Protective laminates

Abstract

A laminate including a) a first textile layer; b) a layer of heat reactive material; c) a carrier layer comprising a meltable material; d) an adhesive layer; and e) a flame retardant textile layer; wherein the layer of heat reactive material is between the first textile layer and the carrier layer.

Description

PROTECTIVE LAMINATESTECHNICAL FIELD OF THE DISCLOSURE

[0001] The present disclosure relates to protective laminates comprising multiple textile layers. In particular, the protective laminates can provide protection from flash fires and the discharge of an electric arc.BACKGROUND OF THE DISCLOSURE

[0002] In order to reduce injuries, protective laminates and clothing is desired for professionals working in hazardous environments where short duration exposure to flames or electric arc flash is possible. Protective gear for workers exposed to these conditions should provide some enhanced protection to allow the wearer to get away from the hazard quickly and safely, rather that repair the hazard.

[0003] Traditionally, garments that provide protection from an exposure to a short duration flash fire or an electrical flash are relatively heavy and require multiple layers, each layer providing an additional level of protection against the heat from the exposure. Such garments are made with multiple layers comprising non-combustible, non-melting fabric made of, for example, aramids, polybenzimidazole (PBI), poly p- phenylene-2,6-benzobisoxazole (PBO), modacrylic blends, polyamines, carbon, polyacrylonitrile (PAN), and blends and combinations thereof. These fabrics may be inherently flame resistant and are often used in the firefighting community but have several limitations. Specifically, in order to achieve the desired level of protection, relatively heavy weight, bulky fabrics are required. Typically, these fabrics can have a basis weight in excess of 400 grams per square meter. The fibers used to form these fabrics may be very expensive, difficult to dye and print, and may not have adequate abrasion resistance. Additionally, these fibers pick up more water and offer unsatisfactory tactile comfort as compared to nylon or polyester based fabrics. For optimum user performance in environments with a potential arc flash exposure and / orflash fires, a lightweight, breathable, water resistant garment with enhanced burn protection may be desired. There is a continuing need for waterproof, flame resistant (FR), arc flash resistant, protective clothing that minimizes or eliminates the use of typical non-combustible, non-melting fabric textiles such as those used in firefighting community.SUMMARY OF THE DISCLOSURE

[0004] In some embodiments, a laminate includes a) a first textile layer; b) a layer of heat reactive material; c) a carrier layer comprising a meltable material; d) an adhesive layer; and e) a flame retardant textile layer; wherein the layer of heat reactive material is between the first textile layer and the carrier layer.

[0005] In some embodiments, the layer of heat reactive material is applied in a continuous manner or a discontinuous manner. In some embodiments, the layer of heat reactive material is in the form of a pattern of discontinuous dots, lines, or grids. In some embodiments, the heat reactive material includes expandable graphite, and the expandable graphite expands at least about 900 micrometers upon heating to about 280°C, as measured in the TMA expansion test. In some embodiments, at least one of b) the layer of heat reactive material, c) the carrier layer including a meltable material, or d) the adhesive layer includes a flame retardant additive. In some embodiments, the carrier layer is a porous film, a nonporous film, or a nonwoven layer.

[0006] In some embodiments, the carrier layer includes a breathable polymer. In some embodiments, the first textile layer includes at least one meltable fiber. In some embodiments, the carrier layer includes porous polyethylene, and the porous polyethylene is an expanded ultrahigh molecular weight polyethylene. In some embodiments, the breathable polymer is a polyurethane, polyamide, polyester, polyether, ionomer, or a copolymer or a combination thereof.

[0007] In some embodiments, the layer of heat reactive material covers greater than or equal to 25% of a surface of the first textile layer. In some embodiments, the flame retardant textile comprises one or more of aramids, p-aramid, m-aramid, polybenzimidazole (PBI), polybenzoxazole (PBO), polyetheretherketone,polyetherketoneketone, polyphenylene sulfide, polyimide, polyamide imide, melamine, fluoropolymer, polytetrafluoroethylene, modacrylic, cellulose, flame retardant cellulose, flame retardant viscose, flame retardant polyester, flame retardant polyamide, polyvinylacetate, polyacrylonitrile (PAN), melamine, fiberglass, carbon fibers, mineral fibers, protein fibers, or a combination thereof.

[0008] In some embodiments, the carrier layer includes a film that is nonporous, a film that is porous, and / or a nonwoven layer. In some embodiments, the laminate passes an Arc Flash Box test Class 1 according to I EC 61482-1 . In some embodiments, the laminate passes a Box test Class 2 according to I EC 61482-1-2 and has a laminate weight of between 250 grams per square meter and 400 grams per square meter.

[0009] In some embodiments, the present disclosure is also directed to an article, wherein the article includes the laminate. In some embodiments, the article is a garment.

[0010] In some embodiments, a method includes i) adhering a first textile layer to a carrier layer with a heat reactive material to form a precursor laminate; and ii) adhering the precursor laminate to a flame retardant textile using a flame retardant adhesive; wherein the flame retardant textile is applied to the precursor laminate adjacent to the carrier layer of the precursor laminate.

[0011] In other embodiments, the disclosure relates to a laminate comprising a) a first textile layer, b) a layer of heat reactive material, c) a flame retardant textile layer, d) a first adhesive layer, and e) a carrier layer comprising a meltable material, wherein the layer of heat reactive material is between the first textile layer and the flame retardant textile layer. In further embodiments, this laminate may further comprise a second textile layer, wherein the second textile layer is adhered to the carrier layer on the side opposite from the flame retardant layer.

[0012] In other embodiments, the disclosure relates to a method, wherein the method includes, 1 ) adhering a first textile to a flame retardant textile layer with a heat reactive material to form a precursor laminate; and ii) adhering the precursor laminate to a carrier layer using a flame retardant adhesive, wherein the carrier layer is applied to the precursor laminate adjacent to the flame retardant textile layer.BRIEF DESCRIPTION OF THE FIGURES

[0013] Figure 1 shows an example of embodiments of the laminate with the carrier layer located between the first textile layer and the flame retardant textile layer.

[0014] Figure 2 shows an example of embodiments of the laminate with the carrier layer located between the first textile layer and the flame retardant textile layer.

[0015] Figure 3 shows an example of embodiments of the laminate with the carrier layer located between the first textile layer and the flame retardant textile layer.

[0016] Figure 4 shows an example of embodiments of the laminate with the flame retardant textile layer located between the first textile layer and the carrier layer.

[0017] Figure 5 shows an example of embodiments of the laminate with the flame retardant textile layer located between the first textile layer and the carrier layer and the optional second textile layer.

[0018] Figure 6 shows an example of embodiments of the laminate with the flame retardant textile layer located between the first textile layer and the carrier layer and the optional second textile layer.

[0019] Figure 7 shows an example of embodiments of the laminate with the flame retardant textile layer located between the first textile layer and the carrier layer and the optional second textile layer.

[0020] Figures 8A and 8B show examples of patterns of the heat reactive material.DETAILED DESCRIPTION

[0021] The disclosures of all cited patent and non-patent literature are incorporated herein by reference in their entirety.

[0022] 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.

[0023] 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.

[0024] 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 element. Conversely, various features of the disclosure that are, for brevity, described 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.

[0025] 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 proceeded 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.

[0026] As used herein, the terms “fiber”, “filament” and “yarn” may be used interchangeably, unless specifically stated otherwise. A fiber is intended to mean a thin thread having a finite length, for example, from a few millimeters to about 30 centimeters in length. The term “filament” is intended to mean a thin thread having a length from about 30 centimeters up to an essentially endless length. A filament may be thousands of meters long. The term “yarn” means a continuous strand comprising one or more fibers and / or filaments. Any of the known yarns can be used, for example, single-ply yarns, plied yarns, cord yarns, stretch yarns or any combinations thereof. Fibers and / or filaments can be used to make the yarns.

[0027] As used herein, the term “textile” means a cloth that is woven, knit, or nonwoven. The textile may be made from fibers, filaments, yarns, or a combination thereof. In general, an adhesive layer applied to one side of a textile will adhere the textile to a substrate that is placed on the same side of the textile as the layer of adhesive and the adhesive will penetrate into at least a portion of the thickness of the textile, but the adhesive will not penetrate the entire thickness of the textile.

[0028] As used herein, the term “membrane” means a polymer in the form of an essentially two-dimensional sheet, 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 membrane is a porous membrane having a structure of pores that allows, for example, water vapor to pass through the thickness of the membrane without liquid water being able to penetrate from one side of the membrane to the other. On average, the pore size is on the order of several nanometers to approximately one micrometer. In other embodiments, the membrane is nonporous and breathable, allowing water vapor to transfer from one side of the membrane to the other side of the membrane.

[0029] As used herein, the term “film” means a porous membrane having a structure of pores wherein the pores have been at least partially filled with a polymer such that the flow of gases or liquids does not occur through open pore channels in the membrane. In some embodiments, the polymer at least partially filling the pores can be a breathable polymer.

[0030] The term “breathable” refers to a material, for example, a polymer, a film, a membrane, or a laminate that can allow substantial amounts of water to be transferred through the thickness of the material by absorbing water on one side where the water concentration is higher and desorbing or evaporating the water on the opposite side where the water vapor concentration is lower. In some embodiments, the breathable polymer, film, or laminate can have a moisture vapor transmission rate of greater than or equal to 1 ,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.

[0031] 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.

[0032] As used herein, the term “meltable”, when used in relation to an article, for example, a fiber, a filament, a yarn, a textile, or a material means that the article melts at less than or equal to 280°C or less than or equal to 300°C, according to the melting and thermal stability test described herein. In embodiments wherein the article is madefrom a single material, for example, 100% nylon, the melting point of the material is the melting point of the nylon. However, in textile embodiments comprising a mixture of both meltable and non-meltable fibers, filaments or yarns, the presence of the non- meltable component may mask the melting of the meltable material. For example, in the case of a textile comprising a 50 / 50 blend of nylon 6.6 and cotton, the melt of melted nylon 6.6 may be absorbed by the cotton component and, when subjected to the melting and thermal stability test described herein, may appear to show that the textile sample is not meltable. Therefore, when there is a meltable fiber present in a blend of meltable and non-meltable fibers, the blend material will be considered to be a meltable material for the purposes of this disclosure.

[0033] As used herein, the term “precursor laminate” means a layered structure comprising two layers adhered by a layer of heat reactive material or by a layer of an adhesive. The two layers of the precursor laminate can be the meltable textile and the carrier layer, the meltable textile and the flame retardant textile layer, or the flame retardant textile layer and the carrier layer. Precursor laminates are typically produced during a stepwise process for making the laminates described herein.

[0034] The disclosure describes textiles that are used in various layers of the laminate. As used herein, each of the first textile layer, the second textile layer, and the flame retardant textile layer can independently be a single textile layer or a multilayer textile layer in a woven, knit, nonwoven or laminate form. Unless otherwise stated, textiles can be produced from fibers, filaments and / or yarns that can be meltable, nonmeltable, or a combination thereof. The fibers, filaments or yarns can be synthetic and / or natural. Depending upon the type and the composition of the fibers, filaments or yarns, the corresponding textiles can have a variety of different properties. The textiles can be meltable, nonmeltable, flammable, flame-resistant, abrasion-resistant, heat-resistant, shrink-resistant or the textiles can have combinations of those properties. For example, the textile layer can be a meltable and abrasion resistant textile; or a meltable and flammable textile; or a flame-resistant and shrink-resistant textile.

[0035] As use herein, the term “shrink-resistant” means that the textiles and / or laminates shrink less than 20%, or less than 10%, or less than 5% of their width, their length or both, when exposed to a high energy event. In some embodiments, thelaminates described herein shrink less than 20%, or less than 10%, or less than 5% when subjected to the shrink test according to ISO 17493 at 180°C. In other embodiments, the laminates described herein shrink less than 20%, or less than 10%, or less than 5% when subjected to the shrink test according to ISO 17493 at 260°C. As used herein, the term “high energy” or “high energy event” means an exposure of greater than or equal to 0.1 seconds to a temperature of greater than or equal to 180°C.

[0036] The present disclosure relates to a laminate comprising a) a first textile, b) a layer of heat reactive material; c) a carrier layer comprising a meltable material; d) an adhesive layer; and e) a flame retardant textile layer, wherein the layer of heat reactive material is between the first textile layer and the carrier layer comprising porous polyethylene. In other embodiments, the present disclosure relates to a laminate comprising a) a first textile layer, b) a layer of heat reactive material, c) a flame retardant textile layer, d) an adhesive layer, and e) a carrier layer comprising a meltable material. The laminates can be used to make protective articles, including protective garments, wherein the first textile layer is typically the outermost layer of the garment, and the flame retardant textile layer is an inner, but not necessarily the innermost layer of the clothing article. Protective articles can include, for example, clothing, garments, tents, blankets, and / or coverings. Protective clothing includes garments like jackets, trousers, shirts, vests, overalls as well as gloves, gaiters, hoods, footwear and shoes. Protective clothing comprising the laminates may be waterproof or water resistant, and breathable.

[0037] Protective clothing needs to be lightweight to be widely used, especially in cases where the danger of an exposure to a flash fire or a high heat incident, for example, exposure to an electrical arc flash is present, but of a low probability. In some embodiments, the laminates can have a weight of, for example, less than or equal to 500 grams per square meter (gsm). In some embodiments, the laminates can have a weight of in the range of from 125 gsm to 500 gsm, or from 150 gsm to 500 gsm, or from 200 gsm to 500 gsm, or from 200 gsm to 475 gsm, or from 200 gsm to 450 gsm or from 200 gsm to 425 gsm, or from 200 gsm to 400 gsm. In still further embodiments, the laminate can have a weight in the range of from 225 gsm to 400 gsm, or from 250 gsm to 375 gsm, or from 275 gsm to 375 gsm, or from 275 gsm to 350 gsm.

[0038] To reduce the weight of the laminates, the weight has to be reduced without losing the protective properties or decreasing breathability or waterproofness. As described herein, the weight of one or more of the first textile layer, the carrier layer, the flame retardant textile layer, and / or the second textile layer can be reduced without sacrificing the ability of the laminate to provide the wearer with protection from a high heat incident or electric arc flash exposure. By utilizing relatively lightweight layers, the overall weight of the laminates can be reduced. However, when the weight of the laminates is too low, there can be an increased risk during a flash fire or other high heat condition that enough heat or energy from the incident can affect the wearer.Therefore, the present laminates provide additional protection by utilizing a layer of heat reactive material and a layer of a flame retardant textile. The layer of heat reactive material absorbs at least a portion of the heat from the incident, while the flame retardant textile can provide a layer that can help to minimize the heat transferred to a wearer, provide a layer that is shrink-resistant and is able to resist the formation of holes.

[0039] FIRST TEXTILE LAYER

[0040] Laminates described herein comprise a first textile layer. Suitable fibers, filaments or yarns for the first textile layer can comprise nylon, nylon 6, nylon 6.6, nylon 12, nylon 6.12, polyester, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyurethane, elastane, acrylic, polyolefin, elastolefin, polyethylene, polypropylene, aramids, meta-aramids, para-aramids, NOMEX® aramid, KEVLAR® aramid, polyamide-imides, KERMEL® polyamid-imides, polybenzimidazole (PBI), polybenzoxazole (PBO), flame retardant (FR) viscose, FR cotton, modacrylic, polyamine, carbon fiber, fiberglass, polyacrylonitrile (PAN), oxidized polyacrylonitrile, PTFE, viscose, rayon, cotton, wool, silk, cellulose, jute, flax, bamboo, hemp or a combination thereof. The fibers, filaments, and / or yarns used may be virgin or recycled. The fibers and / or filaments can be combined using known methods to form yarns. A yarn can be produced from a single type of fiber or filament, or the yarn may be produced from a blend of two or more different types of fibers or filaments. Similarly, the first textile layer may be formed from a single type of fibers, filaments, and / or yarnsor from multiple different fibers, filaments and / or yarns to provide the desired properties of the first textile layer. The textiles can be woven, knits or nonwoven textiles.

[0041] The first textile layer forms a portion of the laminate that is intended to be an outer layer of a protective article, exposed directly to a high energy event, for example, exposure to heat, flame, an electrical discharge, or a combination thereof. In some embodiments, the first textile layer comprises a meltable textile layer, i.e., a textile layer that comprises meltable fibers according to the definition of meltable as provided herein. In some embodiments, the first textile layer comprises a nonmeltable textile layer, for example, a cotton textile. In other embodiments, the first textile layer can comprise a combination of meltable and nonmeltable fibers, filaments and / or yarns, for example, a nylon / cotton blend or a polyester / cotton blend. In some embodiments, the first textile layer is a textile that is a no melt and / or no drip textile according to the melting and thermal stability test as defined herein. In some embodiments, the first textile layer includes a textile that is made from meltable fibers, filaments or yarns and is considered to be a no melt and / or no drip textile according to the melting and thermal stability test as defined herein.

[0042] In any of the previous embodiments, the first textile layer can comprise in the range of from 0% to 100% meltable fibers, based on the total weight of the meltable and nonmeltable fibers in the first textile layer. In other embodiments, the first textile layer can comprise in the range of from greater than 0% to 100% meltable fibers, or from 0.5% to 100% meltable fibers, or from 1 % to 100%, or from 1 % to 99% meltable fibers, or from 3% to 100% meltable fibers, or from 5% to 100% meltable fibers, or from 10% to 100% meltable fibers, or from 20% to 100% meltable fibers, or from 25% to 100% meltable fibers, or from 30% to 100% meltable fibers, or from 35% to 100% meltable fibers, or from 40% to 100% meltable fibers, or from 50% to 100% meltable fibers, or from 60% to 100% meltable fibers, or from 70% to 100% meltable fibers, or from 80% to 100% meltable fibers, or from 90% to 100% meltable fibers. In other embodiments, the first textile comprises a combination of meltable and nonmeltable fibers in the range of from 1 to 99% nonmeltable fibers and from 1 to 99% meltable fibers, wherein the percentages by weight are based on the total weight of the fibers in the first textile layer. Each of the percentages are based on the total weight of the fibers in the first textilelayer. In some embodiments, the first textile layer comprises at least one meltable fiber, filament or yarn.

[0043] In some of the previous embodiments, the first textile layer can comprise a 100% nylon textile. In some of the previous embodiments, the first textile layer can be a 100% polyester textile. In other embodiments, the first textile layer can be a cotton textile comprising up to 100% cotton. In other embodiments, the first textile layer can be a wool textile comprising up to 100% wool.

[0044] In still further embodiments, the first textile layer can comprise a mixture of nylon and cotton, for example in the range of from 30% to 70% nylon and 30% to 70% cotton; or from 30% to 68% nylon, from 30% to 68% cotton and up to about 5% by weight, based on the total weight of the textile of an antistatic additive.

[0045] In a further embodiment, the first textile layer may comprise a mixture of polyester and cotton, for example in the range of from 30% to 70% polyester and 30% to 70% cotton; or from 30% to 68% polyester, from 30% to 68% cotton and up to about 5% by weight, based on the total weight of the textile of an antistatic additive.

[0046] In still further embodiments, the first textile layer can comprise a mixture of nylon and another fiber, for example, cotton, wool, modacrylic, or any other fiber used in fabric blends in the range of from 30% to 70% nylon and 30% to 70% another fiber; or from 30% to 68% nylon, from 30% to 68% another fiber and up to about 10% by weight, based on the total weight of the textile of an antistatic additive. In further embodiments, the first textile layer can comprise a mixture of nylon and another fiber, for example, cotton, wool, modacrylic, or any other fiber used in fabric blends in the range of from 30% to 70% nylon and 30% to 70% another fiber; or from 30% to 68% nylon, from 30% to 68% another fiber and up to about 5% by weight, based on the total weight of the textile of an antistatic additive.

[0047] In a further embodiment, the first textile layer may comprise a mixture of polyester and another fiber, for example, cotton, wool, modacrylic, or any other fiber used in fabric blends, in the range of from 30% to 70% polyester and 30% to 70% another fiber; or from 30% to 68% polyester, from 30% to 68% another fiber and up to about 5% by weight, based on the total weight of the textile of an antistatic additive.

[0048] In still further embodiments, the laminate comprises a first textile layer comprising a combination of meltable and nonmeltable fibers in the range of from 1 to 99% nonmeltable fibers and from 1 to 99% meltable fibers. In other embodiments, the first textile layer can comprise meltable fibers in the range of from 5% to 100%, or from 10% to 100%, or from 20% to 100%, or from 25% to 100%, or from 30% to 100%, or from 35% to 100%, or from 40% to 100%, or from 50% to 100%, or from 60% to 100%, or from 70% to 100%, or from 80% to 100%, or from 90% to 100%. Each of the percentages are based on the total weight of the meltable and nonmeltable fibers in the first textile layer.

[0049] In still further embodiments, the first textile layer can comprise a woven textile that is a combination of meltable fibers, filaments, or yarns and flame retardant, nonmeltable fibers, filaments, or yarns. For example, the first textile layer can be a woven textile with flame retardant filaments or yarns in the warp and / or weft direction in a regular repeating pattern, for example every n warp and / or weft courses, wherein each n is independently 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19 or 20, with the remaining fibers, filaments, or yarns being meltable. The placement of a flame retardant filament or yarn every nthwarp and or weft course is similar to a rip-stop woven textile. For example, the first textile layer can be a woven textile comprising nylon fibers, filaments or yarns in the warp and weft direction, wherein at every 10thwarp and weft yarn, a flame retardant filament or yarn is inserted. As another example, the first textile layer can be a woven textile comprising polyester fibers, filaments or yarns in the warp and weft direction, wherein at every 10thwarp and weft, a flame retardant filament or yarn is inserted. In other embodiments, the first textile is a textile as described in US 2022 / 0363042, the disclosure of which is herein incorporated by reference.

[0050] In further embodiments, the first textile layer can be a knit, e.g., a nylon knit, a polyester knit, a polyurethane knit or knits containing combinations of one or more nylons, polyesters, cotton, and / or polyurethanes. A knit construction may provide a relatively lightweight textile that helps to reduce the overall weight of the laminate while still retaining the desired flame resistant and / or arc resistant properties of the laminate. In some embodiments, the laminate comprises a first textile layer that is free from oressentially free from flame retardant or flame resistant additives. In some embodiments, the first textile layer may be produced from one or more recycled fibers, filaments, or yarns.

[0051] In some embodiments, the first textile layer comprises a textile produced from fibers, filaments or yarns having a denier (weight in grams of 9,000 meters of the fiber, filament, or yarn) in the range of from 5 denier (D) to 400D. In other embodiments, the fibers, filaments, or yarns can have a denier in the range of from 5D to 300D or from 5D to 250D or from 5D to 200D or from 7D to 150D or from 7D to 100D.

[0052] In some embodiments, the first textile layer can be a woven or a knit textile comprising nylon fibers, filaments, or yarns with a denier of in the range of from 5D to 400D. In some embodiments the first textile layer comprises a woven or knit textile made from nylon yarns with a denier in the range of from 5D to 400D or from 5D to 300D or from 5D to 250D or from 5D to 200D or from 7D to 150D or from 7D to 100D. In other embodiments, the first textile layer can be a woven or a knit textile made from polyester fibers, filaments, or yarns, wherein the yarns have a denier in the range of from 5D to 400D or from 5D to 300D or from 5D to 250D or from 5D to 200D or from 7D to 150D or from 7D to 100D. Optionally, any of the embodiments for the first textile layers described herein can be waterproof and / or the first textile layer can be water resistant by applying a durable water resistant (DWR) treatment to the first textile layer or to the laminate. This DWR coating can be on the outer side of the first textile layer, on the side that is opposite the layer of heat reactive material. In another embodiment, the first textile layer comprises a waterproof material.

[0053] The first textile layer may also comprise antistatic agents, antistatic particles, antistatic fibers, or antistatic polymers as a filler, as a coating, or as part of the fibers, filaments, or yarns that make up the first textile layer. Suitable antistatic materials can comprise, for example, carbon black, conductive fibers, metal particles, or electrically conductive polymers.

[0054] The first textile layer is lightweight, having a weight less than or equal to 200 grams / square meter (gsm), e.g., less than 200 gsm, less than 190 gsm, less than 180 gsm, less than 170 gsm, less than 160 gsm, less than 150 gsm, less than 140 gsm, less than 130 gsm, less than 125 gsm, less than 120 gsm, less than 110 gsm, less than 100gsm, less than 90 gsm or less than 85 gsm. In order for the first textile layer to have sufficient strength and durability, the textile weight should be greater than or equal to 15 gsm, or greater than or equal to 20 gsm, or greater than or equal to 25 gsm, or greater than or equal to 30 gsm, or greater than or equal to 35 gsm, or greater than or equal to 40 gsm, or greater than or equal to 45 gsm, or greater than or equal to 50 gsm, or greater than or equal to 55 gsm. It should be noted that with increasing amounts of nonmeltable fibers, the weight of the textile generally needs to be higher in order to have a first textile layer with adequate durability, strength, and abrasion-resistance. For example, with a 50 / 50 nylon / cotton blend, the textile weight should be in the range of 120 to about 150 gsm.

[0055] Despite the first textile comprising a meltable, flammable material, it has been found that increasing the weight of the first textile, that is, adding more meltable, flammable materials to the laminate, can help the laminate pass higher energy exposure events. For example, when the weight of the first textile layer is relatively low, the laminates are able to pass a Class 1 arc flash Box test, but may not pass a Class 2 arc flash Box test, which is a higher energy exposure event than the Class 1 test. If, however, the weight of the first textile layer is increased, thereby adding additional meltable, flammable materials to the laminate, the samples can surprisingly be made to pass the Class 2 arc flash Box test. In those samples having a relatively higher weight first textile layer, a slight increase in the amount of the heat reactive material may be required.

[0056] Laminates described herein may further comprise a second textile layer. The second textile layer may be independently chosen from any of the textile materials described as useful for the first textile layer. In some embodiments, the second textile is a nylon textile, a polyester textile, a cotton textile, or a textile made from a blend of two or more of nylon, polyester, and cotton.

[0057] HEAT REACTIVE MATERIAL

[0058] Laminates according to any of the embodiments described herein also comprise a layer of heat reactive material. The layer of the heat reactive material comprises a mixture of a polymer resin and a graphite, for example, an expandable graphite. If tested using the Furnace Expansion Test described herein, expandable graphitesuitable for use in the protective articles has an average expansion of at least 9 cc / g at 300°C. In one example, Asbury 3626 expandable graphite (available from Asbury Graphite Mills, Inc) has an average expansion of about 19 cc / g at 300°C, whereas Asbury 3538 expandable graphite (available from Asbury Graphite Mills. Inc.) has an average expansion of about 4 cc / g at 300°C, when tested according to the Furnace Expansion Test as described herein.

[0059] Suitable expandable graphite expands at least 300%, or at least 350% or at least 400%, or at least 450% or at least 500%, according to the TMA expansion test provided herein.

[0060] In some embodiments the heat reactive material is in the form of a mixture of a polymer resin and an expandable graphite. Expandable graphite particle size should be chosen so that the heat reactive material may be applied with the selected application method. For example, where the heat reactive material is applied by a gravure printing technique, the expandable graphite particle size should be small enough to fit in the gravure cells.

[0061] In certain embodiments, the heat reactive materials comprise expandable graphite having at least the expansion as described above and an endotherm of at least about 100 Joules / gram (J / g) when tested according to the Differential Scanning Calorimetry (DSC) Endotherm Test method described herein. In other embodiments, it may be desirable to use expandable graphite with an endotherm greater than or equal to about 150 J / g or greater than or equal to about 200 J / g or an endotherm greater than or equal to about 250 J / g.

[0062] In some embodiments, laminates comprising heat reactive material with expandable graphite has expansion of at least 300% according to the TMA expansion test and an endotherm greater than 100 J / g, have an average afterflame value of less than 20 seconds or an average char length of less than 20 centimeters (cm) or both, when tested according to the Edge Ignition Test described herein.

[0063] In other embodiments, the laminates can have an average afterflame of less than 10 seconds, or less than 2 seconds and / or the laminates may have an average char length less than 15 cm or less than 10 cm, when tested according to the Edge Ignition Test.

[0064] The layer of heat reactive material comprises a polymer resin and expandable graphite. Polymer resins having a melt or softening temperature of less than 280°C (as measured by DSC) are suitable for use in the heat reactive material. In some embodiments, the polymer resins are sufficiently flowable or deformable to allow the expandable graphite to expand substantially upon heat exposure at or below 280°C. It may be desirable that the extensional viscosity of a polymer resin is low enough to allow for the expansion of expandable graphite and high enough to maintain the structural integrity of the heat reactive material after expansion of the mixture of polymer resin and expandable graphite.

[0065] In other embodiments, a polymer resin is used which has a storage modulus between 103and 108dyne / cm2and Tan delta between 0.1 and 10 at 200°C. In other embodiments, the polymer resin has a storage modulus between 103and 106dyne / cm2. In another embodiment, a polymer resin is used that has a storage modulus between 103and 104dyne / cm2.

[0066] Polymer resins suitable for use in some embodiments are elastomeric. Other polymer resins suitable for use in some embodiments are cross-linkable, such as crosslinkable polyurethane, for example, MOR-MELT® R7001 E adhesive (from Rohm & Haas). In other embodiments, suitable polymer resins are thermoplastic having a melt temperature between 50°C and 250°C, such as DESMOMELT® VP KA 8702 adhesive (from Covestro AG, Leverkusen, DE). Polymer resins suitable for use in embodiments described herein comprise polymers which include but are not limited to polyesters, thermoplastic polyurethanes and cross-linkable polyurethanes, and combinations thereof. Other polymer resins may comprise one or more polymers selected from polyester, polyamide, acrylic, vinyl polymer, polyolefin, silicone or epoxy.

[0067] In other embodiments, the polymer resin may be an aqueous polymer resin, for example, an aqueous acrylic resin such as the acrylic resins taught in EP4030952, the disclosure of which is herein incorporated in its entirety.

[0068] In some embodiments, the aqueous acrylic resin may be a water-based acrylic polymer resin. The aqueous acrylic resin may include acrylamide repeat units. The aqueous acrylic resin may include N-methylol acrylamide repeat units. The aqueous acrylic resin may be a water-based acrylic polymer resin and may contain N-methylolacrylamide repeat units such as, for example, EDOLAN® AM acrylic resin available from Tanatex Chemicals B.V., Ede, Netherlands. The aqueous acrylic resin may be an acrylic copolymer comprising styrene in different amounts. The aqueous acrylic resin may be an acrylic copolymer comprising acrylamide monomers in different amounts. The aqueous acrylic resin may further comprise acrylonitrile, vinyl acetates, styrene or a combination thereof.

[0069] In some embodiments, the aqueous acrylic resin may be a thermoplastic. The aqueous acrylic resin may be self-crosslinked. The acrylic polymer may be a crosslinkable acrylic polymer. The term “self-crosslinking” means that the aqueous acrylic resin comprises functional groups that can react with another functional group under certain conditions, for example, elevated temperature, hydrolysis conditions, etc., as is known in the art, to form a crosslinked polymer. In some aspects, the selfcrosslinking can start cross-linking by applying an elevated temperature of, for example, about 120°C or higher without any additional chemicals. The aqueous acrylic resin may comprise a cross-linker. The aqueous acrylic resin may be uncrosslinked. The aqueous acrylic resin may be self-crosslinked and may further comprise a cross-linker. An additional cross-linker may improve the bonding to textiles. The heat reactive composition may comprise a crosslinker in order to form a crosslinked aqueous acrylic resin.

[0070] In some embodiments, the heat reactive material may comprise or consist essentially of an aqueous acrylic resin, expandable graphite, at least one FR additive and a crosslinking agent. Suitable crosslinking agents may include, for example, one or more of: polyisocyanate based crosslinking agents, blocked polyisocyanate based crosslinking agents. Other suitable crosslinking agents are the following materials: N- methoxymethylmelamine, methylolmelamine, carbodiimide, polycarbodiimide, isocyanate, polyisocyanate, diaminocarbamate, propylenimine, aliphatic propylenimine, aromatic propylenimine derivatives, reaction products between polyfunctional acrylates and propylenimine, (cyclo)aliphatic bisamide crosslinker or a combination thereof.

[0071] In some embodiments, the heat reactive composition may comprise a crosslinking agent at equal to or less than about 10% by weight, or equal to or less than about 9% by weight, or equal to or less than about 8% by weight, or equal to or lessthan about 7% by weight, or equal to or less than about 6% by weight, or equal to or less than about 5% by weight, or equal to or less than about 4% by weight, or equal to or less than about 3% by weight, or equal to or less than about 2% by weight, or equal to or less than about 1 % by weight, based on the total weight of the aqueous acrylic resin and the crosslinking agent.

[0072] Aqueous acrylic resins having a melt or softening temperature of less than about 280°C may be used. The aqueous acrylic resins may allow expandable graphite to expand at least about 900 micrometers upon heating to about 280°C, as measured in the TMA expansion test.

[0073] The heat reactive material may comprise a flame retardant material. In some embodiments, the flame retardant materials may be optionally incorporated in the polymer resin. In some embodiments, the polymer resins may include at least one flame retardant component or additive. The at least one flame retardant component or additive can be one or more of a chlorinated compound, a brominated compound, antimony oxide, an organic phosphorous-based compound, a phosphate ester, resorcinol bis(diphenyl phosphate), zinc borate, ammonium polyphosphate, melamine cyanurate, melamine polyphosphate, a molybdenum compound, alumina trihydrate and magnesium hydroxide, or any combination thereof. In some embodiments, the flame retardant materials are melamine polyphosphate, resorcinol bis(diphenyl phosphate), or a combination thereof. The flame retardant materials may be present in an amount in the range of from 0% to 60% by weight, based on the total weight of the heat reactive material. In other embodiments, the flame retardant materials may be present in an amount in the range of from 10% to 55% by weight, based on the total weight of the heat reactive material.

[0074] In some embodiments, upon exposure of the laminate to flames and / or heat, for example, at a temperature greater than or equal to 280°C, a meltable portion of the first textile layer, if present, melts and absorbs into the heat reactive material. At the same time, the expandable graphite in the heat reactive material can expand. In other embodiments, upon exposure of the laminate to flames and / or heat, for example, at a temperature greater than or equal to 300°C, a meltable portion of the first textile layer, if present, melts and absorbs into the heat reactive material. At the same time, the heatreactive material can expand. These processes can form a char comprised of the first textile layer and the heat reactive material. In embodiments where a non-meltable fiber, for example, a cotton fiber or yarn is present in the first textile, the exposure to flames and / or heat can cause the cotton to burn or smolder thus forming a char, and the heat can cause the expandable graphite to expand which then covers or envelopes the burning / smoldering cotton, thereby extinguishing any flames.

[0075] The char, resulting from exposure of the first textile layer and the layer of heat reactive material to heat and / or high temperatures, for example, greater than or equal to 280°C or greater than or equal to 300°C, is a heterogeneous mixture of the first textile layer and the expanded layer of heat reactive material. Char, according to this disclosure, is meant to refer to the carbonaceous material remaining after exposing the first textile layer and the heat reactive material to a temperature of greater than or equal to 280°C or greater than or equal to 300°C. The char is a mixture of the expanded graphite and one or both of the melted polymer resin and any meltable and / or non- meltable portion of the first textile layer. At temperatures greater than or equal to 280°C or greater than or equal to 300°C, one or both of the first textile layer and polymer resin may also oxidize or participate in the combustion process forming additional carbonaceous material that becomes part of the char. The formation of the char can help to insulate the layers behind the char from exposure to heat.

[0076] Upon exposure of the laminate to flames and / or extreme heat, the layer of heat reactive material can expand within (or mix with) the melt of the first textile layer. In doing so the layer of heat reactive material mixes with the melted first textile layer and protects the layers beneath and the wearer of the article. In some embodiments, laminates can have a break-open time that is increased by at least 20 seconds, or increased by at least 30 seconds, over a laminate constructed of substantially the same materials, but without the expandable graphite material, in which the expansion process described above does not occur, when tested according to the method for Horizontal Flame Test described herein.

[0077] In some embodiments, the mixture of polymer resin and expandable graphite, upon expansion, forms a plurality of tendrils comprising expanded graphite. The total surface area of the heat reactive material increases significantly when compared to thesame mixture prior to expansion. In some embodiments, the surface area of the mixture is increased at least five times after expansion. In other embodiments, the surface area of the mixture increases at least ten times after expansion. In addition, tendrils will often extend outward from the expanded mixture. In an embodiment where the heat reactive material is situated on a substrate in a discontinuous form, the tendrils will extend to at least partially fill the open areas between the discontinuous domains. In a further embodiment, the tendrils will be elongated, having a length to width aspect ratio of at least 5 to 1.

[0078] During exposure to a high energy event, for example, exposure to heat, flame and / or an arc flash, the combination of the first textile layer and the layer of heat reactive material and, optionally, the melting of the carrier layer, may dissipate or absorb at least a portion of the incident energy being transferred during the high energy event, due to the melting and / or expansion described above. If the energy and / or heat transferred through the carrier layer is high enough, then the combination of the flame retardant adhesive and the flame retardant textile can provide a final protective layer to help to minimize the amount of incident energy experienced by a wearer of a protective garment comprising the laminate.

[0079] In some embodiments, the heat reactive material may be produced by a method that provides an intimate blend of polymer resin and expandable graphite, without causing substantial expansion of the expandable graphite. Suitable mixing methods include but are not limited to paddle mixer, blending and other low shear mixing techniques. In one method, the intimate blend of polymer resin and expandable graphite particles is achieved by mixing the expandable graphite with a monomer or prepolymer prior to polymerization of the polymer resin. In another method, the expandable graphite may be blended with a dissolved polymer, wherein the solvent is removed after mixing. In another method, expandable graphite is blended with a hot melt polymer at a temperature below the expansion temperature of the expandable graphite and above the melting temperature of the polymer. In methods which provide an intimate blend of polymer resin and expandable graphite particles or agglomerates of expandable graphite, the expandable graphite is coated or encapsulated by the polymerresin prior to expansion of the expandable graphite. In other embodiments, the intimate blend is achieved prior to applying the heat reactive material to a substrate.

[0080] The heat reactive material comprises less than or equal to 50 weight percent (wt%), or less than or equal to 40 wt%, or less than or equal to 30 wt% of the expandable graphite based on the total weight of the heat reactive material, and the balance substantially comprising the polymer resin and flame retardant materials. In other embodiments, the expandable graphite comprises less than or equal to 20 wt%, or less than or equal to 10 wt%, or less than or equal to 5 wt% of the heat reactive material, and the balance substantially comprising the polymer resin and flame retardant materials. Generally, from 5 wt% to 50 wt% of expandable graphite based on the total weight of the heat reactive material, is desired. In some embodiments, desirable flame resistance performance may be achieved with even lower amounts of expandable graphite. Loadings as low as 1 wt% may be useful. Depending on the properties desired and the construction of the resulting laminates, other levels of expandable graphite may also be suitable for other embodiments. Other additives such as pigments, fillers, antimicrobials, processing aids and stabilizers may also be added to the heat reactive material. If present, the other additives are generally present in amounts of less than about 10% by weight, based on the total weight of the heat reactive material.

[0081] The layer of heat reactive material and, more particularly, the polymer resin may function as an adhesive, for example, for attaching or bonding one layer to an adjacent layer. For example, the layer of heat reactive material may adhere the first textile layer to the carrier layer, or the layer of heat reactive material may adhere the first textile layer to the flame retardant textile layer. The layer of heat reactive material may be in the form of a discontinuous adhesive, for example, a series of individual dots or shapes that do not touch or overlap one another. In other embodiments, the layer of heat reactive material may be a continuous layer extending across a majority of the length and / or the width of the laminate. In still further embodiments, the layer of heat reactive material may be in the form of a series of lines or grids extending across a majority of the length and / or width of the laminate. The lines or grids may be straight, curved, may be essentially parallel to each other, and / or they may overlap one another. When thelayer of heat reactive material is applied in a discrete discontinuous manner, the shape of the dot of the heat reactive material may take essentially any form. In some embodiments, the shape may be a circle, an oval, a triangle, a square, a rectangle, a star, a polygon, a four-sided polygon or any other discrete shape.

[0082] An amount of the heat reactive material should be applied to adhere the first textile layer to the carrier layer to provide the desired protection from a high energy event. Typically, the layer of heat reactive material is applied so as to provide a laydown of at least 20 grams per meter2(gsm) of the heat reactive material. In some embodiments, the amount of the layer of heat reactive material can be in the range of from 20 gsm to about 130 gsm. In other embodiments, the amount of the layer of heat reactive material can be in the range of from 30 gsm to 120 gsm, or from 40 gsm to 110 gsm, or from 50 gsm to 110 gsm, or from 60 gsm to 110 gsm, or from 70 gsm to 110 gsm.

[0083] CARRIER LAYER

[0084] The laminate comprises a carrier layer that is located between the layer of heat reactive material and the adhesive layer, or the laminate comprises a carrier layer that is located on the flame retardant layer on a side that is opposite the first textile layer. The carrier layer according to any of the embodiments disclosed herein comprises a meltable material and can provide the laminate with strength and durability before an exposure to a high energy event that causes expansion of the layer of the heat reactive material. As used herein, the phrase “meltable material” means a polymeric structure in the form of a membrane or a film that has a melting point or a softening point as measured by Differential Scanning Calorimetry (DSC). In some embodiments, the melting point of the meltable material is less than or equal to 400°C. In other embodiments, the melting point of the meltable material is less than 350°C or less than 300°C. Prior art laminates comprising the disclosed heat reactive material have utilized a heat stable layer or a thermally stable layer laminated to a meltable material in order to provide strength after exposure to a high energy event, that is, the thermally stable layer maintained structural integrity after the exposure to the high energy event. It is surprising that laminates comprising a layer that is not thermally stable and, in fact may melt during exposure to a high energy event can be used in the disclosed laminates andstill retain a level of the thermal protection properties required for the laminates that are exposed to high energy events.

[0085] In some embodiments, the carrier layer can comprise i) a membrane that is nonporous, ii) a membrane that is porous, and / or iii) a nonwoven layer. In some embodiments, the carrier layer can comprise a polymer that is breathable. Suitable polymers that can be used as the carrier layer can include breathable examples of polyesters, polyamides, polyethers, polyurethanes, ionomers, polyacrylic acids, ethylene vinyl acetate copolymers, ethylene acrylic acid copolymers, polyphenylene sulfide, polyolefins modified with hydrophilic groups such as, hydroxyl, carboxylic acid, amide, amine, and / or sulfonic acid groups, or a copolymer or a blend thereof. In some embodiments, the breathable polymer can include, for example, copolymers of polyesters and polyethers, copolymers of polyethers and polyamides; copolymers of polyethers, polyesters and polyurethanes; copolymers of polyethers, polyamides, polyurethanes and / or polyureas; or any combination thereof comprising polyethers with one or more ester, amide, urethane and / or urea groups in the backbone or side chains. The polymers listed above can be thermoplastic polymers or they can be crosslinked during or after the formation of the membrane. Additionally, any of the polymers listed herein can comprise one or more virgin polymers, recycled polymers, can be made from one or more monomers that are derived from bio-based sources, or a combination thereof. Any of the breathable polymers may be formed into nonporous membranes using one or more of the known processes, for example, solvent casting, spray coating, blow molding and slitting, melt extrusion, and / or calendering.

[0086] In other embodiments, the laminate can comprise a carrier layer that comprises a porous film. The term “porous film” means a film that has a continuous pathway of pores from one side of the film to the opposite side of the film, wherein the pores are small enough to exclude liquid water, but large enough to allow water vapor to pass from one side of the film to the other side. The porous film can comprise a polymer that is breathable, or the porous film can comprise a polymer that is not breathable. Suitable porous polymers can include, for example, any of those polymers that are described as being breathable as described above, but can also include porous polymers that are not breathable, for example, porous polyolefins, poly(meth)acrylates, polyesters,polyamides, polyurethanes, polyacrylonitrile or a copolymer or a blend thereof. In some embodiments, at least a portion of the pores of the porous polymers can be imbibed with one or more of the breathable polymers also previously described. For example, a porous polypropylene polymer may be imbibed with a breathable polymer, for example, a breathable polyurethane polymer. In another example, a porous polyethylene membrane may be imbibed with a breathable polymer, for example, a breathable polyurethane polymer. In other embodiments, the pores of a porous polymer may comprise a coating on the pore walls, without occluding the entirety of the pores, allowing water vapor to pass from one side of the film to the other, thus retaining a continuous pathway of pores from one side of the film to the opposite side.

[0087] In other embodiments, the carrier layer can be a film comprising a porous polymer wherein at least a portion of the pores are filled with a hydrophilic polymer. The film may be an expanded ultrahigh molecular weight polyethylene polymer as described in WO 2020 / 028328 and / or WO 2020 / 028331 , the contents of both of which are incorporated herein in by reference their entirety. By imbibing at least a portion of the pores with a breathable polymer, the waterproofness and breathability may be made more durable, as it is known that dirt and oils can contaminate the pores of a porous membrane and help to transport liquid water from one side of the membrane to the other. In some embodiments, the film is a porous thermoplastic membrane that is imbibed with a breathable polymer, wherein the breathable polymer is a crosslinked polymer. The polyethylene membranes described in WO 2020 / 028328 and / or WO 2020 / 028331 are particularly useful, and can comprise membranes with i) a weight average molecular weight greater than 500,000 g / mol; ii) a porosity of at least 40%; and iii) a Gurley number of less than 200 seconds. Under magnification, the porous polyethylene membrane shows a fibril lated 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.

[0088] In some embodiments, the carrier layer can be a polymer film that is a porous polymer membrane and has a first side and a second side. Any of the polymers listed above as breathable polymers can be used to fill at least a portion of the pores of theporous polymer. In order to fill a porous polymer, a melt, a dispersion, or a solution of the breathable polymer can be coated or otherwise applied to one or both sides of the porous polymer and allowed to cool and / or dry, for example, by removal or evaporation of the dispersing liquid or the solvent. This can result in a coating of the breathable polymer on the pore walls of the porous polymer, it can result in the breathable polymer completely filling at least a portion of the pores of the porous polymer, or it can result in at least a portion of the pores of the porous polymer being filled and a portion of the pore walls coated with the breathable polymer. In some embodiments, the breathable polymer can be applied to the first side of the porous polymer resulting in the first side comprising a cap layer of the breathable polymer on the first side of the film. The thickness of the cap layer or amount of the breathable polymer that remains as a coating on the first side of the porous polymer has essentially no upper limit. However, if the cap layer is too thick, then the beneficial properties of the porous polymer may not be realized. Therefore, the upper limit of the cap is about 50 micrometers. In some embodiments, the cap layer of the breathable 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 porous polymer. In some embodiments, the cap layer of the breathable polymer can be up to about 10 micrometers thick on the first side of the porous polymer. In other embodiments, the cap layer on the first side of the porous polymer 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 of the breathable polymer is present on the first surface of the porous polymer.

[0089] The second side of the porous polymer can be essentially free from any of the breathable polymer on the surface, for example, no breathable polymer of a thickness more than 1 micrometer above the surface of the porous polymer. In some embodiments, less than the entire thickness of the porous polymer is filled with the breathable polymer, for example, less than or equal to 90% of the thickness of the porous polymer may be filled with the breathable polymer, with the proviso that enough breathable polymer is imbibed so as to provide the porous polymer with a Gurley number of greater than or equal to 1000 seconds. In other embodiments, essentiallythe entire thickness of the porous polymer is filled with the breathable polymer. As used herein, the phrase “essentially the entire thickness” means that at least 90% of the thickness of the porous polymer is filled with the breathable polymer. In other embodiments, a breathable polymer can be applied to the second side of the porous polymer as well as the first side. The breathable polymer applied to the second side may be the same or different from the breathable polymer applied to the first side. In still further embodiments, the porous polymer can be a composite film wherein a breathable polymer is applied to a first side of a first porous polymer with a sufficient amount of the breathable polymer applied to the first side of the porous polymer so as to form a cap layer and a second porous polymer that may be the same or different as the first porous polymer, is thereafter bonded via the cap layer of the breathable polymer. This can result in a 3-layer composite film having 2 porous polymers adhered to one another with the breathable polymer as the layer in between the two porous polymers. If desired, an additional layer or layers of breathable polymer may be applied to one or both of the exterior sides of the composite film.

[0090] In some embodiments, the breathable polymer may be applied to the porous polymer in a continuous manner, so that essentially 100 percent of the surface area of the porous polymer comprises the breathable polymer. As used in this context, the term “continuous” means that the full width or nearly the full width of the porous polymer is coated with the breathable 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 film to be coated. In other embodiments, the breathable polymer may be applied to the porous polymer 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 polymer is coated with the breathable polymer and that portions of the non-edge areas of the porous polymer do not contain the breathable polymer. For example, a breathable polymer applied to the porous polymer as a series of dots or as a grid of orthogonal lines are to be considered as discontinuous coatings. The area percent of the porous polymer that is filled with the breathable 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 toless 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 breathable 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 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.

[0091] As a weight ratio, the porous polymer can have a ratio of the weight of the breathable polymer to the weight of the porous polymer in the range of from 30.0 to 0.5. In other embodiments, the weight ratio of the breathable polymer to the porous polymer 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.

[0092] In still further embodiments, any of the polymers listed above as being useful for the carrier layer may be formed into a nonwoven layer. The nonwoven layer may be waterproof and breathable due to the formation of a network of fine fibers that have passages or open spaces between the fibers that are small enough to exclude liquid water from penetrating, but large enough to allow water vapor to pass through the thickness of the nonwoven layer. In other embodiments, the nonwoven layer may be formed where the density of the fine fibers is too high to allow water vapor to pass through the thickness of the nonwoven layer. In these cases, the nonwoven layer should be formed from polymers that are breathable so that water vapor can be transported through the nonwoven layer by an adsorption / desorption process, wherein water is adsorbed on one side of a nonwoven layer where the water concentration and / or temperature is relatively high, transported through the nonwoven layer and desorbed and / or evaporated on the other side where the water concentration and / or temperature is relatively lower. The nonwoven layer can be produced using known methods, for example, electro spinning or melt blowing processes.

[0093] Many examples of waterproof and breathable polymers are known in the art, however, they are typically not used in applications where the threat of a high energy event is a possibility, due to their inherent meltability and potential flammability. The use of a first layer of the heat reactive material and a flame retardant textile layer canhelp to allow the use of carrier layers that are not typically used where high energy exposure is a possibility.

[0094] In some embodiments, the carrier layer is free from or essentially free from flame retardant or flame resistant additives. In other embodiments, the carrier layer can be a porous film with pores that are at least partially filled with a breathable polymer. In still further embodiments, the breathable polymer that fills at least a portion of the pores comprises a flame retardant additive.

[0095] In some embodiments, the carrier layer can have a relatively light weight, for example, less than or equal to 80 grams per meter2(gsm). In other embodiments, the carrier layer can have a weight of less than or equal to 75 gsm or less than 70 gsm or less than 65 gsm or less than 60 gsm or less than 55 gsm or less than 50 gsm or less than 45 gsm or less than or equal to 40 gsm or less than or equal to 35 gsm or less than or equal to 30 gsm or less than or equal to 25 gsm or less than or equal to 20 gsm or less than or equal to 19 gsm or less than or equal to 18 gsm or less than or equal to 17 gsm or less than or equal to 16 gsm or less than or equal to 15 gsm or less than or equal to 14 gsm or less than or equal to 13 gsm or less than or equal to 12 gsm or less than or equal to 11 gsm or less than or equal to 10 gsm.

[0096] Suitable breathable polymers can include, for example, polyurethane, polyamide, polyester, or a copolymer or a combination thereof. In other embodiments, any of the breathable polymers listed above could be used, provided that the breathable polymer is capable of having a moisture vapor transmission rate of greater than or equal to 1 ,500 grams / meter2 / day or greater than or equal to 5,000 grams / meter2 / day or greater than or equal to 10,000 grams / meter2 / day or greater than or equal to 15,000 grams / meter2 / day or greater than or equal to 20,000 grams / meter2 / day or greater than or equal to 25,000 grams / meter2 / day. The breathable polymer can be a thermoplastic or a crosslinkable polymer. In some embodiments, the breathable polymer is a polyurethane and in further embodiments, the polyurethane is a crosslinked polyurethane. Suitable polyurethane polymers can be, for example, polyesterurethanes, polyetherurethanes or polyether-polyesterurethanes.

[0097] In embodiments where coloring is desired for the carrier layer, the color can be added using any of the known methods. In embodiments comprising a porous polymer,the desired color can be added via a pigmented breathable polymer which can then be coated onto the porous polymer and / or imbibed within the pores of the porous polymer, or the desired color can be added to the porous polymer using known methods, for example, master-batching. Color can be added to the polymer using pigments, dyes or a combination thereof. Therefore, one or both of the porous polymer and the breathable polymer can be colored or uncolored. If both the porous polymer and the breathable polymer are colored, they can be colored in the same or a similar shade or the colors can be chosen independently of one another. In other embodiments, the nonporous polymer and / or the nonwoven layer can be colored during the formation of the nonporous polymer or the nonwoven layer according to known methods. Any of the known pigments or dyes can be used, including, for example, organic pigments and dyes, inorganic pigments or dyes, metals, metal oxides, carbon black, titanium dioxide or combinations thereof.

[0098] The resulting carrier layer 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 / meter2and, 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 1500 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.

[0099] In some embodiments and as exemplified in Figure 1 , the laminate (10) comprises a first textile layer (20), a layer of heat reactive material (30), a carrier layer (40), an adhesive layer (50) and a flame retardant textile layer (60).

[0100] The carrier layer may also comprise antistatic agents, antistatic particles, antistatic polymers, or antistatic fibers as a filler or as a coating. Suitable antistatic agents, particles or polymers can comprise, for example, carbon black, conductive fibers, metal particles, or electrically conductive polymers.

[0101] In some embodiments, the carrier layer can also comprise a flame retardant material. The flame retardant material can be any of those flame retardant materials that are listed above. In embodiments where the carrier layer is a nonporous polymer, the flame retardant material can be added to the polymer according to known methods for example, the flame retardant material can be a filler in the polymer. In embodiments, wherein the carrier layer is a porous polymer optionally filled with a breathable polymer, the flame retardant material can be a filler added to one or both of the porous polymer, to the breathable polymer or to both the porous polymer and the breathable polymer, according to known methods. In embodiments wherein the carrier layer is a nonwoven layer, the flame retardant agent can be added as a filler to the polymer prior to the nonwoven formation process, i.e., as a filler to the polymer melt, or it can be added after the formation of the nonwoven layer where the flame retardant material can adhere to the cooling polymer before the polymer cools below the melting point.

[0102] In some embodiments, the carrier layer is free from the flame retardant materials listed above. It has been surprisingly found that flame retardant materials added to the carrier layer can affect the flame performance of the laminate at least initially. However, over time, the flame retardant materials may not be persistent in the carrier layer and the flame retardant properties may diminish over time.

[0103] ADHESIVE LAYER

[0104] The disclosed laminate comprises d) an adhesive layer; wherein the adhesive layer connects, joins, adheres or otherwise secures a first layer to a second layer that is directly adjacent to the first layer, for example, the carrier layer to the flame retardant textile layer. The adhesive layer can be added to one or both of the layers that are to be adhered to one another by the adhesive layer when producing the laminate. The adhesive layer can be any textile adhesive that is known the art. Suitable textileadhesives can include for example, polyurethanes, acrylics, epoxies, cyanoacrylates, silicone or a combination thereof.

[0105] In some embodiments, the adhesive may comprise one or more flame retardant materials to provide flame resistance. Typical flame retardant materials include any of those listed above. In some embodiments, the flame retardant materials can be, for example, phosphorous-based flame retardants, amine-based flame retardants, or a combination thereof. In some embodiments, the adhesive layer is free from an intumescent compound, for example, expandable graphite.

[0106] The flame retardant adhesive layer can be applied as a continuous or a discontinuous layer. In some embodiments, a continuous layer of the adhesive can be applied to essentially the entire length and width of one or both of the carrier layer and / or the flame retardant textile layer. In other embodiments, a discontinuous layer of the adhesive can be applied to essentially the entire length and width of the carrier layer and / or the flame retardant textile layer.

[0107] A discontinuous layer of the adhesive means that the adhesive layer is applied in a series of dots, lines and / or grids. As used herein, the term “dots” means any discrete or disconnected shape that can be round, linear, polygonal, square, rectangular, pentagonal, hexagonal, etc. that does not overlap or touch an adjacent shape. The dots may have a regular or irregular repeating pattern. The shape of each dot may be the same or the shapes of each dot may be chosen independently of the others. The adhesive layer may be applied using known methods, for example, screen printing, gravure printing, coating, dip coating, roller coating, spray coating, or a combination thereof. As examples of discontinuous adhesive layers, Figures 8A and 8B show two different examples. Figure 8A shows a repeating pattern of round dots of adhesive 830, with areas 820 free from adhesive 830. Figure 8B shows the adhesive 830 applied in a grid pattern and areas 820 free from adhesive 830.

[0108] The adhesive layer may be applied in a discontinuous manner so that the adhesive covers in the range of from 10% to 100% of the surface of one or both of the carrier layer and the flame retardant textile layer. In some embodiments, the adhesive layer covers in the range of from 20% to 90%, or 20% to 80% or from 20% to 75% of the surface of one or both of the carrier layer and the flame retardant textile layer. Inother embodiments, the adhesive layer covers in the range of from 20% to 30% or from 25% to 35% or from 30% to 40% or from 35% to 45% or from 40% to 50% or from 45% to 55% or from 50% to 60% or from 55% to 65% or from 60% to 70% or from 65% to 75% or from 70% to 80% of the surface of one or both of the carrier layer and the flame retardant textile layer.

[0109] At least one of the carrier layer and / or the adhesive layer should contain a flame retardant material. In some embodiments, the laminate comprises a carrier layer that includes flame retardant materials. In some embodiments, the laminate comprises an adhesive layer, wherein the adhesive includes flame retardant materials. In still further embodiments, the laminate comprises a carrier layer and an adhesive layer, wherein both the carrier layer and the adhesive layer include flame retardant materials.

[0110] FLAME RETARDANT TEXTILE LAYER

[0111] The disclosed laminate also comprises a flame retardant textile layer. Flame retardant textiles are well-known and can include fibers, filaments, or yarns made from inherently flame-retardant materials, from materials that have been treated with one or more flame retardant materials to be made flame retardant or from a combination thereof. The flame retardant textile layer can be an inner layer of the laminate, that is, adjacent to the carrier layer on the opposite side of the first textile layer, or the flame retardant textile layer can be located in between the first textile layer and the carrier layer. In those embodiments where the flame retardant textile layer is an inner layer of the laminate, garments produced from the laminate would have the flame retardant textile layer as the layer closest to the wearer and the first textile layer would be an outer layer, preferably the outermost layer. In those embodiments where the flame retardant textile layer is in between the first textile layer and the carrier layer, garments produced with this laminate would have the carrier layer as the layer closest to the wearer and the first textile layer would be an outer layer, preferably the outermost layer.

[0112] Suitable fibers, filaments, or yarns that can be used to make the flame retardant textile can include, for example, aramids, p-aramid, m-aramid, polybenzimidazole (PBI), polybenzoxazole (PBO), polyetheretherketone, polyetherketoneketone, polyphenylene sulfide, polyimide, polyamide imide, melamine, fluoropolymer, polytetrafluoroethylene, modacrylic, cellulose, FR cellulose, FR viscose, FR polyester, FR polyamide,polyvinylacetate, polyacrylonitrile (PAN), melamine, oxidized polyacrylonitrile fiber, alumina fibers, fiberglass, carbon fibers, mineral fibers, protein fibers, or a combination thereof. A small proportion, for example, less than 50%, less than 40%, less than 30%, or less than 20% by weight, of the fibers, filaments or yarns may be materials that are typically considered to be meltable materials, for example, the meltable materials described above for the first textile layer, wherein the percentage by weight is based on the total weight of the flame retardant textile layer.

[0113] In still further embodiments, a small proportion, for example, less than 10% by weight of antistatic fibers, filaments or particles may be added to the flame retardant textile, wherein the percentage by weight of the antistatic fibers or filaments is based on the total weight of the flame retardant textile. Suitable antistatic fibers / filaments are known in the art and can include, for example, conductive metals, copper, nickel, stainless steel, steel, gold, silver, titanium, carbon fibers, or a combination thereof.

[0114] In some embodiments, the flame retardant textile layer can be a knit, a woven or a nonwoven textile. Suitable examples of a flame retardant textile can comprise 20% to 50% of an aramid, 50% to 80% FR viscose and optionally, 5% to 15% nylon. In other embodiments, the flame retardant textile can include 20% to 30% aramid, 60% to 70% FR viscose, and 10 to 20% nylon. Suitable examples of a flame retardant textile can comprise 20% to 50% of an aramid, 50% to 80% FR viscose and optionally, 5% to 15% polyester. In other embodiments, the flame retardant textile can include 20% to 30% aramid, 60% to 70% FR viscose, and 10 to 20% polyester. All percentage by weight are based on the total weight of the flame retardant textile.

[0115] The flame retardant textile can have a weight in the range of from 20 grams per square meter (gsm) to about 300 gsm. In other embodiments, the flame retardant textile can have a weight in the range of from 25 gsm to about 275 gsm, or from 30 gsm to 275 gsm, or from 40 gsm to about 275 gsm, or from about 50 gsm to about 275 gsm, or from 55 gsm to about 275 gsm, or from 60 gsm to about 275 gsm, or from 65 gsm to about 275 gsm, or from 70 gsm to about 285 gsm, or from 75 gsm to about 275 gsm, or from 80 gsm to about 275 gsm, or from 85 gsm to about 275 gsm, or from 90 gsm to about 250 gsm, or from 90 gsm to about 240 gsm, or from 90 gsm to about 230 gsm, or from 90 gsm to about 225 gsm, or from 90 gsm to about 220 gsm.

[0116] In some embodiments, as exemplified by Figure 1 , the laminate (10) comprises a first textile layer (20), a layer of heat reactive material (30), a carrier layer (40), an adhesive layer (50) as a series of discontinuous dots, and a flame retardant textile layer (60). In a further embodiment, as exemplified in Figures 2 and 3, the laminate (10) may comprise a first textile layer (20), a layer of heat reactive material (30), a carrier layer (40) that may include a porous layer (42), an adhesive layer (50), and a flame retardant textile layer (60). The carrier layer (40) comprises a porous layer (42, shown as a dark colored rectangle outline) and a breathable polymer layer (44, shown as cross-hatched pattern), which may form a cap layer (45) on one side of the porous layer. While Figures 2 and 3 show the cap layer oriented toward the direction of the flame retardant textile layer (60), in other embodiments, the cap layer can be oriented toward the first textile layer (20). In some embodiments, such as shown in Figure 2, the breathable polymer layer (44) spans the entire thickness of the porous layer (42). In other embodiments, such as shown in Figure 3, the breathable polymer layer (44) spans less than the entire thickness of the porous layer (42). The breathable polymer layer (44) may be waterproof or air impermeable or both. The breathable polymer layer (44) may be a polyurethane or a layer of polyurethane that contains one or more flame retardant agents.

[0117] In other embodiments, and as shown in Figure 4, the laminate (10) comprises a first textile layer (20), a layer of the heat reactive material (30), a flame retardant textile layer (60), an adhesive layer (50) (e.g., applied discontinuously, such as in a series of discontinuous dots), and a carrier layer (40). The carrier layer (40) can be any of the carrier layers described herein, including the carrier layers (40) described with reference to Figures 2, 3, 6, or 7. In still further embodiments, and as shown in Figure 5, the laminate (10) comprises a first textile layer (20), a layer of the heat reactive material (30), a flame retardant textile layer (60), an adhesive layer (50) (e.g., applied discontinuously, such as in a series of discontinuous dots), a carrier layer (40), an adhesive layer (70), and a second textile layer (80). In embodiments of Figure 5, the adhesive layer (70) can be the same or different as adhesive layer (50) and the second textile layer (80) can be chosen from the same materials as described for the first textilelayer. The textile used in the second textile layer (80) can be chosen independently from the textile used in the first textile layer (20).

[0118] In embodiments shown in Figures 6 and 7, the laminate (10) may comprise a first textile layer (20), a layer of heat reactive material (30), a flame retardant textile layer (60), an adhesive layer (50), and a carrier layer (40). In some embodiments, such as shown in Figures 6 and 7, the laminate (10), includes an optional second textile layer (80) adhered by a further adhesive layer (70). In some embodiments, the second textile layer (80) and the further adhesive layer (70) are omitted. The carrier layer (40) comprises a porous layer (42, shown as a dark colored rectangle outline) and a breathable polymer layer (44, shown as cross-hatched pattern), which may form a cap layer (45) on one side of the porous layer. While Figures 6 and 7 show the cap layer (45) oriented toward the direction of the second textile layer (80), in other embodiments, the cap layer (45) can be oriented toward the first textile layer (20). In some embodiments, such as shown in Figure 6, the breathable polymer layer (44) spans the entire thickness of the porous layer (42). In other embodiments, such as shown in Figure 7, the breathable polymer layer (44) spans less than the entire thickness of the porous layer (42). The breathable polymer layer (44) may be waterproof or air impermeable or both. The breathable polymer layer (44) may be a polyurethane or a layer of polyurethane that contains one or more flame retardant agents.

[0119] SECOND TEXTILE LAYER

[0120] In some embodiments, the laminate comprises the first textile layer, the layer of heat reactive material, the flame retardant textile layer, the first adhesive layer, the carrier layer, and further comprises a second layer of adhesive and a second textile layer. The second textile layer can independently be selected from any of the previously described in the section describing the first textile layer. In embodiments comprising the second textile layer, articles made from laminates and intended to be worn as protective garments are formed so that the first textile layer is an outer layer of the garment, and the second textile layer is an inner layer of the garment.

[0121] LAMINATE FORMATION

[0122] The disclosure also relates to methods of making the laminate of any of the embodiments described herein. The laminate may be made in a stepwise method or acontinuous method. In some embodiments, the stepwise method for forming the laminate comprises i) adhering the first textile layer to the carrier layer with a layer of the heat reactive material to form a precursor laminate; and ii) adhering the precursor laminate to the flame retardant textile layer with the adhesive layer. In other embodiments, the stepwise method for forming the laminate comprises i) adhering the flame retardant textile layer to the carrier layer with the adhesive layer to form a precursor laminate; and ii) adhering the precursor laminate to the first textile layer with a layer of the heat reactive material.

[0123] In other embodiments, the stepwise method for forming the laminate comprises i) adhering the first textile layer to the flame retardant textile layer with a layer of the heat reactive material to form the precursor laminate; and ii) adhering the precursor laminate to the carrier layer with the adhesive layer. In some embodiments, the method may further comprise iii) optionally adhering a second textile layer to the carrier layer using an adhesive layer. In still further embodiments, a stepwise method for forming the laminate comprises i) adhering the carrier layer to the flame retardant layer with the adhesive layer to form a precursor laminate; and ii) adhering the precursor laminate to the first textile layer with the heat reactive material. The method may further comprise iii) optionally adhering a second textile layer to the carrier layer using an adhesive layer.

[0124] In any of the above stepwise methods, a layer of the heat reactive material can be applied to the first textile layer, to the carrier layer, and / or to the flame retardant textile layer, depending upon the final configuration of the laminate or the precursor laminate. The desired layers can then be adhered together by the application of pressure and / or heat to produce the precursor laminate including the first textile layer, the heat reactive layer and the carrier layer or to produce the precursor laminate comprising the first textile layer, the heat reactive layer, and the flame retardant textile layer. Care should be taken if heat is used so that the heat will sufficiently soften and / or begin to cure the polymer resin of the heat reactive layer, but does not cause the expandable graphite to expand. The precursor laminate can then be used as is, or stored for a length of time from hours to days or longer.

[0125] Once the precursor laminate is formed, then the remaining layers can be adhered to form the laminate. In some embodiments, the adhesive layer can be appliedto the carrier layer side of the precursor laminate, to the flame retardant textile layer or to both the carrier layer side of the precursor laminate and the flame retardant textile layer. After application of the adhesive layer, the precursor laminate and the flame retardant textile can then be applied together via the adhesive layer with the application of pressure, heat or pressure and heat. As before, if heat is applied, it should be high enough to bond the two layers together, without causing the expansion of the expandable graphite. In other embodiments, the adhesive layer can be applied to the flame retardant textile layer side of the precursor laminate, to the carrier layer, or to both the flame retardant textile layer side of the precursor laminate and the carrier layer. After application of the adhesive layer, the precursor laminate and the carrier layer can be applied together via the adhesive layer with the application of pressure, heat, or pressure and heat. If desired, the second textile layer can be applied to the carrier layer using an adhesive in a similar manner as described for adhering the carrier layer to the precursor laminate, with the second textile layer being applied adjacent to the carrier layer.

[0126] In other embodiments, the flame retardant textile layer and the carrier layer can first be joined together with the adhesive layer so that the precursor laminate comprises the flame retardant textile layer and the carrier layer. In a second step, the first textile layer can be adhered to the precursor laminate via a layer of the heat reactive material, with the first textile layer being placed on the carrier layer side of the precursor laminate, or the first textile layer being placed on the flame retardant textile layer side of the precursor laminate.

[0127] In other embodiments, the laminate can be produced in a continuous manner according to processes known for the lamination of roll goods. For example, the process can comprise adding a layer of the heat reactive material to the first textile layer, to a first side of the carrier layer, or to both the first textile layer and to the first side of the carrier layer; adding the adhesive layer to a second side of the carrier layer, to the flame retardant textile layer, or to both the second side of the carrier layer and to the flame retardant textile layer; and adhering the first textile layer to the carrier layer via the heat reactive material and adhering the flame retardant textile layer to the carrier layer via the adhesive layer. The step of adhering the various layers can be donesimultaneously, within a few seconds, or within minutes of each other via a series of rolls or rollers, optionally with the application of heat.

[0128] In still further embodiments, the laminate can be produced in a continuous manner by adding a layer of the heat reactive material to the first textile layer, to a first side of the flame retardant textile layer, or to both the first textile layer and the first side of the flame retardant textile layer; adding the adhesive layer to a second side of the flame retardant textile layer, to the carrier layer, or to both the second side of the flame retardant textile layer and the carrier layer; and adhering the first textile layer to the flame retardant layer via the heat reactive material and adhering the flame retardant textile layer to the carrier layer via the adhesive layer. The step of adhering the various layers can be done simultaneously, within a few seconds, or within minutes of each other via a series of rolls or rollers, optionally with the application of heat.

[0129] In any of the above embodiments, the layer of heat reactive material can be applied in a discontinuous manner so that covers greater than or equal to 25% of the surface area of the first textile layer and / or the carrier layer. In other embodiments, the heat reactive material can be applied so that it covers from about 25% to about 75% of the surface area of the first textile layer and / or the carrier layer. In a similar manner, the adhesive layer can be applied in a discontinuous manner so that it covers greater than or equal to 25% of the surface area of the carrier layer and / or the flame retardant textile layer. In other embodiments, the adhesive layer can be applied so that it covers from about 25% to about 75% of the surface area of the flame retardant textile layer and / or the carrier layer.

[0130] In some embodiments, the laminate has a weight of less than or equal to 500 grams / meter2(gsm). In other embodiments, the laminates have a weight of less than or equal to 450 gsm, or less than or equal to 425 gsm or less than or equal to 400 gsm, or less than or equal to 375 gsm, or less than or equal to 350 gsm, or less than or equal to 325 gsm.

[0131] The laminates described herein can provide a lightweight laminate that can provide protection against an electric arc as measured by I EC 61482-2 in the Electric Arc Box test (I EC 61482-1-2:2014) and / or the Open Arc Test (I EC 61482-1-1 :2009, method A). In some embodiments, the laminates described herein complies with thestandards IEC 61482-1-1 :2014 and / or IEC 61482-1-2:2014 and has a weight of less than or equal to 500 gsm. In some embodiments, the laminates described herein complies with the standards IEC 61482-1 -1 :2014 and / or IEC 61482-1-2:2014 and has a weight of less than or equal to 475 gsm. In some embodiments, the laminates described herein complies with the standards IEC 61482-1-1 :2014 and / or IEC 61482-1 - 2:2014 and has a weight of less than or equal to 450 gsm. In some embodiments, the laminates described herein complies with the standards IEC 61482-1-1 :2014 and / or IEC 61482-1-2:2014 and has a weight of less than or equal to 425 gsm. In some embodiments, the laminates described herein complies with the standards IEC 61482- 1-1 :2014 and / or IEC 61482-1-2:2014 and has a weight of less than or equal to 400 gsm. In some embodiments, the laminates described herein complies with the standards IEC 61482-1-1 :2014 and / or IEC 61482-1-2:2014 and has a weight of less than or equal to 375 gsm. In some embodiments, the laminates described herein complies with the standards IEC 61482-1 -1 :2014 and / or IEC 61482-1-2:2014 and has a weight of less than or equal to 350 gsm. In some embodiments, the laminates described herein complies with the standards IEC 61482-1-1 :2014 and / or IEC 61482-1 - 2:2014 and has a weight of less than or equal to 325 gsm. In some embodiments, the laminates described herein complies with the standards IEC 61482-1-1 :2014 and / or IEC 61482-1-2:2014 and has a weight of less than or equal to 300 gsm. In some embodiments, the laminates described herein complies with the standards IEC 61482- 1-1 :2014 and / or IEC 61482-1-2:2014 and has a weight of less than or equal to 275 gsm. In some embodiments, the laminates described herein complies with the standards IEC 61482-1-1 :2014 and / or IEC 61482-1-2:2014 and has a weight of less than or equal to 265 gsm. In some embodiments, the laminates described herein complies with the standards IEC 61482-1 -1 :2014 and / or IEC 61482-1-2:2014 and has a weight of less than or equal to 250 gsm. In some embodiments, the laminates described herein complies with the standards IEC 61482-1-1 :2014 and / or IEC 61482-1- 2:2014 and has a weight between 250 gsm and 400 gsm.

[0132] USES

[0133] Laminates as described herein can be useful to make an article, for example, a protective article. The protective articles can include, for example, garments such asshirts, jackets, pants, coveralls, overalls, aprons, hats, gloves and footwear; covers, blankets, tents and more. In each of these applications, the laminate should be oriented such that the first textile layer faces the potential high energy event. For example, wherein the laminate is used to form a jacket, the first textile layer should be oriented to face an outer portion of the jacket with the remaining layers, for example, the carrier layer and / or flame retardant textile layer closer to a wearer so that in the event of exposure to a high energy or high temperature event, the first textile layer is exposed to the energy or high temperature before the other layers.

[0134] TEST METHODS

[0135] Gurley

[0136] The Gurley air flow test measures the time it takes in seconds for 100 cm3of air to flow through a 6.45 cm2sample 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 automatic digital timer. The reported results are the average of multiple measurements.

[0137] Melting and Thermal Stability TestThe test was used to determine the thermal stability of textile materials. This test was based on thermal stability test as described in section 8.3 of NFPA 1975, 2004 Edition. The test oven was a hot air circulating oven as specified in ISO 17493. The test was conducted according to ASTM D 751 , Standard Test Methods for Coated Fabrics, using the Procedures for Blocking Resistance at Elevated Temperatures (Sections 89 to 93), with the following modifications:

[0138] Borosilicate glass plates measuring 100 millimeters (mm) x 100 mm x 3 mm (4 inches (in) x 4 in x 1 / 8 in) were used; and

[0139] An internal oven test temperature of 280°C ± 5°C was used. The specimens were allowed to cool a minimum of 1 hour after removal of the glass plates from the oven.

[0140] Any sample side sticking to the glass plate, sticking to itself when unfolded or showing evidence of melting or dripping was considered as meltable. Any sample lacking evidence of melting was then retested (using a new sample of the material) at an internal oven test temperature of 300°C. After removal from the oven and cooling for1 hour, any sample side sticking to the glass plate, sticking to itself when unfolded or showing evidence of melting or dripping was considered as meltable. Any sample not showing one of these melting criteria was considered to be a non-meltable sample and / or no-drip sample.

[0141] TMA Expansion test:TMA (Thermo-mechanical analysis) was used to measure the expansion of expandable graphite particles. Expansion was tested with TA Instruments TMA 2940 instrument. A ceramic (alumina) TGA pan, measuring roughly 8mm in diameter and 12mm in height was used for holding the sample. Using the macro-expansion probe, with a diameter of roughly 6mm, the bottom of the pan was set to zero. Flakes of expandable graphite about 0.1 -0.3mm deep, as measured by the TMA probe applying a compressive load of 0.005 N, were placed in the pan. The furnace was closed, and initial sample height was measured. The furnace was heated from about 25°C to 600°C at a ramp rate of 10°C / min. The TMA probe displacement was plotted against temperature; and the dimension change normalized for the initial sample height was used as a measure of expansion.

[0142] DSC Endotherm Test:Tests were run on a Q2000 DSC from TA Instruments using TZERO T™ hermetic pans. For each sample, about 3 milligrams (mg) of expandable graphite were placed in the pan. The pan was vented by pressing the corner of a razor blade into the center, creating a vent that was approximately 2 mm long and less than 1 mm wide. The DSC was equilibrated at 20°C. Samples were then heated from 20°C to 400°C at 10°C / min. Endotherm values were obtained from the DSC curves.

[0143] Weight:Weight measurements on materials were conducted as specified in ASTM D751 , section 10. The units given are in grams per square meter.

[0144] Electric Arc Box Tests were performed using IEC 61482-1-2:2014.

[0145] The electric arc box test provides information about the performance of the material relative to the Stoll curve, a result of “below” means that the material passes that portion of the test, while a result of “above” means that material failed the test. The box test also provides a measure of the burn time (pass <5 seconds, fail >5 seconds);hole formation (tested material passes this part of the test with no hole larger than 5mm); and an overall pass / fail designation.

[0146] Open arc test was performed according to IEC 61482-1-1 :2009, method A.

[0147] The data is provided as the Arc Thermal Performance Value and is provide in units of calories per square centimeter (cal / cm2).

[0148] Furnace Expansion Test

[0149] A nickel crucible was heated in a hot furnace at 300°C for 2 minutes. A measured sample (about 0.5 g) of expandable graphite was added to the crucible and placed in the hot furnace at 300°C for 3 minutes. After the heating period, the crucible was removed from the furnace and allowed to cool and then the expanded graphite was transferred to a measuring cylinder to measure expanded volume. The expanded volume was divided by the initial weight of the sample to get expansion in cc / g units.

[0150] Air Permeability Test:To test the air permeability of a carrier film layer after thermal exposure, a 381 mm (15 in.) square specimen was clamped in a metal frame and then suspended in a forced aircirculating oven set to a temperature of 260°C. Following a 5-minute exposure, the specimen was removed from the oven. After allowing the specimen to cool down, the air permeability of the specimen was tested according to test methods entitled ISO 9237 (1995).

[0151] Vertical Flame Test

[0152] Testing was performed in accordance with the ASTM D6413. Samples were exposed to flame for 12-seconds. After-flame time was averaged for 3 samples. Laminates with after-flame of greater than 2 seconds were considered as flammable. Char length was also determined by this test. Samples were tested in both the warp and weft directions.

[0153] Horizontal flame Test

[0154] Procedure was followed according to ISO 15025 and the tests were performed on the face side and separately on the back side of the laminate. The test provided information on afterflame and the duration in seconds (if any); afterglow; hole formation; the presence of flaming debris; and the presence of flaming to the upper or vertical edge of the material.

[0155] Moisture Vapor Transmission Rate (MVTR)

[0156] A description of the test employed to measure moisture vapor transmission rate (MVTR) is given below. The procedure has been found to be suitable for testing films, coatings, and coated products.

[0157] In the procedure, approximately 70 ml of a solution consisting of 35 parts by weight of potassium acetate and 15 parts by weight of distilled water are placed into a 133 ml polypropylene cup, having an inside diameter of 6.5 cm at its mouth. An expanded polytetrafluoroethylene (PTFE) membrane having a minimum MVTR of approximately 85,000 g / m2 / 24 hrs. as tested by the method described in U.S. Patent 4,862,730 (to Crosby), is heat sealed to the lip of the cup to create a taut, leakproof, porous barrier containing the solution.

[0158] A similar expanded PTFE membrane is mounted to the surface of a water bath. The water bath assembly is controlled at 23°C plus 0.2°C, utilizing a temperature controlled room and a water circulating bath.

[0159] The sample to be tested is allowed to condition at a temperature of 23°C and a relative humidity of 50% prior to performing the test procedure. Samples are placed so the porous polymeric membrane is in contact with the expanded polytetrafluoroethylene membrane mounted to the surface of the water bath and allowed to equilibrate for at least 15 minutes prior to the introduction of the cup assembly.

[0160] The cup assembly is weighed to the nearest 1 / 1000g and placed in an inverted manner onto the center of the test sample.

[0161] Water transport is provided by the driving force between the water in the water bath and the saturated salt solution providing water flux by diffusion in that direction. The sample is tested for 15 minutes, and the cup assembly is then removed, weighed again within 1 / 1000g. The MVTR of the sample is calculated from the weight gain of the cup assembly and is expressed in grams of water per square meter of sample surface area per 24 hours.

[0162] Edge Ignition Test

[0163] The edge ignition test was performed according to ISO 11612. This test provided information on afterflame and the duration in seconds (if any); afterglow; holeformation; the presence of flaming debris; and the presence of flaming to the upper or vertical edge of the material.

[0164] EXAMPLES

[0165] Heat Reactive Material

[0166] A flame retardant polyurethane resin was prepared by first forming a resin in accordance with the examples of commonly owned U. S. Pat. No. 4,532,316 and adding in the reactor a phosphorus-based additive FYROLFLEX® RDP, phosphate ester in an amount of about 20% by weight. After the polyurethane resin was formed, 65 parts by weight of the polyurethane resin was mixed with 24 parts by weight of expandable graphite (the expandable graphite having an expansion of greater than 900 micrometers at 280°C as determined by the TMA Expansion test) and an additional 17 parts by weight of another phosphorus-based flame retardant agent at 80°C in a stirring vessel. The mixture was cooled and used as is.

[0167] Heat Reactive Material #2

[0168] An aqueous acrylic-based heat reactive material comprising expandable graphite and using melamine phosphate as a flame retardant additive was produced according to US 2024 / 0165917, the content of which are incorporated herein by reference, in its entirety.

[0169] Flame retardant (FR) AdhesiveA flame retardant adhesive prepared by first forming a polyurethane resin according to commonly owned U.S. Patent No. 4,532,316 and adding in to the reactor a phosphorus- based flame retardant material, in an amount of about 20% by weight.

[0170] Polyethylene film #1

[0171] A waterproof breathable porous polyethylene membrane was prepared according to co-owned WO 2020 / 028328, which is incorporated herein in its entirety. The porous membrane comprised an ultrahigh molecular weight porous polyethylene film and the pores of the porous polyethylene were filled with a breathable polyurethane polymer that formed a cap layer on one side of the film.

[0172] Polyethylene #2

[0173] A waterproof breathable porous polyethylene membrane was prepared according to co-owned WO 2020 / 028328, which is incorporated herein in its entirety.The porous membrane comprised an ultrahigh molecular weight porous polyethylene film and the pores of the porous polyethylene were filled with a breathable polyurethane polymer that formed a cap layer on one side of the film. The breathable polyurethane polymer was filled with a mixture of titanium dioxide and aluminum flakes to provide a film having a silver / grey color.

[0174] Laminate #1

[0175] The heat reactive material was applied using a gravure roll and having a pattern of repeating dots providing an adhesive area coverage of about 40%-45% and an adhesive laydown of 35-40 grams per meter2(gsm) to the surface of polyethylene film #1 as the carrier layer on the side opposite the cap layer of breathable polyurethane polymer. A first textile layer comprising a meltable 90 gsm plain weave polyester (item no. RJ47PmbG-T from Na Ya Plastics Corp., Taipei City, Taiwan) was applied to the dots of heat reactive material and rolled between the nip of two rollers. The precursor laminate was allowed to cure for at least 24 hours.

[0176] A flame retardant textile was then adhered to the carrier layer opposite the first textile by applying a layer of a flame retardant polyurethane adhesive with a discontinuous dot pattern of the flame retardant polyurethane adhesive. The flame retardant textile was a 93 gsm knit comprising 23% TWARON® aramid, 65% flame retardant viscose and 12% polyamide (item #12643, available from Fuchshuber Techno-Tex, Wurttemberg, Germany). The laminate was rolled through the nip of two rollers and allowed to cure at least 24 hours.

[0177] Laminate #2

[0178] The heat reactive material was applied using a gravure roll and having a pattern of repeating dots providing an adhesive area coverage of about 50%-55% and an adhesive laydown of 50-55 grams meter2(gsm) to the surface of polyethylene film #1 as the carrier layer on the side opposite the cap layer of breathable polyurethane polymer. A first textile layer comprising a meltable 90 gsm plain weave polyester (item no. RJ47PmbG-T from Na Ya Plastics Corp., Taipei City, Taiwan) was applied to the dots of heat reactive material and rolled between the nip of two rollers. The precursor laminate was allowed to cure for at least 24 hours.

[0179] A flame retardant textile was then adhered to the carrier layer opposite the first textile by applying a layer of a flame retardant polyurethane adhesive with a discontinuous dot pattern of the flame retardant polyurethane adhesive. The flame retardant textile was a 93 gsm knit comprising 23% TWARON® aramid, 65% flame retardant viscose and 12% polyamide (item #12643, available from Fuchshuber Techno-Tex, Wurttemberg, Germany) The laminate was rolled through the nip of two rollers and allowed to cure at least 24 hours.

[0180] Laminate #3

[0181] A precursor laminate was produced by screen printing a layer of heat reactive material #2 onto an 85 gsm 100% polyester woven fabric (part # P87pb, available from Nan Ya Plastics Corp., Taipei City, Taiwan). The screen printing was a discontinuous dot pattern designed to apply about 55 gsm of the dried heat reactive material. After the layer of heat reactive material #2 was applied to the polyester woven textile, a 60 gsm jersey knit flame retardant textile (50% KERMEL / 50% FR viscose, part #233006077-A, available from Life Textiles GmbH, Helmbrechts, Germany) was applied to the exposed heat reactive material side to form a precursor laminate A. Precursor laminate A was allowed to cure for at least 24 hours.

[0182] The laminate was prepared by gravure printing the FR adhesive to the non-cap side of polyethylene #2. Following the application of the FR adhesive, precursor laminate A was applied, with the jersey knit FR textile side applied directly to the adhesive and the laminate was run through rollers to ensure good adhesion. The laminate was allowed to age for at least 24 hours prior to testing and had a basis weight of 220 gsm.

[0183] Laminate #4

[0184] A precursor laminate was produced by screen printing a layer of heat reactive material #2 onto an 85 gsm 100% polyester woven fabric (part # P87pb, available from Nan Ya Plastics Corp., Taipei City, Taiwan). The screen printing was a discontinuous dot pattern designed to apply about 55 gsm of the dried heat reactive material. After the layer of heat reactive material #2 was applied to the polyester woven textile, a 93 gsm knit flame retardant textile (65% Lenzing FR / 23% p-aramid / 12% polyamide, part #V00014-58, available from Fuchshuber Techno-Tex, GmbH, Baden-Wurttemberg,Germany) was applied to the exposed heat reactive material side to form a precursor laminate B. Precursor laminate B was allowed to cure for at least 24 hours.

[0185] Laminate #4 was prepared by gravure printing the FR adhesive to the non-cap side of polyethylene #2. Following the application of the FR adhesive, precursor laminate B was applied, with the knit FR textile side applied directly to the adhesive and the laminate was run through rollers to ensure good adhesion. The laminate was allowed to age for at least 24 hours prior to testing and had a basis weight of 245 gsm.

[0186] Laminates #3 and #4 were tested according to the horizontal flame testing of ISO 15025-A. With the flame being applied to the polyester woven side of the laminates. According to this test, laminates #3 and #4 exhibited 0 seconds afterflame, no hole formation, no melting and no dripping.

Claims

Claims1. A laminate comprising: a) a first textile layer; b) a layer of heat reactive material; c) a carrier layer comprising a meltable material; d) an adhesive layer; and e) a flame retardant textile layer; wherein the layer of heat reactive material is between the first textile layer and the carrier layer.

2. The laminate of claim 1 wherein the layer of heat reactive material is applied in a continuous manner or a discontinuous manner.

3. The laminate of claim 1 or 2 wherein the layer of heat reactive material is in a pattern of discontinuous dots, lines, or grids.

4. The laminate of any one of claims 1 to 3 wherein the heat reactive material comprises expandable graphite, and wherein the expandable graphite expands at least about 900 micrometers upon heating to about 280°C, as measured in a TMA expansion test.

5. The laminate of any one of claims 1 to 4 wherein at least one of b) the layer of heat reactive material, c) the carrier layer comprising a meltable material, or d) the adhesive layer comprises a flame retardant additive.

6. The laminate of any one of claims 1 to 5, wherein the carrier layer is a porous film, a nonporous film, or a nonwoven layer.

7. The laminate of any one of claims 1 to 6, wherein the carrier layer comprises a breathable polymer.

8. The laminate of any one of claims 1 to 7, wherein the first textile layer comprises at least one meltable fiber.

9. The laminate of any one of claims 1 to 8, wherein the carrier layer comprises porous polyethylene and the porous polyethylene is an expanded ultrahigh molecular weight polyethylene.

10. The laminate according to any one of claims 7, 8 or 9, wherein the breathable polymer is a polyurethane, polyamide, polyester, polyether, ionomer, or a copolymer or a combination thereof.11 . The laminate of any one of claims 1 to 10 wherein the layer of heat reactive material covers greater than or equal to 25% of a surface of the first textile layer.

12. The laminate of any one of claims 1 to 11 , wherein the flame retardant textile comprises one or more of aramids, p-aramid, m-aramid, polybenzimidazole (PBI), polybenzoxazole (PBO), polyetheretherketone, polyetherketoneketone, polyphenylene sulfide, polyimide, polyamide imide, melamine, fluoropolymer, polytetrafluoroethylene, modacrylic, cellulose, flame retardant cellulose, flame retardant viscose, flame retardant polyester, flame retardant polyamide, polyvinylacetate, polyacrylonitrile (PAN), melamine, fiberglass, carbon fibers, mineral fibers, protein fibers, or a combination thereof.

13. The laminate of any one of claims 1 to 12, wherein the carrier layer comprises a film that is nonporous, a film that is porous, and / or a nonwoven layer.

14. The laminate of any one of claims 1 to 13, wherein the laminate passes an Arc Flash Box test Class 1 according to I EC 61482-1 .

15. The laminate of any one of claims 1 to 14, wherein the laminate passes a Box test Class 2 according to I EC 61482-1-2 and has a laminate weight of between 250 grams per square meter and 400 grams per square meter.

16. An article comprising the laminate of any one of claims 1 to 15.

17. The article of claim 16, wherein the article is a garment.

18. A method comprising: i) adhering a first textile layer to a carrier layer with a heat reactive material to form a precursor laminate; and ii) adhering the precursor laminate to a flame retardant textile using a flame retardant adhesive; wherein the flame retardant textile is applied to the precursor laminate adjacent to the carrier layer of the precursor laminate.

19. A laminate comprising: a) a first textile layer; b) a layer of heat reactive material; c) a flame retardant textile layer; d) a first adhesive layer; e) a carrier layer comprising a meltable material; and wherein the layer of heat reactive material is between the first textile layer and the flame retardant textile layer.

20. The laminate of claim 19, wherein the laminate further comprises f) a second adhesive layer on the carrier layer on a side opposite the first adhesive layer and g) a second textile layer adjacent to the second adhesive layer.

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