High Energy Protective Laminate

Abstract

To provide a waterproof, flame-retardant, and arc-flash resistant protective garment that minimizes or eliminates the use of traditional non-flammable and non-melting fabric textiles used in the fire fighting industry. The present disclosure relates to flame-retardant textiles and flame-retardant laminates that can be used to make flame-retardant garments. The laminates described herein enable non-flame-retardant textiles to be used in the manufacture of flame-retardant laminates. The use of non-flame-retardant textiles can provide laminates that are significantly lighter, more comfortable against the skin, more breathable, more durable, available in a wider range of colors, have better moisture management properties and mechanical strength, and are more environmentally friendly than flame-retardant laminates made with inherently flame-retardant textiles.

Description

[Technical Field]

[0001] The present disclosure relates to lightweight protective laminates comprising multiple layers of textiles, which can provide protection against flash fires and electrical arcs, among other things. [Background technology]

[0002] For professional work in hazardous environments where brief exposure to flames or electrical arc flashes is possible, protective laminates and garments are desirable to reduce injury. Protective equipment for workers exposed to these conditions should provide a level of enhanced protection that allows the wearer to quickly and safely escape from the hazard, rather than react to it.

[0003] Traditionally, garments offering protection against short-term flash fire and electrical flash exposure have been relatively heavy and require multiple layers, with each layer providing an additional level of protection against the heat of the exposure. Such garments are manufactured with multiple layers containing flame-resistant, non-melting fabrics made from, for example, aramid, polybenzimidazole (PBI), poly-p-phenylene-2,6-benzobisoxazole (PBO), modacrylic blends, polyamines, carbon, polyacrylonitrile (PAN), and blends and combinations thereof. While these fibers can be inherently flame-resistant and are often used in the firefighting industry, they have several limitations. Specifically, to achieve the desired level of protection, relatively heavy and bulky fabrics are required. Traditionally, these fabrics can have a basis weight exceeding 400 grams per square meter. The fibers used to form these fabrics can be very expensive, difficult to dye or print, and may not be sufficiently abrasion-resistant. Furthermore, these fibers absorb more water and do not provide satisfactory tactile comfort compared to nylon or polyester based fabrics. Summary of the Invention [Problem to be solved by the invention]

[0004] For optimal wearer performance in environments where arc flash exposure is a possibility, lightweight, breathable, water-resistant garments with enhanced burn protection may be desirable. There remains a need for waterproof, flame-retardant (FR), arc-flash resistant protective apparel that minimizes or eliminates the use of customary flame-resistant and non-melting fabric textiles used in the firefighting industry. [Means for solving the problem]

[0005] In a first embodiment, the present disclosure relates to a laminate including: a) a first textile layer; b) a first layer of a thermally reactive material; c) a carrier layer; d) a second layer of a thermally reactive material; and e) a second textile layer. In the embodiments described herein, the first and second layers of a thermally reactive material each independently comprise a polymer resin and expandable graphite. Furthermore, the first layer of a thermally reactive material is positioned between the first textile layer and the carrier layer, and the second layer of a thermally reactive material is positioned between the carrier layer and the second textile layer.

[0006] In a second embodiment, each layer of thermally reactive material is applied independently, either continuously or discontinuously.

[0007] In any of the foregoing embodiments, each layer of thermally reactive material may be in the form of a pattern of discontinuous dots, lines, or grids.

[0008] In any of the foregoing embodiments, at least one of the first and second layers of thermally reactive material includes a flame retardant additive.

[0009] In any of the foregoing embodiments, the first textile layer comprises or consists essentially of meltable fibers. In any of the foregoing embodiments, the first textile layer comprises or consists essentially of non-meltable fibers. In any of the foregoing embodiments, the first textile layer comprises or consists essentially of a mixture of meltable and non-meltable fibers.

[0010] In any of the foregoing embodiments, the first textile layer can include 0% to 100% meltable fibers, based on the total weight of meltable and non-meltable fibers in the first textile layer. In other embodiments, the first textile layer can include greater than 0% to 100% meltable fibers, or 0.5% to 100% meltable fibers, or 1% to 100% meltable fibers, or 1% to 99% meltable fibers, or 3% to 100% meltable fibers, or 5% to 100% meltable fibers, or 10% to 100% meltable fibers, or 20% to 100% meltable fibers, or 25% to The first textile layer may comprise 100% meltable fibers, or 30%-100% meltable fibers, or 35%-100% meltable fibers, or 40%-100% meltable fibers, or 50%-100% meltable fibers, or 60%-100% meltable fibers, or 70%-100% meltable fibers, or 80%-100% meltable fibers, or 90%-100% meltable fibers. In other embodiments, the first textile layer may comprise a combination of meltable and non-meltable fibers, ranging from 1-99% non-meltable fibers and 1-99% meltable fibers, where the weight percentages are based on the total weight of fibers in the first textile layer. Each percentage is based on the total weight of fibers in the first textile layer.

[0011] In some of the foregoing embodiments, the first textile layer can comprise 100% nylon textile. In some of the foregoing embodiments, the first textile layer can be 100% polyester textile. In yet other embodiments, the first textile layer can comprise, based on the total weight of the textile, 30% to 70% nylon and 30% to 70% cotton; or 30% to 68% nylon and 30% to 68% cotton, and up to about 5% antistatic additive; or 30% to 70% polyester and 30% to 70% cotton; or 30% to 68% polyester and 30% to 68% cotton, and up to about 5% antistatic additive, based on the total weight of the 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 may be a wool textile comprising up to 100% wool.

[0012] In any of the foregoing embodiments, the second textile layer comprises or consists essentially of meltable fibers. In any of the foregoing embodiments, the second textile layer comprises or consists essentially of non-meltable fibers. In any of the foregoing embodiments, the second textile layer comprises or consists essentially of a mixture of meltable and non-meltable fibers.

[0013] In any of the foregoing embodiments, the second textile layer can comprise 0% to 100% meltable fibers, based on the total weight of meltable and non-meltable fibers in the second textile layer. In other embodiments, the second textile layer can comprise greater than 0% to 100% meltable fibers, or 0.5% to 100% meltable fibers, or 1% to 100% meltable fibers, or 1% to 99% meltable fibers, or 3% to 100% meltable fibers, or 5% to 100% meltable fibers, or 10% to 100% meltable fibers, or 20% to 100% meltable fibers, or 25% to The second textile layer may comprise 100% meltable fibers, or 30%-100% meltable fibers, or 35%-100% meltable fibers, or 40%-100% meltable fibers, or 50%-100% meltable fibers, or 60%-100% meltable fibers, or 70%-100% meltable fibers, or 80%-100% meltable fibers, or 90%-100% meltable fibers. In other embodiments, the second textile layer may comprise a combination of meltable and non-meltable fibers, ranging from 1-99% non-meltable fibers and 1-99% meltable fibers, where the weight percentages are based on the total weight of the fibers in the second textile layer. Each percentage is based on the total weight of the fibers in the second textile layer.

[0014] In some of the foregoing embodiments, the second textile layer can comprise 100% nylon textile. In other embodiments, the second textile layer can be 100% polyester textile. In yet another embodiment, the second textile layer can comprise, based on the total weight of the textile, 30% to 70% nylon and 30% to 70% cotton; or 30% to 68% nylon and 30% to 68% cotton, and up to about 5% antistatic additive; or 30% to 70% polyester and 30% to 70% cotton, based on the total weight of the textile; or 30% to 68% polyester and 30% to 68% cotton, and up to about 5% antistatic additive; or 40% to 60% nylon and 40% to 60% cotton, and up to about 5% antistatic additive; or 30 to 68% aramid and 30 to 68% flame-retardant viscose, and up to about 5% antistatic additive. In other embodiments, the second textile layer may be a cotton textile comprising up to 100% cotton. In other embodiments, the second textile layer may be a wool textile comprising up to 100% wool.

[0015] In any of the foregoing embodiments, layers a) and c) are bonded to one another using a first layer of thermally reactive material, and layers c) and e) are bonded to one another using a second layer of thermally reactive material.

[0016] In any of the foregoing embodiments, the layer of first thermally responsive material covers 25% or more of the first textile layer and / or carrier layer.

[0017] In any of the foregoing embodiments, the layer of second thermally responsive material covers 25% or more of the second textile layer and / or carrier layer.

[0018] In any of the foregoing embodiments, the expandable graphite expands by at least about 900 micrometers when heated to about 280° C. as measured by a TMA expansion test.

[0019] In any of the foregoing embodiments, the carrier layer comprises a film, a textile, or a combination thereof. In some embodiments, the carrier layer may be a film, such as a film comprising a fluoropolymer, a polyimide, a silicone, a polyurethane, polytetrafluoroethylene (PTFE), expanded PTFE (ePTFE), or a combination thereof. In any of the foregoing embodiments, the carrier layer may be a nonwoven textile, such as an aramid nonwoven. In other embodiments, the carrier layer may be a laminate of one or more films and one or more textiles. In some embodiments, the carrier layer may comprise a meltable or non-meltable film, a textile, or a combination thereof.

[0020] In any of the foregoing embodiments, the laminate can further include one or more additional layers of thermally responsive material and textile layers, wherein each subsequent additional layer is disposed adjacent to at least one of the first and / or second textile layers.

[0021] The present disclosure also relates to a method of forming a laminate, the method comprising: i) adhering a first textile layer to a carrier layer with a first heat-reactive material to form a precursor laminate; and ii) adhering the precursor laminate to a second textile layer with a second heat-reactive material, wherein the first and second heat-reactive materials independently comprise a polymer resin and an expandable graphite.

[0022] In any of the foregoing embodiments, the laminate can be used in a protective article, where the first textile layer is an outer portion of the protective article, while the second textile layer forms an inner portion of the protective article. Protective articles can include, for example, garments such as shirts, jackets, pants, coveralls, overalls, aprons, hats, gloves, and footwear; covers, blankets, and tents.

[0023] The present disclosure also provides a method for improving the thermal conductivity of a protective article comprising the laminate by 100 cal / cm 2 The present invention relates to the use of any of the aforementioned laminates to provide improved thermal protection against arc discharge up to 1000 kJ / cm compared to a protective article that does not use the first and second layers of thermally reactive material.

[0024] The present disclosure relates to a garment comprising the laminate of any one of the preceding embodiments.

[0025] Laminates according to the present disclosure are useful for use as flame-retardant articles, such as flame-retardant garments, blankets, or covers. Traditionally, the production of flame-retardant garments has required the use of flame-retardant textiles. The laminates described herein allow for the production of laminates using non-flame-retardant textiles. The use of non-flame-retardant textiles allows for the provision of laminates that may have one or more of the following advantages: the laminates are much lighter, more comfortable against the skin, more breathable, more durable, available in a wider range of colors, have better moisture management properties and mechanical strength, and are more environmentally friendly. The disclosed laminates can also help reduce the environmental footprint by utilizing recycled content in the textile layers that make up the product, which has a relatively low MSI HIGG index. [Brief explanation of the drawings]

[0026] [Figure 1] 1 is a schematic cross-sectional view of one embodiment described herein. [Figure 2]1 is a schematic cross-sectional view of one embodiment described herein. [Figure 3] 1A and 1B are schematic illustrations of thermally reactive material laydowns according to two different embodiments. [Figure 4] 1A-1C are schematic diagrams of overlapping, partially overlapping, and non-overlapping dots of thermally responsive material.

[0027] The disclosures of all cited patent and non-patent publications are incorporated herein in their entirety.

[0028] As used herein, the terms "embodiment" or "disclosure" are not meant to be limiting and apply broadly to any of the embodiments defined in the claims or described herein. These terms are used interchangeably herein.

[0029] Unless otherwise disclosed, the terms "a" and "an" as used herein are intended to encompass one or more (i.e., at least one) of the referenced feature.

[0030] The features and advantages of the present disclosure will be readily understood by those skilled in the art upon consideration of the following detailed description. It should be understood that, for clarity, certain features of the present disclosure that are described above and below in the context of separate embodiments may also be provided in combination in a single element. Conversely, for brevity, various features of the present disclosure that are described in the context of a single embodiment may also be provided separately or in any subcombination. Furthermore, references to the singular may also include the plural (e.g., "a" and "an" may refer to one or more) unless the context specifically dictates otherwise.

[0031] The use of various ranges of numerical values ​​specified in this application, unless otherwise specified, are presented as approximations and are expressed as if the word "about" preceded both the minimum and maximum values ​​within the specified range. In this manner, slight variations of the ranges specified above and below can be used to achieve substantially the same results as the values ​​within the range. Also, the disclosure of ranges is intended as a continuous range, including each and every value between the minimum and maximum values.

[0032] As used herein, the terms "fiber," "filament," and "yarn" can be used interchangeably unless otherwise specified. Fiber is intended to mean a thin thread having a finite length, e.g., a few millimeters to about 30 centimeters. The term "filament" is intended to mean a thin thread having a substantially infinite length. Filaments may be thousands of meters long. The term "yarn" means a continuous strand comprising one or more fibers and / or filaments. Any known yarn can be used, e.g., single-ply yarn, ply yarn, cord yarn, stretch yarn, or any combination thereof. Fibers and / or filaments can be used to produce yarns.

[0033] As used herein, "meltable," when used in reference to a fiber, filament, yarn, or textile, refers to a fiber that melts at 280°C or below or 300°C or below. In embodiments in which the yarn or textile is made from a single material, e.g., 100% nylon 6, the melting point of the material is that of nylon 6. However, in embodiments of yarns or textiles that contain a mixture of both meltable and non-meltable fibers, the presence of the non-meltable component may obscure the melting of the meltable material. For example, in the case of a textile containing a 50 / 50 blend of nylon 6,6 and cotton, the melted nylon 6,6 may be absorbed by the cotton component, causing the textile sample to appear non-meltable when subjected to the melting and thermal stability tests described herein. Thus, when meltable fibers are present in a blend of meltable and non-meltable fibers, the material is considered a meltable material in this disclosure.

[0034] This disclosure describes textiles used in various layers of laminates. As used herein, each of the first and second textile layers may independently be a single layer or a multi-layer textile in the form of a woven, knitted, or nonwoven fabric. Textiles are made from fibers, filaments, and / or yarns, which may be meltable, non-meltable, or a combination thereof. The fibers, filaments, or yarns may be synthetic and / or natural. Depending on the type and composition of the fibers, filaments, or yarns, the corresponding textiles may have a variety of different properties. Textiles may be meltable, non-meltable, flammable, flame-retardant, abrasion-resistant, heat-resistant, shrink-resistant, or may have a combination of these properties. As used herein, the term "shrink resistant" means that a textile and / or laminate exhibits less than 20%, or less than 10%, or less than 5% shrinkage in its width, its length, or both when exposed to a high-energy event. As used herein, the term "high energy" or "high-energy event" means exposure to a temperature of 180°C or greater for 0.1 seconds or greater. In other embodiments, the laminates described herein exhibit less than 20%, or less than 10%, or less than 5% shrinkage when subjected to a shrinkage test according to ISO 17493 at 180°C. In other embodiments, the laminates described herein exhibit less than 20%, or less than 10%, or less than 5% shrinkage when subjected to a shrinkage test according to ISO 17493 at 260°C.

[0035] Described herein is a laminate having: a) a first textile layer; b) a first layer of a thermally reactive material; c) a carrier layer; d) a second layer of a thermally reactive material; and e) a second textile layer, wherein the first and second layers of thermally reactive material each independently comprise a polymer resin and expandable graphite, and the first layer of thermally reactive material is between the first textile layer and the carrier layer, and the second layer of thermally reactive material is between the carrier layer and the second textile layer. The laminate can be used to manufacture protective articles, including protective clothing, where the first textile layer is typically the outermost layer of the garment and the second textile layer is typically the inner layer of the garment. Protective articles can include, for example, clothing, garments, tents, blankets, and / or covers. Protective clothing can include garments such as jackets, pants, shirts, vests, and overalls, as well as gloves, gaiters, hoods, footwear, and shoes. Protective garments comprising the laminate can be waterproof or water resistant and can also be breathable. Protective garments need to be lightweight, especially for widespread use in situations where there is a low probability of exposure to flash fires or extreme heat events, such as electrical arc flashes. In some embodiments, the laminate can be lightweight, e.g., 500 g / m 2 (gsm) or less. In some embodiments, the laminate can have a weight ranging 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 yet other embodiments, the laminate can have a weight ranging 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.

[0036] To reduce the weight of a laminate, the weight must be reduced without losing protective properties and without reducing breathability or waterproofness. As described herein, the weight of each of the first textile layer, carrier layer, and second textile layer can be reduced without sacrificing the laminate's ability to provide the wearer with protection from high-heat extreme events or electrical arc flash exposure. By utilizing relatively lightweight layers, the overall weight of the laminate can be reduced. However, if the weight of layers a), c), and / or e) is too low, the risk that significant heat or energy from the extreme event may affect the wearer during a flash fire or other high-heat condition may increase. Therefore, the laminate of the present invention provides additional protection by utilizing at least two layers of heat-reactive material. The first layer of heat-reactive material absorbs at least a portion of the heat from the extreme event, while the second layer of heat-reactive material can absorb additional heat that may have been transferred through the carrier layer, helping to minimize heat transferred to the wearer.

[0037] First textile layer The laminates described herein include a first textile layer. Suitable fibers, filaments, or yarns for the first textile layer can include nylon, nylon 6, nylon 6,6, nylon 12, nylon 6,12, polyester, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyurethane, elastane, acrylic, polyolefin, polyethylene, polypropylene, aramid, meta-aramid, para-aramid, NOMEX® aramid, KEVLAR® aramid, polyamideimide, polybenzimidazole (PBI), polybenzoxazole (PBO), FR viscose, FR cotton, modacrylic, polyamine, carbon fiber, glass fiber, polyacrylonitrile (PAN), PTFE, viscose, rayon, cotton, wool, silk, cellulose, jute, flax, bamboo, hemp, or combinations thereof. The fibers and / or filaments can be combined using known yarn-forming methods. The yarns can be made from a single type of fiber or filament, or they can be made from a blend of two or more different types of fibers or filaments. Similarly, the first textile layer can be formed from a single type of fiber, filament, and / or yarn, or from multiple different fibers, filaments, and / or yarns to provide desired textile properties. The textile can be a woven textile, a knitted textile, or a nonwoven textile.

[0038] The first textile layer forms part of a laminate intended to be the outer layer of an article directly exposed to high-energy events, such as heat and / or flame. In some embodiments, the first textile layer comprises a meltable textile layer, i.e., a textile layer comprising meltable fibers according to the meltability definitions provided herein. In some embodiments, the first textile layer comprises a non-meltable textile layer, such as a cotton textile. In other embodiments, the first textile layer can comprise a combination of meltable and non-meltable fibers, filaments, and / or yarns, such as a nylon / cotton blend or a polyester / cotton blend. In some embodiments, the first textile is a textile that is a non-melt and / or non-drip textile according to the Melt and Heat Stability Test defined herein. In some embodiments, the first textile is a textile comprising meltable fibers, filaments, or yarns that is evaluated as a non-melt and / or non-drip textile according to the Melt and Heat Stability Test defined herein.

[0039] In yet another embodiment, the laminate includes a first textile layer comprising a combination of meltable and non-meltable fibers, the combination comprising 1-99% non-meltable fibers and 1-99% meltable fibers. In other embodiments, the first textile layer can comprise 5-100% meltable fibers, or 10-100% meltable fibers, or 20-100% meltable fibers, or 25-100% meltable fibers, or 30-100% meltable fibers, or 35-100% meltable fibers, or 40-100% meltable fibers, or 50-100% meltable fibers, or 60-100% meltable fibers, or 70-100% meltable fibers, or 80-100% meltable fibers, or 90-100% meltable fibers. Each percentage is based on the total weight of the meltable and non-meltable fibers in the first textile layer. In further embodiments, the first textile layer may be a knitted fabric, such as a nylon knitted fabric, a polyester knitted fabric, a polyurethane knitted fabric, or a knitted fabric comprising one or more combinations of nylon, polyester, cotton, and / or polyurethane. The knitted fabric structure can provide a relatively lightweight textile, which helps reduce the overall weight of the laminate while still maintaining the desired flame retardancy and / or arc resistance of the laminate. In some embodiments, the laminate includes a first textile layer that is free or substantially free of flame retardants or flame retardant additives. In some embodiments, the first textile layer can be made from one or more recycled fibers, recycled filaments, or recycled textiles.

[0040] In some embodiments, the first textile layer comprises a textile made from fibers, filaments, or yarns having a denier (weight in grams of 9,000 meters of fiber, filament, or yarn) ranging from 5 denier (D) to 400D. In other embodiments, the fibers, filaments, or yarns can have a weight ranging 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 some embodiments, the first textile layer can be a woven or knit textile comprising nylon fibers, filaments, or yarns having a denier weight ranging from 5D to 400D. In some embodiments, the first textile layer comprises a woven or knit textile made from nylon yarn, the yarn ranging 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 may be a woven or knit textile made from polyester fibers, filaments, or yarns, the yarn ranging 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 first textile layers described herein may be waterproof, and / or the first textile layer may be made water resistant by coating with a durable water repellent (DWR) coating layer. The DWR coating can be present on the exterior side of the first textile layer opposite the first layer of thermally reactive material. In another embodiment, the first textile layer comprises a waterproof material.

[0041] The first textile layer can also include antistatic agents, antistatic particles, antistatic fibers, or antistatic polymers, either as fillers, coatings, or as part of the fibers that make up the first textile layer. Suitable antistatic materials can include, for example, carbon black, conductive fibers, metal particles, or conductive polymers.

[0042] The first textile layer is lightweight, having a weight of 200 grams per square meter (gsm) or less, for example, 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 100 gsm, less than 90 gsm, or less than 85 gsm. For the first textile layer to have sufficient strength and durability, the weight of the textile should be 15 gsm or more, or 20 gsm or more, or 25 gsm or more, or 30 gsm or more, or 35 gsm or more, or 40 gsm or more, or 45 gsm or more, or 20 gsm or more, or 55 gsm or more. It should be noted that increasing the amount of non-fusible fiber generally requires an increase in textile weight to provide a first textile layer with adequate durability, strength, and abrasion resistance. For example, for a 50 / 50 nylon / cotton blend, the textile weight should be in the range of 120 to about 150 gsm.

[0043] Heat-Reactive Materials The laminates described herein also include a first layer of thermally reactive material and a second layer of thermally reactive material. The first and second layers of thermally reactive material can be selected independently and can be the same or different. In this disclosure, unless otherwise specified, the following description of thermally reactive materials is intended to describe materials that can be used for the first and / or second layers of thermally reactive material.

[0044] The laminates described herein include at least two layers of thermally responsive material. Each layer of thermally responsive material independently comprises a mixture of a polymer resin and graphite, such as expandable graphite. Expandable graphite suitable for use in the laminates and methods disclosed herein has an average expansion coefficient of at least 9 micrometers per degree Celsius (μm / °C) between 180°C and 280°C. Depending on the desired properties of the laminate, it may be desirable to use expandable graphite having an expansion coefficient of greater than 9 μm / °C between 180°C and 280°C, greater than 12 μm / °C between 180°C and 280°C, or greater than 15 μm / °C between 180°C and 280°C. One expandable graphite suitable for use in certain embodiments expands by at least 900 micrometers (μm) when heated to 280°C in the thermomechanical analysis (TMA) expansion test described herein. Another expandable graphite suitable for use in certain embodiments expands by at least 400 μm when heated to 240°C in the TMA expansion test described herein.

[0045] Another expandable graphite suitable for use in certain embodiments expands at least 400 μm when heated to 240° C. in the TMA Expansion Test described herein. When tested using the Furnace Expansion Test described herein, expandable graphite suitable for use in articles exhibits an average expansion of at least 9 cc / g at 300° C. In one example, when tested according to the Furnace Expansion Test described herein, Asbury 3626 expandable graphite (available from Asbury Graphite Mills, Inc.) exhibits an average expansion of about 19 cc / g at 300° C., while Asbury 3538 expandable graphite (available from Asbury Graphite Mills, Inc.) exhibits an expansion of only about 4 cc / g at 300° C.

[0046] In one embodiment, the thermally reactive material is in the form of a mixture of a polymer resin and expandable graphite. The particle size of the expandable graphite suitable for the present invention should be selected so that the thermally reactive material can be applied by the selected application method. For example, if the thermally reactive material is applied by gravure printing technology, the particle size of the expandable graphite should be small enough to fit into the gravure cell.

[0047] In certain embodiments, the thermally responsive material comprises expandable graphite that exhibits at least the above-described expansibility and exhibits an endothermic capacity of at least about 100 Joules per gram (J / g) when tested in accordance with the DSC Endothermic Test Method described herein. In other embodiments, it may be desirable to use expandable graphite that exhibits an endothermic capacity of at least about 150 J / g, at least about 200 J / g, or at least about 250 J / g.

[0048] In some embodiments, a laminate including a thermally reactive material having expandable graphite that exhibits an expansion of greater than 900 micrometers (μm) at 280° C. and an endothermic heat of greater than 100 J / g has an average afterflame value of less than 20 seconds, an average char length of less than 20 centimeters (cm), or both, and an afterflame value of less than 20 seconds and an average char length of less than 20 cm when tested in accordance with the Edge Ignition Test described herein.

[0049] In other embodiments, when tested in accordance with the Edge Ignition Test, the laminate may have an average afterflame of less than 10 seconds, or less than 2 seconds, and / or the laminate may have an average char length of less than 15 cm, or less than 10 cm.

[0050] The first and second layers of thermally reactive material each independently comprise a polymer resin and expandable graphite. Polymer resins having a melting or softening temperature of less than 280°C are suitable for use in the thermally reactive material. In some embodiments, the polymer resin is sufficiently fluid or deformable to allow the expandable graphite to expand significantly upon exposure to heat at 280°C or less. It may be desirable for the extensional viscosity of the polymer resin to be low enough to allow expansion of the expandable graphite, yet high enough to maintain the structural integrity of the thermally reactive material after expansion of the polymer resin and expandable graphite mixture. In other embodiments, the polymer resin may have a storage modulus of 10 at 200°C or less. 3 ~10 8 dyne / cm 2and a polymer resin having a tan delta of 0.1 to 10 is used. 3 ~10 6 dyne / cm 2 In another embodiment, the storage modulus is 10 3 ~10 4 dyne / cm 2 A polymer resin having a storage modulus of 1000 .mu.m or less is used. Polymer resins suitable for use in some embodiments are elastomers. Other polymer resins suitable for use in some embodiments are crosslinkable, such as crosslinkable polyurethanes, such as MOR-MELT® R7001E (manufactured by Rohm & Haas). In other embodiments, suitable polymer resins are thermoplastic resins having a melting temperature of 50°C to 250°C, such as DESMOMELT® VP KA 8702 (manufactured by Covestro AG, Leverkusen, Germany). Polymer resins suitable for use in the embodiments described herein include polymers including, but not limited to, polyesters, thermoplastic polyurethanes, and crosslinkable polyurethanes, as well as combinations thereof. Other polymer resins may include one or more polymers selected from polyesters, polyamides, acrylics, vinyl polymers, polyolefins, silicones, or epoxies.

[0051] The thermally responsive material can include a flame-retardant material. In some embodiments, the flame-retardant material can be optionally incorporated into the polymer resin. In some embodiments, the polymer resin can include at least one component or additive selected from the group consisting of chlorinated compounds, brominated compounds, antimony oxide, organophosphorus compounds, phosphate esters, resorcinol bis(diphenyl phosphate), zinc borate, ammonium polyphosphate, melamine cyanurate, melamine polyphosphate, molybdenum compounds, alumina trihydrate, and magnesium hydroxide, which can improve the flame retardancy of the composite article. In some embodiments, the flame-retardant material is melamine polyphosphate, resorcinol bis(diphenyl phosphate), or a combination thereof. The flame-retardant material can be present in an amount ranging from 0% to 60% by weight, based on the total weight of the thermally responsive material. In other embodiments, the flame-retardant material can be present in an amount ranging from 10% to 55% by weight, based on the total weight of the thermally responsive material. In some embodiments, at least one of the first or second layers of thermally reactive material comprises a flame retardant material.

[0052] In some embodiments, when the laminate is exposed to flame and / or extreme heat, for example, at temperatures above 280°C, meltable portions of the first textile layer, if present, are absorbed by the heat-reactive material. At the same time, the heat-reactive material can expand. In other embodiments, when the laminate is exposed to flame and / or extreme heat, for example, at temperatures above 300°C, meltable portions of the first textile layer, if present, are absorbed by the heat-reactive material. At the same time, the heat-reactive material can expand. These processes can also result in a char composed of the first textile layer and the heat-reactive material.

[0053] The char formed by exposing the first textile layer and the first layer of thermally reactive material to heat and / or elevated temperatures, e.g., 280°C or higher or 300°C or higher, is a heterogeneous molten mixture of the first textile layer and the expanded layer of thermally reactive material. According to the present disclosure, char refers to the carbonaceous material remaining after the melt of the layer and thermally reactive material is exposed to temperatures of 280°C or higher or 300°C or higher. The char is a mixture of expanded graphite and one or both of the molten polymer resin and the meltable portion of the first textile layer. At elevated temperatures of 280°C or higher or 300°C or higher, one or both of the first textile layer and the polymer resin may oxidize or participate in a combustion process, which may form additional carbonaceous material that becomes part of the char. The formation of the char can help insulate the layer behind the char from heat exposure.

[0054] When the laminate is exposed to flame and / or extreme heat, the first layer of thermally reactive material can expand within (or intermingle with) the melt of the first textile layer. In doing so, the first layer of thermally reactive material intermingles with the molten first textile layer, protecting the underlying layers and the wearer of the article. In one embodiment, the laminate can have a break-open time that is at least 20 seconds longer, or at least 30 seconds longer, than a laminate composed of substantially the same materials but lacking the expandable graphite material, which does not experience the expansion process described above, when tested in accordance with the Horizontal Burn Test method described herein.

[0055] In some embodiments of the thermally reactive material, the mixture forms a plurality of tendrils comprising expanded graphite upon expansion. The total surface area of ​​the thermally reactive material increases significantly when compared to the same mixture before expansion. In one embodiment, the surface area of ​​the mixture increases by at least five times after expansion. In another embodiment, the surface area of ​​the mixture increases by at least ten times after expansion. Additionally, the tendrils often extend outward from the expanded mixture. In embodiments in which the thermally reactive material is located on the substrate in a discontinuous form, the tendrils extend to at least partially fill the open areas between the discontinuous domains. In a further embodiment, the tendrils are elongated, with a length-to-width aspect ratio of at least 5:1.

[0056] During exposure to a high-energy event, such as heat, flame, and / or arc flash, the combination of the first textile layer and the first thermally reactive material layer can dissipate or absorb at least a portion of the abnormal event energy transmitted during the high-energy event due to the melting and / or expansion. If the energy and / or heat transmitted through the carrier layer is substantial, the expandable graphite particles in the second thermally reactive material layer, as well as the expandable graphite in the first thermally reactive material layer, can expand, thereby forming an additional barrier layer and absorbing a further portion of the energy from the high-energy event, thereby providing a higher level of thermal protection to the wearer. In some embodiments, the second textile layer can include meltable fibers, filaments, and / or yarns. If the second textile layer also melts, the second thermally reactive material layer can absorb the melting second textile layer, minimizing injury to the wearer.

[0057] In one embodiment, the thermally reactive material can be produced by a method that provides an intimate blend of expandable graphite with a polymer resin without causing significant expansion of the expandable graphite. Suitable mixing methods include, but are not limited to, paddle mixers, blending, and other low-shear mixing techniques. In one method, an intimate blend of expandable graphite particles with a polymer resin is achieved by mixing the expandable graphite with a monomer or prepolymer before polymerization of the polymer resin. In another method, the expandable graphite may be blended with a molten polymer, with the solvent being removed after mixing. In another method, the 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 a method that provides an intimate blend of expandable graphite particles or agglomerates with a polymer resin, the expandable graphite is coated or encapsulated by the polymer resin before expansion of the expandable graphite. In another embodiment, the intimate blend is achieved before applying the thermally reactive material to a substrate.

[0058] The thermally reactive material comprises 50 weight percent (wt%) or less, or 40 wt% or less, or 30 wt% or less of expandable graphite, based on the total weight of the thermally reactive material, with the remainder consisting essentially of polymer resin and flame-retardant material. In other embodiments, the expandable graphite comprises 20 wt% or less, or 10 wt% or less, or 5 wt% or less of the thermally reactive material, with the remainder consisting essentially of polymer resin and flame-retardant material. Overall, 5 wt% to 50 wt% of expandable graphite, based on the total weight of the thermally reactive material, is desirable. In some embodiments, even smaller amounts of expandable graphite can be used to achieve the desired flame-retardant performance. Addition amounts as low as 1 wt% may be useful. Other levels of expandable graphite may be suitable for other embodiments, depending on the desired properties and structure of the resulting laminate. Other additives, such as pigments, fillers, antimicrobial agents, processing aids, and stabilizers, can also be added to the thermally reactive material. If present, the other additives are generally present in an amount less than about 10 wt% based on the total weight of the thermally reactive material.

[0059] The first and second layers of thermally reactive material, more specifically the polymeric resin, can function as a binder, for example, to attach or bond one layer to an adjacent layer. For example, the first layer of thermally reactive material can adhere a first textile layer to a carrier layer, and the second layer of thermally reactive material can adhere a carrier layer to a second textile layer. The first and second layers of thermally reactive material can independently be in the form of a discontinuous adhesive, e.g., a series of individual dots or shapes that do not touch or overlap each other. In other embodiments, the first and / or second layers of thermally reactive material can be continuous layers extending across a majority of the length and / or width of the laminate. In yet other embodiments, the first and / or second layers of thermally reactive material can 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 can be straight or curved, substantially parallel to each other, and / or overlapping each other. When the first and / or second layers of thermally reactive material are applied individually and discontinuously, the shape of the dots of thermally reactive material can be virtually any shape. In some embodiments, the shape can be a circle, oval, triangle, square, rectangle, star, polygon, quadrilateral, or any other discrete shape. The shape of the first layer of thermally reactive material can be selected independently of the shape of the second layer of thermally reactive material.

[0060] A quantity of heat-reactive material should be applied to bond each of the first textile layer, carrier layer, and second textile layer of the laminate and to provide the desired protection against high-energy events. Conventionally, at least 20 grams / m 2Each of the first and second layers of thermally reactive material is applied to provide a total thickness of thermally reactive material of about 1000 psi (1 gsm). In some embodiments, the amount of each of the first and second layers of thermally reactive material can independently range from 20 gsm to about 130 gsm. In other embodiments, the amount of each of the first and second layers of thermally reactive material can independently range 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.

[0061] Carrier Layer The laminate includes a carrier layer positioned between the first and second layers of thermally reactive material. The carrier layer can provide strength and durability to the laminate both before and after exposure to a high-energy event that causes expansion of one or more layers of thermally reactive material. The carrier layer can be a film, a textile, or a carrier composite layer including at least a film and a textile. As used herein, the term "film" refers to a continuous substrate having a length and width that are much greater than its thickness. A film can be monolithic (i.e., nonporous) or microporous, and can have monolithic and microporous regions. In some embodiments, the carrier layer can be a microporous film having pores filled or at least partially filled with one or more particulate fillers and / or polymers. A microporous film can be a substrate having a node and fibril structure. It should be noted that a microporous film having a node and fibril structure is different from a textile. In some embodiments, the carrier layer is free or substantially free of flame retardants or flame retardant additives. In other embodiments, the carrier layer may be a microporous film at least partially filled with a polymer, wherein the polymer filling at least a portion of the pores includes a flame retardant additive.

[0062] In some embodiments, the carrier layer includes at least one convective barrier film, which can include, for example, a heat-resistant film such as a fluoropolymer, a polyimide, a silicone, a polyurethane, polytetrafluoroethylene (PTFE), expanded PTFE (ePTFE), or a combination thereof.

[0063] In some embodiments, the carrier layer comprises a waterproof, breathable and non-breathable film; a non-breathable film; a breathable film; or a waterproof, breathable and breathable film.As an example of a waterproof, breathable and non-breathable film, the carrier layer can comprise the three-layer film taught in U.S. Patent No. 9,782,947 to Gunzel et al., which comprises two layers of ePTFE and one layer of polyurethane or flame-retardant polyurethane bonded thereto, and the entire contents of this patent document are incorporated herein by reference.As another embodiment of a waterproof and breathable film, the carrier layer can comprise an expanded fluoropolymer substrate, for example, an expanded polytetrafluoroethylene substrate comprising a node and fibril structure, wherein the pores are filled or at least partially filled with a polymer, for example, polyurethane or flame-retardant polyurethane. In some embodiments, the carrier layer is a waterproof, moisture-permeable, and breathable carrier film, which includes an expanded fluoropolymer or expanded PTFE film and has two or more layered regions, each region having a different microstructure. For example, a first layer can have a microstructure with a relatively large average pore size and a relatively small node size, compared to a second layer having a microstructure with a relatively small average pore size and a correspondingly larger average node size. In some embodiments, the carrier layer includes a waterproof, moisture-permeable, and breathable carrier film, which can have three different microstructure regions; for example, two outer layers can have relatively large pore sizes, and a central layer can have a relatively smaller pore size than the outer microstructure layers. A suitable barrier film having two or more different microstructure layers is taught in U.S. Patent No. 9,440,044 to Hodgins et al., the entire contents of which are incorporated herein by reference. In some embodiments, the carrier layer comprises a breathable carrier film, such as a microporous fluoropolymer or microporous ePTFE membrane.In other embodiments of the breathable carrier film, the carrier layer comprises a microporous fluoropolymer or microporous ePTFE membrane that is free or substantially free of pore-filling polymers. In yet other embodiments, any of the expanded or microporous carrier layers described above can include a coating of fluoropolymer on the pore walls, i.e., on the nodes and fibrils of the microporous film.

[0064] When the laminate is used in a garment, upon exposure to a high-energy event, the carrier layer comprising the thermally stable convective barrier can help minimize convective heat transfer from the outer layer, i.e., the first textile layer, to the layer closer to the wearer, i.e., the second textile layer. The film-based convective barrier layers described herein exhibit a permeability of about 10 Frazier (liters per meter) after thermal exposure when tested in accordance with the Breathability Test described herein. 2 / second(l / m 2 / s)). Preferably, the film-based convective barrier layer exhibits a maximum breathability of less than 5 Frazier after heat exposure. More preferably, the film-based convective barrier layer exhibits a maximum breathability of less than 3 Frazier after heat exposure.

[0065] In some embodiments, as illustrated in Figure 1, the laminate (10) includes a first textile layer (20), two layers (30) and (30') of thermally responsive material, a carrier layer (40), and a second textile layer (50). In a further embodiment, as illustrated in Figure 2, the laminate (10) can include a first textile layer (20), a carrier layer (40), which may be a thermally stable multilayer barrier, two layers (30) and (30') of thermally responsive material, and a second textile layer (50). The carrier layer (40) includes two thermally stable expanded microporous films (42) and (42') and a polymer layer (44) therebetween. The polymer layer (44) has been found to extend at least partially into the pores of the expanded microporous films (42) and (42'). The polymer layer 44 may be waterproof, non-breathable, or both. The polymer layer 44 may be polyurethane or a layer of polyurethane containing one or more flame retardants.

[0066] The carrier layer can also include a textile-based carrier layer or a textile carrier layer. Fibers, filaments, or yarns suitable for use in a textile-based carrier layer can include nylon, nylon 6, nylon 6,6, nylon 12, nylon 6,12, polyester, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyurethane, elastane, acrylic, polyolefin, polyethylene, polypropylene, aramid, meta-aramid, para-aramid, NOMEX® aramid, KEVLAR® aramid, polyamideimide, polybenzimidazole (PBI), polybenzoxazole (PBO), FR viscose, FR cotton, modacrylic, polyamine, carbon fiber, glass fiber, polyacrylonitrile (PAN), PTFE, viscose, rayon, cotton, wool, silk, cellulose, jute, flax, bamboo, hemp, or combinations thereof. The fibers and / or filaments can be combined using known yarn-forming methods. The yarns can be made from a single type of fiber or filament, or they can be made from a blend of two or more different types of fibers or filaments. Similarly, the textile-based carrier layer can be formed from a single type of fiber, filament, and / or yarn, or from multiple different fibers, filaments, and / or yarns to provide desired textile properties. The textile-based carrier layer can be a woven textile, a knitted textile, or a nonwoven textile.

[0067] In some embodiments, the textile-based carrier layer can include a combination of one or more meltable fibers and one or more non-meltable fibers. In some embodiments, the textile-based carrier layer can be a nylon / cotton blend or a polyester / cotton blend. In some embodiments, the textile-based carrier layer can be a woven ripstop textile made with meltable yarns, such as nylon or polyester, and flame-resistant yarns, such as aramid yarns, placed every 5-30 warp and / or weft yarns as ripstop yarns. In yet another embodiment, the textile-based carrier layer can be a textile including a combination of meltable fibers, filaments, or yarns and abrasion-resistant, heat-resistant, and flame-resistant (FR) fibers, filaments, or yarns. In some embodiments, the textile-based carrier layer can be a textile comprising a non-meltable fiber, such as aramid, polybenzimidazole (PBI), polybenzoxazole (PBO), FR viscose, FR cotton, modacrylic, polyamine, carbon fiber, glass fiber, polyacrylonitrile (PAN), PTFE, or a combination thereof. In some embodiments, the textile-based carrier layer can be a nonwoven textile made from aramid. In other embodiments, the textile-based carrier layer can be a nonwoven textile made from meta-aramid.

[0068] The carrier layer is 3 g / m 2 (gsm) to 100 gsm. In other embodiments, the carrier layer can have a weight ranging from 4 gsm to 90 gsm, or 4 gsm to 80 gsm, or 4 gsm to 75 gsm, or 4 gsm to 70 gsm, or 4 gsm to 65 gsm, or 4 gsm to 60 gsm, or 4 gsm to 58 gsm, or 4 gsm to 56 gsm, or 4 gsm to 55 gsm, or 4 gsm to 50 gsm.

[0069] The carrier layer can also include antistatic agents, antistatic particles, antistatic polymers, or antistatic fibers as fillers or as a coating. Suitable antistatic agents, antistatic particles, or antistatic polymers can include, for example, carbon black, conductive fibers, metal particles, or conductive polymers.

[0070] Second textile layer The laminate further includes a second textile layer adjacent to the second layer of thermally reactive material on the side opposite the carrier layer. The second textile layer forms one of the outer layers of the laminate and is located opposite the first textile layer. Thus, the laminate has two "outer" layers, i.e., the first textile layer and the second textile layer, and the two layers of thermally reactive material and the carrier layer form the "inner" layers of the laminate. When the laminate is formed into an article, such as a garment, the first textile layer is intended to be the outer layer of the garment, and the second textile layer is intended to be the inner layer of the garment. However, because the laminate is a three-layer laminate and an adhesive layer connects the three layers (first textile layer, carrier layer, and second textile layer), in certain embodiments, the second textile layer can be used as the outer layer and the first textile layer can be the inner layer of the garment.

[0071] The second textile layer can be any single-layer or multi-layer textile commonly used in the textile industry. Suitable fibers, filaments, or yarns for the second textile layer can include nylon, nylon 6, nylon 6,6, nylon 12, nylon 6,12, polyester, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyurethane, elastane, acrylic, polyolefin, polyethylene, polypropylene, aramid, meta-aramid, para-aramid, NOMEX® aramid, KEVLAR® aramid, polyamideimide, polybenzimidazole (PBI), polybenzoxazole (PBO), FR viscose, FR cotton, modacrylic, polyamine, carbon fiber, glass fiber, polyacrylonitrile (PAN), PTFE, viscose, rayon, cotton, wool, silk, cellulose, jute, flax, bamboo, hemp, or combinations thereof. The fibers and / or filaments can be combined using known yarn-forming methods. The yarns can be made from a single type of fiber or filament, or they can be made from a blend of two or more different types of fibers or filaments. Similarly, the second textile layer can be formed from a single type of fiber, filament, and / or yarn, or from multiple different fibers, filaments, and / or yarns to provide desired textile properties. The textile can be a woven textile, a knitted textile, or a nonwoven textile. In some embodiments, the second textile layer is free or substantially free of flame retardants or flame retardant additives.

[0072] In some embodiments, the second textile layer may be a flame-retardant textile layer comprising one or more flame-retardant natural or synthetic fibers or filaments. In some embodiments, the second textile layer may be a textile comprising 45-90% polyester and 10-55% cotton. In other embodiments, the second textile may be a textile comprising 40-60% polyamideimide, 40-60% viscose, and 1-5% antistatic agent. In other embodiments, the second textile layer may be a textile comprising 50-70% viscose and 30-50% polyester. In other embodiments, the second textile may be a textile comprising meta-aramid or para-aramid, viscose, and nylon. In other embodiments, the second textile layer may be a meltable textile layer. In some embodiments, the first textile layer and the second textile layer comprise meltable textile layers. In some embodiments, the second textile is a textile that is a non-melting and / or non-drip textile according to the Melt and Heat Stability Test defined herein. In some embodiments, the second textile is a textile that includes meltable fibers, filaments, or yarns, and is evaluated as a non-melting and / or non-drip textile according to the Melt and Heat Stability Test defined herein.

[0073] In yet another embodiment, the laminate includes a second textile layer comprising a combination of meltable and non-meltable fibers, the combination comprising 1-99% non-meltable fibers and 1-99% meltable fibers. In other embodiments, the second textile layer can comprise 5%-100% meltable fibers, or 10%-100% meltable fibers, or 20%-100% meltable fibers, or 25%-100% meltable fibers, or 30%-100% meltable fibers, or 35%-100% meltable fibers, or 40%-100% meltable fibers, or 50%-100% meltable fibers, or 60%-100% meltable fibers, or 70%-100% meltable fibers, or 80%-100% meltable fibers, or 90%-100% meltable fibers. Each percentage is based on the total weight of the fibers in the second textile layer. In further embodiments, the second textile layer may be a knitted fabric, such as a nylon knitted fabric, a polyester knitted fabric, a polyurethane knitted fabric, or a knitted fabric comprising one or more combinations of nylon, polyester, and / or polyurethane. The knitted fabric structure can provide a relatively lightweight textile, which helps reduce the overall weight of the laminate while still maintaining the desired flame retardancy and / or arc resistance of the laminate. In some embodiments, the laminate includes a second textile layer that is free or substantially free of flame retardants or flame retardant additives. In some embodiments, the second textile layer can be made from one or more recycled fibers, recycled filaments, or recycled textiles.

[0074] The second textile layer can also include antistatic agents, antistatic particles, antistatic polymers, or antistatic fibers as fillers or coatings. Suitable antistatic agents, antistatic particles, or antistatic polymers can include, for example, carbon black, conductive fibers, metal particles, or conductive polymers. In some embodiments, the second textile layer can include meltable fibers and one or more antistatic agents.

[0075] The second textile layer may be a woven, knitted, or nonwoven textile. In some embodiments, the second textile is a relatively lightweight textile made from one or more synthetic fibers, such as a knitted fabric containing a blend of cotton and polyester. In another embodiment, the second textile layer may be an inherently flame-retardant layer containing flame-retardant fibers or filaments. In one embodiment, the second textile layer may be a woven textile containing a blend of aramid and flame-retardant viscose and an antistatic additive. The second textile layer is lightweight, having a weight of 200 grams per square meter (gsm) or less, for example, 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 100 gsm, less than 90 gsm, or less than 85 gsm. For the second textile layer to have sufficient strength and durability, the weight of the textile should be 15 gsm or more, or 20 gsm or more, or 25 gsm or more, or 30 gsm or more, or 35 gsm or more, or 40 gsm or more, or 45 gsm or more, or 20 gsm or more, or 55 gsm or more. It should be noted that increasing the amount of non-fusible fiber generally requires an increase in textile weight to provide a second textile layer with adequate durability, strength, and abrasion resistance. For example, for a 50 / 50 nylon / cotton blend, the textile weight should be in the range of 120 to about 150 gsm.

[0076] Additional Layers One or more additional layers can be adhered to the laminate, and the additional layers can be adhered to the first textile layer, the second textile layer, or both. If the one or more additional layers are adhered to the first textile layer, the one or more additional layers can be selected from the list of materials described as useful for the first textile layer. If the one or more additional layers are adhered to the second textile layer, the one or more additional layers can be selected from the list of materials described as useful for the second textile layer. The one or more additional layers can be adhered to the laminate, and this adhesion can be achieved using known laminating adhesives, one or more additional layers of a heat-reactive material described herein, or any other conventional technique, such as stitching, quilting, gluing, hook-and-loop fasteners, buttons, snaps, or a combination thereof.

[0077] Application of the first and second HRM layers The first layer of thermally reactive material can be applied to the carrier layer, the first textile layer, or both. The second layer of thermally reactive material can be applied to the carrier layer (opposite the first layer of thermally reactive material), the second textile layer, or both. In some embodiments, the first and / or second layers of thermally reactive material can be applied as continuous layers. However, in embodiments where breathability and / or pleasant hand feel are desired, the first and / or second layers of thermally reactive material can be applied discontinuously to form a layer of thermally reactive material having less than 100% surface coverage. The discontinuous application providing less than 100% surface coverage can take various forms, including, but not limited to, dots, grids, lines, or combinations thereof. In some embodiments involving discontinuous coverage, the average spacing between adjacent regions of the discontinuous pattern is less than 5 millimeters (mm), or preferably less than 3.5 mm, less than 2.5 mm, less than 1.5 mm, or less than 0.5 mm. The average spacing between adjacent regions can be determined by measuring the edge spacing between adjacent dots. In embodiments where properties such as hand, breathability, and / or laminate weight are important, surface coverages of less than 90%, or less than 80%, or less than 70%, or less than 60%, or less than 50%, or less than 40%, or less than 30% can be used. In some embodiments, the first layer of thermally reactive material covers 25% or more of the surface of the first textile layer. In some embodiments, the second layer of thermally reactive material covers 25% or more of the surface of the second textile layer. Coverage can be calculated by measuring the geometry of a gravure cell or a screen printing mask, depending on which application method is used. One method for achieving less than 100% coverage includes applying the thermally reactive material to the surface of the first textile layer or the surface of the carrier layer by printing, for example, by gravure printing. 3A and 3B show examples in which a layer of heat-reactive material (330) is provided in a discontinuous pattern of dots (FIG. 3A) and grids (FIG. 3B) on a layer, such as a first textile layer (320).Each individual layer of thermally reactive material can be applied at a rate to achieve an add-on weight of 20 gsm to 120 gsm of thermally reactive material. In some embodiments, the layers of thermally reactive material can be applied at a rate to achieve an add-on weight of less than 120 gsm, or less than 100 gsm, or less than 90 gsm, or less than 80 gsm. The add-on weight can be determined by weighing identically sized samples of the layer before and after application of the thermally reactive material and normalizing the sample size per square meter.

[0078] In some embodiments, a method for forming a laminate including a first textile layer, a carrier layer, a second textile layer, and two layers of thermally reactive material can be achieved in a stepwise process, while in other embodiments, it can be achieved in a continuous process. In some embodiments, the stepwise process can include forming a precursor laminate including a second textile layer, a carrier layer, and a layer of a second thermally reactive material, with the second textile layer and the carrier layer being bonded by a layer of the second thermally reactive material. In this stepwise process, the second layer of thermally reactive material can be applied continuously or discontinuously to the second textile layer, the carrier layer, or both the second textile layer and the carrier layer. The precursor laminate can then be formed by bonding the second textile layer and the carrier layer using any of the known lamination techniques, for example, using a calender roll. The precursor laminate can be used immediately or stored for a period of minutes to several days or months until needed. Following the formation of the precursor laminate, the first textile layer can be applied. In this process, a layer of a first heat-reactive material can be applied continuously or discontinuously to the first textile layer, to the carrier layer side of the precursor laminate, or to both, and then the first textile layer can be bonded to the precursor laminate (on the carrier layer side), for example, using two or more calender rolls.

[0079] In other embodiments, a method for forming a laminate including a first textile layer, a carrier layer, a second textile layer, and two layers of thermally reactive material can be achieved in a stepwise process, where the precursor laminate includes the first textile layer, the first layer of thermally reactive material, and the carrier layer. In these embodiments, the first layer of thermally reactive material can be applied continuously or discontinuously to the first textile layer, the carrier layer, or both the first textile layer and the carrier layer. The precursor laminate can then be formed by adhering the first textile layer and the carrier layer using any known lamination technique, for example, using a calendar roll. The precursor laminate can be used immediately or stored for minutes to days or months until needed. Following formation of the precursor laminate, the second textile layer can be applied. In this process, a layer of a second heat-reactive material can be applied continuously or discontinuously to the second textile layer, to the carrier layer side of the precursor laminate, or to both, and then the second textile layer can be bonded to the precursor laminate (on the carrier layer side), for example, using a calender roll. The step-wise process described herein can be carried out in one facility, or in multiple facilities, optionally at various locations. For example, a precursor laminate can be formed in one facility and then transported to a second facility to form the laminate.

[0080] In other embodiments, a continuous lamination process can be used, in which a first layer of heat-reactive material can be applied to a first textile layer, a carrier layer, or both, and a second layer of heat-reactive material can be applied to a second textile layer, a carrier layer, or both, and the layers are adhered together in one or more lamination steps, with the first and second textile layers forming the outermost layers of the laminate and the carrier layer forming an inner layer between the outermost layers. In some embodiments, the first and second layers of heat-reactive material act as adhesives to adhere the laminate layers together.

[0081] In some embodiments, a method of forming a laminate includes: i) adhering a first textile layer to a carrier layer with a first layer of thermally reactive material to form a precursor laminate; and ii) adhering the precursor laminate to a second textile layer with a second layer of thermally reactive material. In other embodiments, a method of forming a laminate includes: i) adhering a second textile layer to a carrier layer with a second layer of thermally reactive material to form a precursor laminate; and ii) adhering the precursor laminate to the first textile layer with a first layer of thermally reactive material.

[0082] The first and second thermally reactive material layers are separated from each other by a carrier layer. When the first and second thermally reactive material layers are in a discontinuous form, such as a row or array of dots, the dots of the first thermally reactive material layer applied to one side of the carrier layer may be fully aligned, partially aligned, or not aligned at all with the corresponding dots of the second thermally reactive material layer applied to the other side of the carrier layer. As used herein, "fully aligned" means that 10% or less of the surface area of ​​the dots of the first thermally reactive material layer is not aligned with the corresponding dots of the second thermally reactive material layer. As used herein, the dots of the first and second thermally reactive material layers are said to be not aligned when 10% or less of the surface area of ​​the dots of the first thermally reactive material layer is aligned with the corresponding dots of the second thermally reactive material layer. The dots of the first and second thermally reactive material layers are said to be partially aligned if the surface area of ​​the dots of the first thermally reactive material layer extends beyond the surface area of ​​the corresponding dots of the second thermally reactive material layer by more than 10% and less than 90%.

[0083] FIG. 4 shows specific examples of aligned, partially aligned, and misaligned dots of thermally reactive material. FIG. 4 shows a carrier layer (40) having dots (31a), (32a), and (33a) of a first thermally reactive material layer on a first surface (40a) of the carrier layer (40) and dots (31b), (32b), and (33b) of a second thermally reactive material layer on a second surface (40b) of the carrier layer (40). Thermally reactive material (31b) is an example of a dot that is misaligned with the corresponding dot of thermally reactive material (31a). Thermally reactive material (32b) is an example of a dot that is partially aligned with the corresponding dot of thermally reactive material (32a). Thermally reactive material (33b) is an example of a dot that is aligned with the corresponding dot of thermally reactive material (33a). Without wishing to be bound by theory, it is believed that moisture permeability and moisture vapor transmission rate (MVTR) can be increased by increasing the alignment between the dots or lines of the first and second thermally reactive materials.

[0084] In some embodiments, the first and second layers of thermally reactive material are applied discontinuously in the form of distinct shapes, where at least a portion of the distinct shapes of the first layer of thermally reactive material are at least partially aligned with the distinct shapes of the corresponding second layer of thermally reactive material. In other embodiments, the first and second layers of thermally reactive material are applied discontinuously in the form of distinct shapes, where at least a portion of the distinct shapes of the first layer of thermally reactive material are aligned with the distinct shapes of the corresponding second layer of thermally reactive material. In yet other embodiments, the first and second layers of thermally reactive material are applied discontinuously in the form of distinct shapes, where at least a portion of the distinct shapes of the first layer of thermally reactive material are not aligned with the distinct shapes of the corresponding second layer of thermally reactive material. In yet another embodiment, the first and second layers of thermally reactive material are applied discontinuously in the form of discrete shapes, wherein the discrete shapes of the first layer of thermally reactive material comprise a composite of aligned, partially aligned, and unaligned shapes relative to the discrete shapes of the corresponding second layer of thermally reactive material.

[0085] In some embodiments, the laminate has a mass of 500 grams per meter. 2 In other embodiments, the laminate has a weight of 450 gsm or less, or 425 gsm or less, or 400 gsm or less, or 375 gsm or less, or 350 gsm or less, or 325 gsm or less.

[0086] The laminates described herein can provide lightweight laminates that can provide protection against electric arcs as measured by IEC 61482-2 in an arc box test (IEC 61482-1-2:2014) and / or an open arc test (IEC 61482-1-1:2009, Method A). In some embodiments, the laminates described herein comply with standards IEC 61482-1-1:2014 and / or IEC 61482-1-2:2014 and have a weight of 500 gsm or less. In some embodiments, the laminates described herein comply with standards IEC 61482-1-1:2014 and / or IEC 61482-1-2:2014 and have a weight of 475 gsm or less. In some embodiments, the laminates described herein comply with standards IEC 61482-1-1:2014 and / or IEC 61482-1-2:2014 and have a weight of 450 gsm or less. In some embodiments, the laminates described herein comply with standards IEC 61482-1-1:2014 and / or IEC 61482-1-2:2014 and have a weight of 425 gsm or less. In some embodiments, the laminates described herein comply with standards IEC 61482-1-1:2014 and / or IEC 61482-1-2:2014 and have a weight of 400 gsm or less. In some embodiments, the laminates described herein comply with standards IEC 61482-1-1:2014 and / or IEC 61482-1-2:2014 and have a weight of 375 gsm or less. In some embodiments, the laminates described herein comply with standards IEC 61482-1-1:2014 and / or IEC 61482-1-2:2014 and have a weight of 350 gsm or less. In some embodiments, the laminates described herein comply with standards IEC 61482-1-1:2014 and / or IEC 61482-1-2:2014 and have a weight of 325 gsm or less. In some embodiments, the laminates described herein comply with standards IEC 61482-1-1:2014 and / or IEC 61482-1-2:2014 and have a weight of 300 gsm or less.In some embodiments, the laminates described herein comply with standards IEC 61482-1-1:2014 and / or IEC 61482-1-2:2014 and have a weight of 275 gsm or less. In some embodiments, the laminates described herein comply with standards IEC 61482-1-1:2014 and / or IEC 61482-1-2:2014 and have a weight of 265 gsm or less. In some embodiments, the laminates described herein comply with standards IEC 61482-1-1:2014 and / or IEC 61482-1-2:2014 and have a weight of 250 gsm or less.

[0087] use The laminates described herein can be useful for manufacturing protective articles. Protective articles can include, for example, garments such as shirts, jackets, pants, coveralls, overalls, aprons, hats, gloves, and footwear; covers, blankets, tents, and the like. In each of these applications, the laminate should be positioned so that the meltable layer faces a potential threat. For example, if the laminate is used to form a jacket, the first textile layer should be positioned facing the outer portion of the jacket, and the second textile layer is located closer to the wearer, so that during exposure to a high-energy or high-temperature event, the first textile layer will be exposed to energy before the second textile layer.

[0088] Example Melt and Thermal Stability Tests This test was used to determine the thermal stability of textile materials. The test was based on the thermal stability test described in Section 8.3 of NFPA 1975 (2004 Edition). The test oven was a circulating hot air oven as specified in ISO 17493. The test was conducted using the procedure for blocking resistance at elevated temperatures (Sections 89-93) according to ASTM D 751, Standard Test Method for Coated Fabrics, with the following modifications: A borosilicate glass plate measuring 100 mm x 100 mm x 3 mm (4 in x 4 in x 1 / 8 in) was used. The internal oven test temperature was 280±5° C. After the glass plate was removed from the oven, the test specimen was allowed to cool for a minimum of 1 hour.

[0089] Any sample surface that adhered to the glass plate, adhered to itself upon unfolding, or showed evidence of melting or dripping was rated as meltable. Samples that showed no evidence of melting were then retested (using a new sample of material) at the internal oven test temperature of 300°C. After removal from the oven and cooling for one hour, any sample surface that adhered to the glass plate, adhered to itself upon unfolding, or showed evidence of melting or dripping was rated as meltable. Samples that did not exhibit one of these melting criteria were rated as non-melting and / or non-drip samples (e.g., rated as non-melting / non-drip textiles).

[0090] TMA expansion test: Thermomechanical analysis (TMA) was used to measure the expansive properties of expandable graphite particles. The expansive properties were tested using a TA Instruments TMA 2940 instrument. A ceramic (alumina) TGA pan approximately 8 mm in diameter and 12 mm in height was used to hold the sample. A macroexpansive probe approximately 6 mm in diameter was used to zero the bottom of the pan. A thin flake of expandable graphite, approximately 0.1–0.3 mm deep as measured by the TMA probe, was placed in the pan. The furnace was closed, and the initial sample height was measured. The furnace was heated from approximately 25°C to 600°C at a ramp rate of 10°C / min. The displacement of the TMA probe was plotted against temperature, and the displacement was used as an indicator of expansive properties.

[0091] DSC endothermic test: Tests were performed on a TA Instruments Q2000 DSC using TZERO T™ hermetic pans. For each sample, approximately 3 milligrams (mg) of expandable graphite was placed in the pan. The pan was vented by pressing the corner of a razor blade into the center, creating a vent hole approximately 2 mm long and less than 1 mm wide. The DSC was equilibrated at 20°C. The sample was then heated from 20°C to 400°C at 10°C / min. Endotherms were obtained from the DSC curves.

[0092] weight: The weight of the materials was determined as specified in ASTM D751, Section 10. The units given are grams per square meter.

[0093] Electric arc box testing was performed using IEC 61482-1-2:2014.

[0094] The electric arc box test provides information about a material's performance against the stall curve when subjected to an arc discharge, with a "low" result meaning the material passed that portion of the test and an "high" result meaning the material failed the test. The box test also provides a measure of burn time (<5 seconds is a pass, >5 seconds is a fail); pit formation (test material with no pits larger than 5 mm passes this portion of the test); and an overall pass / fail rating.

[0095] The open arc test was carried out in accordance with IEC 61482-1-1:2009, Method A.

[0096] Data is provided as arc thermal performance values, expressed in calories per square centimeter (cal / cm 2 ) units.

[0097] In-furnace expansion test A nickel crucible was heated in a high-temperature furnace at 300°C for 2 minutes. A measurement sample of expandable graphite (approximately 0.5 g) was added to the crucible and placed in the high-temperature furnace at 300°C for 3 minutes. After the heating period, the crucible was removed from the furnace and allowed to cool. The expandable graphite was then transferred to a measuring cylinder to measure its expansion volume. The expansion volume was divided by the initial weight of the sample to obtain the expandability in cc / g.

[0098] Breathability test: To test the breathability of the carrier film layer after thermal exposure, 381 mm (15 inch) square specimens were clamped to a metal frame and suspended in a forced air oven set at 260°C. After 5 minutes of exposure, the specimens were removed from the oven. After allowing the specimens to cool, the breathability of the specimens was tested in accordance with the test method entitled ISO 9237 (1995).

[0099] Vertical Burning Test The test was conducted in accordance with ASTM D6413. Samples were exposed to the flame for 12 seconds. The afterflame time was averaged for three samples. Laminates with an afterflame of more than 2 seconds were rated as flammable. The test also determined the char length. Samples were tested in both the warp and weft directions.

[0100] Horizontal combustion test The procedure was carried out in accordance with ISO 15025, and the test was carried out separately on the top and bottom sides of the laminate. The test provided information on afterflame and its duration in seconds (if any); afterflame; hole formation; presence of flaming debris; and flame spread upward or to the vertical edges of the material.

[0101] Water Vapor Transmission Rate (MVTR) A description of the test used to measure moisture vapor transmission rate (MVTR) is provided below: This procedure has been found to be suitable for testing films, coatings, and coated products.

[0102] In this procedure, approximately 70 ml of a solution consisting of 35 parts by weight of potassium acetate and 15 parts by weight of distilled water is placed in a 133 ml polypropylene cup having an inside diameter of 6.5 cm at its opening. This cup has a yield of approximately 85,000 g / m when tested according to the method described in U.S. Pat. No. 4,862,730 (Crosby). 2 An expanded polytetrafluoroethylene (PTFE) membrane with a minimum MVTR of 1 / 24 hrs is heat sealed to the lip of the cup to create a tensioned, leak-proof microporous barrier that confines the solution.

[0103] A similar expanded PTFE membrane is attached to the surface of a water bath. The water bath assembly is controlled at 23° C.+0.2° C. and utilizes a temperature controlled space and a water circulating bath.

[0104] The specimen to be tested is conditioned at a temperature of 23°C and a relative humidity of 50% prior to performing the test procedure. The specimen is placed with the microporous polymer membrane in contact with the expanded polytetrafluoroethylene membrane attached to the surface of the water bath and allowed to equilibrate for at least 15 minutes before introducing the cup assembly.

[0105] The cup assembly is weighed to the nearest 1 / 1000 g and placed upside down in the center of the test sample.

[0106] Water transport is provided by a driving force between the water in the water bath and the saturated saline solution, which provides water flux by diffusion in that direction. The sample is tested for 15 minutes, then the cup assembly is removed and reweighed to the nearest 1 / 1000 g. The MVTR of the sample is calculated from the weight gain of the cup assembly and is expressed as grams of water per square meter of sample surface area per 24 hours.

[0107] Edge ignition test Edge ignition tests were performed in accordance with ISO 11612. The test provided information on afterflame and its duration in seconds (if present); afterglow; hole formation; presence of flaming debris; and flame spread upward or to the vertical edge of the material.

[0108] Heat-Reactive Materials 1 A flame-retardant polyurethane resin was produced by first forming a resin as described in the examples of commonly owned U.S. Patent No. 4,532,316 and adding approximately 20% by weight of a phosphorus-based additive, FYROLFLEX® RDP, a phosphate ester, to a reactor. After forming the polyurethane resin, 65 parts by weight of the polyurethane resin was mixed with 24 parts by weight of expandable graphite (expandable graphite exhibiting an expandability of greater than 900 micrometers at 280°C as measured by the TMA expansion test) and an additional 17 parts by weight of another phosphorus-based flame retardant in a stirred vessel at 80°C. The mixture was cooled and used as is.

[0109] Adhesive 1 A flame retardant adhesive was produced by first forming a resin as described in commonly owned US Pat. No. 4,532,316 and adding a phosphorus-based flame retardant material in an amount of about 20% by weight to a reactor.

[0110] Manufacturing of laminate 1 A meltable layer of 85 gsm 100% recycled polyester knit fabric (product number RNY04Dmb, Na Ya Plastics Corp., Taiwan) was laminated to a carrier layer of ePTFE membrane (available from W.L. Gore and Associates, Newark, Delaware, part number 4410078). Heat-reactive material 1 was gravure printed onto the ePTFE membrane using a gravure roll with a repeating dot pattern to achieve approximately 40-45% adhesive coverage and 40-45 grams per meter. 2(gsm) adhesive laydown was obtained. The meltable layer was placed on top of the carrier layer and rolled between the nip of two rollers. The laminate was placed on the roll and allowed to cure for at least 24 hours. A second layer of heat-reactive material 1 was printed on the exposed side of the carrier layer, i.e., the side opposite the meltable layer, using the same gravure printing method as previously used. A 65% polyester / 35% cotton textile layer (available from Ames Europe, Enschede, The Netherlands, product number 310.300-000) was adhered to the printed second layer of heat-reactive material, and the laminate was rolled between the nip of two rollers. The laminate was then placed on the roll and allowed to cure for at least 24 hours.

[0111] A fluorine-based durable water repellent was applied to the meltable layer by a kiss coat process. Laminate 1 had a weight of 298 gsm.

[0112] Manufacture of laminate 2 A meltable layer of 85 gsm 100% recycled polyester knit fabric (product number RJ47Pmb, Nan Ya Plastics Corp., Taiwan) was laminated to a carrier layer of ePTFE membrane (available from W.L. Gore and Associates, Newark, Delaware, part number 4410078). Heat-reactive material 1 was gravure printed onto the ePTFE membrane using a gravure roll with a repeating dot pattern to achieve approximately 40-45% adhesive coverage and 40-45 grams per meter. 2 The adhesive laydown was obtained. The fusible layer was placed on top of the carrier layer and rolled between the nip of two rollers. The laminate was placed on the roll and allowed to cure for at least 24 hours. A second layer of heat-reactive material 1 was printed on the exposed side of the carrier layer, i.e., the side opposite the fusible layer, using the same gravure printing method as previously used. A 60% viscose / 40% polyester knitted textile layer (available from Borgini, Italy, item no. 14001) was adhered to the printed second layer of heat-reactive material, and the laminate was rolled between the nip of two rollers. The laminate was then placed on the roll and allowed to cure for at least 24 hours.

[0113] A fluorine-based durable water repellent was applied to the meltable layer by a kiss coat process. Laminate 2 had a weight of 252 gsm.

[0114] Manufacture of laminate 3 A meltable layer of 85 gsm 100% polyester woven fabric (product number RJ47Pmb, Nan Ya Plastics, Taiwan) was laminated to a carrier layer of ePTFE membrane (available from W.L. Gore and Associates, Newark, Delaware, part number 4410078). Heat-reactive material 1 was gravure printed onto the ePTFE membrane using a gravure roll with a repeating dot pattern to achieve approximately 40-45% adhesive coverage and 40-45 grams per meter. 2 The adhesive laydown was obtained. The fusible layer was placed on top of the carrier layer and rolled between the nip of two rollers. The laminate was placed on the roll and allowed to cure for at least 24 hours. A second layer of heat-reactive material 1 was printed on the exposed side of the carrier layer, i.e., the side opposite the fusible layer, using the same gravure printing method as previously used. A 60% viscose / 40% polyester knitted textile layer (available from Borgini, Italy, item no. 14001) was adhered to the printed second layer of heat-reactive material, and the laminate was rolled between the nip of two rollers. The laminate was then placed on the roll and allowed to cure for at least 24 hours.

[0115] A fluorine-based durable water repellent was applied to the meltable layer by a kiss coat process. Laminate 3 had a weight of 251 gsm.

[0116] Manufacture of laminate 4 A meltable layer of 70 gsm weight 100% polyester woven textile (product number 751125, available from Milliken, Spartanburg, South Carolina) was laminated to a carrier layer of 20 gsm weight ePTFE membrane (product number 10898200, available from W.L. Gore and Associates, Inc., Newark, Delaware). Thermally Reactive Material 1 was gravure printed onto the ePTFE membrane using a gravure roll with a pattern of repeating dots to achieve approximately 55-60% adhesive coverage and an adhesive laydown of 70-75 gsm. A second layer of heat-reactive material 1 was printed on the exposed side of the carrier layer, i.e., the side opposite the meltable layer, using a gravure roll with a repeating dot pattern to achieve approximately 40-45% adhesive coverage and an adhesive laydown of 40-45 gsm. A 50% cotton / 50% polyester knit textile layer (product number 6336, available from Sextet Fabrics, Inc., New York, NY) was then adhered to the printed second layer of heat-reactive material, and the laminate was rolled between the nip of two rollers. The laminate was placed on the roll and allowed to cure for at least 24 hours.

[0117] Manufacture of laminate 5 A meltable layer of 70 gsm weight 100% polyester woven textile (product number 751125, available from Milliken, Spartanburg, South Carolina) was laminated to a carrier layer of ePTFE membrane (manufactured according to the teachings set forth in U.S. Pat. No. 9,782,947). Thermally Reactive Material 1 was gravure printed onto the ePTFE membrane using a gravure roll with a pattern of repeating dots to achieve approximately 55-60% adhesive coverage and an adhesive laydown of 70-75 gsm. A second layer of heat-reactive material 1 was printed on the exposed side of the carrier layer, i.e., the side opposite the meltable layer, using a gravure roll with a repeating dot pattern to achieve approximately 40-45% adhesive coverage and an adhesive laydown of 40-45 gsm. A 50% cotton / 50% polyester knit textile layer (product number 6336, available from Sextet Fabrics, Inc., New York, NY) was then adhered to the printed second layer of heat-reactive material, and the laminate was rolled between the nip of two rollers. The laminate was placed on the roll and allowed to cure for at least 24 hours. Laminate No. 5 had a weight of 306 gsm and was used as is.

[0118] Manufacture of comparative laminate A A meltable layer of 151 gsm 100% polyester blend 50% PET / 50% PBT twill woven fabric (product number SKOL004, available from Toray Textiles Europe Ltd., UK) was laminated to a carrier layer of ePTFE membrane (product number 4410078, available from W.L. Gore and Associates, Newark, Delaware). Heat-reactive material 1 was gravure printed onto the ePTFE membrane using a gravure roll with a repeating dot pattern to achieve approximately 40-45% adhesive coverage and 40-45 grams per meter. 2An adhesive laydown of 1000 .mu.m was obtained. The fusible layer was placed on top of the carrier layer and rolled between the nip of two rollers. The laminate was placed on a roll and allowed to cure for at least 24 hours. A second layer of Thermally Reactive Material 1 was printed on the exposed side of the carrier, i.e., the side opposite the fusible layer, using the same gravure printing method as before, and a 93 gsm textile layer of TWARON® aramid / FR viscose / nylon (product number 12634, available from Fuchshuber Techno-Tex GmbH, Liechtenstein, Germany) was placed on the carrier layer, and the laminate was rolled between the nip of two rollers. The laminate was then placed on a roll and allowed to cure for at least 24 hours.

[0119] A fluorine-based durable water repellent was applied to the meltable layer by a kiss coat process. Comparative Laminate A had a weight of 302 gsm.

[0120] Manufacture of comparative laminate B A meltable layer of 70 gsm 100% polyester woven textile (product number 751125, available from Milliken, Spartanburg, SC) was laminated to a carrier layer of 20 gsm ePTFE membrane (product number 10898200, available from W.L. Gore and Associates, Inc., Newark, DE). Thermally reactive material 1 was gravure printed onto the ePTFE membrane using a gravure roll with a repeating dot pattern to achieve approximately 55-60% adhesive coverage and an adhesive laydown of 70-75 gsm. The meltable layer was placed on top of the carrier layer and rolled between the nip of two rollers. The laminate was placed on the roll and allowed to cure for 48 hours. Adhesive Layer 1 was printed on the exposed side of the carrier layer, i.e., the side opposite the meltable layer, using a gravure roll with a repeating pattern of dots to achieve 40-45% adhesive coverage and an adhesive laydown of 7-10 gsm. A 63 gsm knitted textile containing 40% modacrylic, 30% CONEX, and 30% lyocell (available from SSM Industries, Spring City, Tennessee, as part number SD2376.00) was then adhered to the printed second layer of heat-reactive material, and the laminate was rolled between the nip of two rollers. Comparative Laminate B was then placed on the roll and allowed to cure for at least 24 hours. Comparative Laminate B had a weight of 234 gsm.

[0121] Manufacture of comparative laminate C A meltable layer of 70 gsm 100% polyester woven textile (product number 751125, available from Milliken, Spartanburg, SC) was laminated to a carrier layer of 20 gsm ePTFE membrane (product number 10898200, available from W.L. Gore and Associates, Inc., Newark, DE). Thermally reactive material 1 was gravure printed onto the ePTFE membrane using a gravure roll with a repeating dot pattern to achieve approximately 55-60% adhesive coverage and an adhesive laydown of 70-75 gsm. The meltable layer was placed on top of the carrier layer and rolled between the nip of two rollers. The laminate was placed on the roll and allowed to cure for 48 hours. Adhesive Layer 1 was printed on the exposed side of the carrier layer, i.e., the side opposite the meltable layer, using gravure printing with a repeating pattern of dots to achieve 40-45% adhesive coverage and an adhesive laydown of 7-10 gsm. A 50% cotton / 50% polyester knit textile layer (product number 6336, available from Sextet Fabrics, Inc., New York, NY) was then adhered to the printed second layer of heat-reactive material, and the laminate was rolled between the nip of two rollers. The laminate was placed on the roll and allowed to cure for at least 24 hours. Comparative Laminate C had a weight of 242 gsm.

[0122] Manufacture of comparative laminate D A meltable layer of 70 gsm 100% polyester woven textile (product number 751125, available from Milliken, Spartanburg, SC) was laminated to a carrier layer of 20 gsm ePTFE membrane (product number 10898200, available from W.L. Gore and Associates, Inc., Newark, DE). Thermally reactive material 1 was gravure printed onto the ePTFE membrane using a gravure roll with a repeating dot pattern to achieve approximately 55-60% adhesive coverage and an adhesive laydown of 70-75 gsm. The meltable layer was placed on top of the carrier layer and rolled between the nip of two rollers. The laminate was placed on the roll and allowed to cure for 48 hours. Adhesive Layer 1 was printed using gravure on the exposed side of the carrier layer, i.e., the side opposite the meltable layer, to achieve approximately 40-45% area coverage and an adhesive laydown of 40-45 gsm. A 50% cotton / 50% polyester knit textile layer (product number 6336, available from Sextet Fabrics, Inc., New York, NY) was then adhered to the printed second layer of heat-reactive material, and the laminate was rolled between the nip of two rollers. The laminate was placed on the roll and allowed to cure for at least 24 hours. Comparative Laminate D had a weight of 269 gsm.

[0123] [Table 1-1] [Table 1-2] [Table 1-3]

[0124] The results in Table 1 show that, compared to comparative examples which generally only provide one of the arc protection or afterflame measurements (afterflame and / or char length), examples of the present invention can provide a combination of high arc flash protection, short afterflame, and short char length while still providing a relatively low laminate weight.

Claims

1. below: a) a first textile layer; b) a first layer of thermally reactive material; and c) a carrier layer; and d) a second layer of thermally reactive material; and e) a second textile layer; and A laminate comprising: the first and second layers of thermally reactive material each independently comprise a polymer resin and expandable graphite; a first layer of heat-reactive material present between the first textile layer and the carrier layer, and a second layer of heat-reactive material present between the carrier layer and the second textile layer.

2. The laminate of claim 1 , wherein each layer of thermally reactive material is applied independently, continuously or discontinuously.

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

4. The laminate of any one of claims 1 to 3, wherein at least one of the first and second layers of heat-reactive material comprises a flame-retardant material.

5. The laminate of any one of claims 1 to 4, wherein the first textile layer and the second textile layer each comprise at least one meltable fiber.

6. 6. The laminate of any one of claims 1 to 5, wherein the first textile layer comprises a combination of meltable and non-meltable fibers, the combination comprising a weight percentage in the range of 1 to 99% of the non-meltable fibers and a weight percentage in the range of 1 to 99% of the meltable fibers, wherein the weight percentages are based on the total weight of the fibers in the respective textile layer.

7. 7. The laminate of any one of claims 1 to 6, wherein the layers a) and c) are bonded to each other using the first layer of heat-reactive material, and the layers c) and e) are bonded to each other using the second layer of heat-reactive material.

8. The laminate of any one of claims 1 to 7, wherein the first layer of heat-reactive material covers 25% or more of the surface of the first textile layer.

9. The laminate of any one of claims 1 to 8, wherein the layer of second thermoreactive material covers 25% or more of the surface of the second textile layer.

10. 10. The laminate of any one of claims 1 to 9, wherein the expandable graphite expands by at least about 900 micrometers when heated to about 280°C as measured by a TMA expansion test.

11. The laminate of any one of claims 1 to 10, wherein the carrier layer comprises a fluoropolymer, a polyimide, a silicone, a polyurethane, polytetrafluoroethylene (PTFE), expanded PTFE (ePTFE), or a combination thereof.

12. 12. The laminate of any one of claims 1 to 11, wherein the laminate further comprises one or more additional layers of a heat-reactive material and a textile layer, wherein each subsequent additional layer is disposed adjacent to the textile layer.

13. 13. The laminate of any one of claims 1 to 12, wherein the second textile comprises meltable fibers and is rated as a non-melt / non-drip textile by melt and heat stability testing.

14. A method for forming the laminate of any one of claims 1 to 13, comprising the steps of: i) adhering the first textile layer to the carrier layer by the first heat-reactive material to form a precursor laminate; ii) adhering the precursor laminate to the second textile layer with the second heat-reactive material; A method comprising:

15. of an article including the laminate, ２ Use of a laminate according to any one of claims 1 to 13 for improving thermal protection against arc discharges up to 1000 kJ / cm.

16. An article comprising the laminate of any one of claims 1 to 13.

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

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