickness of the reinforcing scaffold, thereby forming a continuous layer free from voids in that portion of the reinforcing scaffold. Contamination resistant as used herein means that the films do not become contaminated with sweat, sebum or oils thereby reducing the waterproofness over time. If at least a portion of the pores of the reinforcing scaffold remain unfilled, then an oleophobic coating on the walls of the unfilled pores can provide contamination resistance to the unfilled pores.
[0079] The laminate also comprises a textile layer In some embodiments, the textile layer is a first textile layer. The first textile layer can be positioned on one side of the film, for example, immediately adjacent to the cap layer or on a side opposite the cap layer. The laminate can also comprise a second textile layer. The second textile layer can be the same or different from the first textile layer and can be positioned on the film on the opposite side of the first textile layer. Each of the first and/or the second textile can independently be a knit textile, a woven textile or a nonwoven textile. Each of the first textile layer and/or the second textile layer can independently be a natural and/or synthetic textile. Suitable natural and/or synthetic textiles can include for example, cotton, wool, silk, jute, polyamide, polyester, acrylic, aramid, viscose, cellulose, rayon, carbon fiber, or a combination thereof. Optionally, any of the previously listed textiles can be treated with one or more flame retardant agents. In some embodiments, the first textile layer, the second textile or both the first and the second textile layers comprise flame retardant textile layers. Suitable flame retardant textile layers can comprise, for example, aramids, p-aramid, m-aramid, polyamide-imide, polybenzoxazole, polybenzimidazole, flame retardant (FR) cotton, FR viscose, or combinations thereof. In some embodiments, the laminate comprises a first textile layer that is an aramid knit and a second textile layer that is an aramid woven textile. In some embodiments, the first textile and/or the second textile can be treated with a durable water repellant composition. The durable water repellant composition can be a fluorine-containing composition or can be a composition that is free from fluorinated compounds.
[0080] Lamination techniques are well known in the art and can include, for example, adhesive lamination, heat bonding, welding, and stitching. In cases wherein a waterproof laminate is needed, stitching may not be desirable, unless care is taken to ensure that the stitch holes are made impenetrable to liquid water, for example, by sealing the stitch holes using seam tape. In some embodiments, the lamination is accomplished via adhesive lamination wherein an adhesive is applied to one or more of the layers to be joined together and the layers are subsequently placed together, optionally with heat and/or pressure, for example, via a nip roller. The adhesive can be applied to the film layer, to the textile layer or to both the film and the textile layer. The adhesive can be applied in a discontinuous manner, for example, a series of adhesive dots, shapes, lines or a combination thereof. In other embodiments, the adhesive can be applied as a continuous layer of adhesive. The adhesive composition can in certain embodiments be a thermoplastic adhesive or a crosslinkable adhesive. In still further embodiments, the hydrophilic polymer can be used as the adhesive material for the formation of the laminate. For example, after application of the hydrophilic polymer to one side of the reinforcing scaffold 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 in order to insure that the hydrophilic polymer sufficiently contacts and adheres to the textile. If the hydrophilic polymer is used as the adhesive for the laminate, then the curing step for 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 step to create the laminate. In other embodiments, one or more rollers can provide the necessary pressure and/or heat to accomplish the same tasks, for example, in a continuous manner.
[0081] In those embodiments where the adhesive is applied in a discontinuous manner, the adhesive can be applied as dots, line, grids, or a combination thereof. In a discontinuous application, the adhesive is applied so that it covers less than 100% of the area of the film layer or of the first textile layer. In some embodiments, the discontinuous adhesive can be applied in the range of from 15% to 60% of the total area of the film layer or of the first textile layer. In still further embodiments, the adhesive can be applied to cover in the range of from 15% to 50% or from 15% to 40% or from 15% to 30% or from 20% to 30% of the total area of the film layer or of the first textile layer. In embodiments where the second textile layer is present, the discontinuous adhesive can be applied in the range of from 15% to 60% of the total area of the film layer or of the second textile layer. In still further embodiments, the adhesive can be applied to cover in the range of from 15% to 50% or from 15% to 40% or from 15% to 35% or from 20% to 35% of the total area of the film layer or of the second textile layer.
[0082] In some embodiments, the laminates can be produced in a stepwise manner wherein the first or the second textile layer is adhered to the film and at a later time, for example, seconds, minutes, days, or a longer time period, the remaining textile layer is adhered. In other embodiments, the laminates can be produced in a continuous process, wherein the first and/or second textile layer is adhered to one side of the film, and the remaining textile layer is adhered at the same time or very shortly thereafter. The adhesive can optionally comprise FR agents. Application of the adhesive to the film or to the textile layer(s) can be done in a continuous or a discontinuous manner. Where the breathability of the laminate is important, the adhesive can be applied in a discontinuous manner, for example, as a series of dots (or other shapes), or as a series of spaced apart lines or grids.
[0083] Due to the high strength of the film, any of the textile or materials listed above and having a relatively low mass can be used to make the laminate. In some embodiments, the laminate can include a relatively low mass textile having a basis weight in the range of from 5 grams/meter2 to 30 grams/meter2 (gsm). In other embodiments, the textile can have a mass 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 or 30 gsm or any value in between two of those values. While relatively low mass textiles can be used, textiles having a weight of 30 gsm or greater can also be used. For example, relatively high mass textiles having a mass of as high as 500 gsm could be used.
[0084] Laminates having stretch and recovery properties can be produced according to known methods. For example, the methods taught in US 4443511 , US 9950504, US 9126390, US 9233520, US 9238344, WO 2018/67529, the contents of which are incorporated herein by reference in their entireties, all teach methods for imparting stretch in prior membranes and laminate constructions, and these teachings can be adapted to provide stretch into laminates comprising a film(s) of this disclosure.
[0085] The laminate as described above can be used to produce an article. In some embodiments, the article can be a garment, a tent, an enclosure, a protective enclosure, a bag, a backpack, a cover, a blanket, or a multilayer laminate for use in a textile application, automotive seats, drapes, curtains, furnishings, etc. The garment can be a jacket, a coat, a shirt, pants, a glove, a hat, a shoe, coveralls or at least a portion thereof. Many articles are made from multiple panels that are sewn or otherwise adhered together to form the finished product. Therefore, “at least a portion of” an article means that at least one panel or part of a panel comprises the laminate. The articles and garments can be produced so that the laminate is on the outside of the garment, on the inside of the garment or wherein the laminate is the middle layer of the garment. One advantage to articles and garments comprising the disclosed laminate is their wash durability. Another advantage of the garments is that the garments can be waterproof and breathable.
[0086] The present disclosure also relates to an article comprising the laminate. 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 an article comprising the disclosed laminate can be washed according to the Wash Durability Testing procedure disclosed herein for at least 15 hours and the laminate will be waterproof as determined according to the Suter test described herein. In other embodiments, the articles remain wash durable after washing for at least 50 hours, or at least 100 hours. In some embodiments, the articles did not develop leaks after over 200 hours of wash testing. The article can also be waterproof and breathable.
Examples
[0087] Test Methods
[0088] Molecular Weight
[0089] Molecular weight determinations were performed according to the procedures given by Mead, D. W., Determination of Molecular Weight Distributions of Linear Flexible Polymers from Linear Viscoelastic Material Functions, Journal of Rheology 1994, 38(6): 1797-1827.
[0090] Porosity
[0091] Porosity was expressed in percent porosity and was determined by subtracting the quotient of the average density of the porous polyethylene membrane and that of the true density of the polymer from 1 , then multiplying that value by 100. For the purposes of this calculation, the true density of polyethylene was taken to be 0.94 grams/cubic centimeter. The density of a sample was calculated by dividing the mass/area of a sample by its thickness.
[0092] Moisture Vapor Transmission Rate Test Protocol (MVTR)
[0093] MVTR is measured according to DIN EN ISO 15496 (2004). As this is a standard test used in the textile industry, reference is made to the detailed description of the MVTR test disclosed in DIN EN ISO 15496 (2004). For a description of the MVTR test, see also WO 90/04175 A1.
[0094] The basic principles are summarized as follows. The sample to be tested together with a highly water vapor permeable, but waterproof microporous membrane is inserted in an annular sample support. Then, the support is immersed in water for 15 minutes (deionized water at 23°C) such that the membrane contacts the water. A cup is filled with a saturated solution of potassium acetate in water such as to produce 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 cup including the potassium acetate solution and the second membrane is weighed and then placed on top of the sample support such that the second membrane contacts the sample. This leads to a transfer of water vapor through the sample from the side of the water into the cup with the potassium acetate. After 15 minutes, the cup with the potassium acetate is removed and its weight is determined. The same procedure is carried out with the first and second membranes, but without the sample, in order to determine moisture vapor permeability of the test setup without the sample. Then, the MVTR of the sample can be determined from the difference of both measurements, also considering the influence of the two additional microporous membranes.
[0095] The moisture vapor transmission rate (MVTR) of the laminate according to the invention was measured in accordance with EN ISO 15496 (2004) and is expressed in g/m2/24hr. In order to be considered as water vapor permeable as used herein, the laminate should generally have a water vapor permeability of at least 3000 g/m2/24hr, preferably at least 8000 g/m2/24hr and more preferably at least 12000 g/m2/24hr. MVTR values may be as high as 20000 g/m2/24hr.
[0096] Gurley [0097] The Gurley air flow test measures the time in seconds for 100 cm3 of air to flow through a 6.45 cm2 sample at 12.4 cm of water pressure. The samples were measured in a Gurley Densometer Model 4110 Automatic Densometer equipped with a Gurley Model 4320 automated digital timer. The reported results are the average of multiple measurements.
[0098] Matrix Tensile Strength (MTS)
[0099] To determine MTS, a sample membrane was cut in the longitudinal and transverse directions using an ASTM D412-Dogbone Die Type F (DD412F). Tensile break load was measured using an INSTRON® 5500R (Illinois Tool Works Inc., Norwood, MA) tensile test machine equipped with flat-faced grips and a “200 lb” (-90.72 kg) load cell. The gauge length for the grips was set to 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 followed by a tensile test at the aforementioned strain rate. Two samples for each condition were tested individually and the average of the maximum load (/.e., the peak force) measurements was used for the MTS calculation. The longitudinal and transverse MTS were calculated using the following equation:
[0100] MTS = (maximum load/cross-sectional area)*(polymer true density/density of the membrane).
[0101] Wash Testing
[0102] A Kenmore Series 80 washing machine was modified so that the timer could be set to allow the machine to run for a designated time. Wash durability was performed by washing samples of the laminates without any laundry detergent in the modified Kenmore washing machine set to a large load, cold water and set on the heavy duty cycle for the desired lengths of time. Once the sample has been washed for the desired length of time, it is removed from the washer and dried at ambient conditions.
[0103] Suter Testing
[0104] The Suter Test Method was used to determine if a sample was liquid-proof. This procedure is based generally on the description in ASTM D 751 -00, Standard Test Methods for Coated Fabrics (Hydrostatic Resistance Procedure B2). [0105] The test sample was clamped and sealed between rubber gaskets in a fixture that held the sample so that water could be applied to a specific area. The circular area to which water was applied was approximately 10.8 centimeters (4.25 inches) in diameter. The water was applied at a pressure of 0.07 bar (1 psig) to one side of the sample. In testing laminates with one textile layer the pressurized water was incident upon the film side.
[0106] The unpressurized side of the sample was observed visually for any sign of water appearing for 3 minutes. If no water was observed the sample was deemed to have passed the test and was considered liquid-proof. The reported values were the average of three measurements.
[0107] Preparation of Hydrophilic Polymer #1
[0108] A hydrophilic polyurethane composition was prepared according to the teachings of US 4194041 . To 70 parts by weight (pbw) hydrophilic polymer, was added 20 pbw FYROL® PNX flame retardant (available from ICL, St. Louis, Missouri) and 10 pbw melamine polyphosphate (available from Century Multech, Inc, Queens, New York) and less than 2 pbw of an antioxidant.
[0109] Preparation of Hydrophilic Polymer #2
[0110] A hydrophilic polyurethane composition was prepared according to the teachings of US 4194041 . To this hydrophilic polymer, was added TiO2 and aluminum flakes.
[0111] Preparation of Film #1
[0112] A film comprising a porous ultrahigh molecular weight polyethylene and Hydrophilic Polymer #1 was prepared according to the teaching of US 2021/0317276 to form a film with a cap layer of the Hydrophilic Polymer #1.
[0113] Preparation of Comparative Film A
[0114] A film comprising a porous ultrahigh molecular weight polyethylene and Hydrophilic Polymer #2 was prepared according to the teaching of US 2021/0317276 to form a film with a cap layer of Hydrophilic Polymer #2.
[0115] Preparation of FR Adhesive #1 [0116] A flame retardant adhesive was prepared by first forming a resin according to commonly owned U.S. Patent No. 4,532,316 and adding into the reactor a phosphorus- based flame retardant material, in an amount of about 20% by weight.
[0117] Preparation of Laminate #1
[0118] Dots of FR Adhesive #1 were applied to Film #1 using a gravure roll. After the application of the adhesive, a NOMEX® nonwoven textile (90-95gsm) (available from Lydall Gutsche GmbH, Fulda, Germany) was placed onto the adhesive dots to form a precursor laminate. A continuous layer of an MDI/PEG-based polyurethane textile adhesive (referred to hereinafter as Adhesive #2) was applied to the ePE side of the precursor laminate. A NOMEX® nonwoven (50 gsm) was applied to the layer of Adhesive #2 and the laminate was placed on a roll and allowed to cure for at least 48 hours.
[0119] Preparation of Comparative Laminate A
[0120] Dots of FR Adhesive #1 were applied to Comparative Film A using a gravure roll. After the application of the adhesive, a NOMEX® nonwoven textile (90-95gsm) (available from Lydall Gutsche GmbH, Fulda, Germany) was placed onto the adhesive dots to form a precursor laminate. A continuous layer of Adhesive #2 was applied to the ePE side of the precursor laminate. A NOMEX® nonwoven (50 gsm) was applied to the layer of Adhesive #2 and the laminate was placed on a roll and allowed to cure for at least 48 hours.
[0121] Vertical Flame testing was performed using ASTM D6413 The results show that Laminate #1 had an afterflame of 0 seconds in the warp and fill directions. Comparative Laminate A had an afterflame of 45.8 seconds in the fill direction and 45.3 seconds in the warp direction.