Aqueous binder system for a flame-retardant composite material

Abstract

A burn protection material and a method for making the same are provided, more specifically a flame retardant composite material comprising a highly flame retardant additive and a water-based aqueous binder system, specifically comprising: a) a meltable layer; b) a thermally reactive material comprising a polymeric resin comprising a water-based acrylic resin, expandable graphite, at least one flame retardant (FR) additive, and at least one polyhydroxy compound; and c) an additional layer disposed on the thermally reactive material such that the thermally reactive material is between the meltable layer and the additional layer, the textile composite having an afterflame of less than about 2 seconds.

Description

Technical Field

[0001] Cross - Reference to Related Applications This application claims the benefit of Provisional Application No. 63 / 161,091, filed on March 15, 2021, and the entire disclosure of which is incorporated herein by reference for all purposes.

[0002] The present disclosure relates to burn - protection materials, and more particularly, to flame - retardant composite materials having highly flame - retardant additives and an aqueous binder system.

Background Art

[0003] To reduce burns associated with flames, protective clothing is desired for professionals who work in dangerous environments where they may be exposed to fire for short periods of time, such as search - and - rescue and police. Protective gear for workers exposed to these situations should enhance protection to some extent so that the wearer can quickly and safely escape from danger, rather than fight the danger.

[0004] Traditionally, flame - retardant protective clothing has been made using an ensemble's outermost layer (flame - contact layer) of non - combustible, non - melting fabrics made from, for example, aramid, polybenzimidazole (PBI), poly - p - phenylene - 2,6 - benzobisoxazole (PBO), modacrylic blends, polyamines, carbon, polyacrylonitrile (PAN), and their blends and combinations. These fibers may be inherently flame - retardant, but there may be some limitations. Specifically, these fibers are very expensive, difficult to dye and print, and may not have sufficient abrasion resistance. Further, these fibers absorb more water and have less tactile comfort compared to nylon or polyester - based fabrics.

[0005] EP2322710 in the name of W.L.Gore and Associates GmbH describes an article comprising a textile made from fibers / filaments having a partial internal discontinuous pattern of an impregnating material penetrating the textile. The non-impregnated areas are air-permeable, the textile is water-vapor permeable, water absorption is reduced, and re-drying time is shortened.

[0006] EP2679109 in the name of W.L.Gore and Associates GmbH describes a material that is breathable, waterproof and flame-retardant, comprising a thermally reactive material containing a polymer resin - expandable graphite mixture, suitable for use in the clothing of workers in dangerous environments, where the expandable graphite has an expansion degree of at least 900 μm when heated to 280 °C.

[0007] To optimize the performance of users in environments that are sometimes exposed to flash flames, lightweight and breathable clothing with enhanced burn protection is desirable. The cost of fire-resistant protective clothing is an important consideration in many applications where exposure to hazards other than fire is involved, and thus the use of typical inherently flame-retardant textiles such as those used in the fire-fighting community has been excluded. Summary of the Invention

[0008] The present invention relates to an article and a method as described in the independent claims, and provides a flame-retardant composite material containing a highly flame-retardant additive and an aqueous binder system, and a method for manufacturing the same.

[0009] In a first aspect, there is provided a textile composite material comprising: a) a fusible layer; b) a thermally reactive material containing a polymer resin containing an aqueous acrylic resin, expandable graphite, at least one flame-retardant (FR) additive and at least one polyhydroxy compound; and c) an additional layer disposed on the thermally reactive material, wherein the thermally reactive material is between the fusible layer and the additional layer, and wherein the textile composite material has a afterflame of less than about 2 seconds.

[0010] The polyhydroxy compound can have a molecular weight of less than about 1000 g / mol, less than about 500 g / mol, less than about 250 g / mol, or less than about 100 g / mol.

[0011] The polyhydroxy compound can be propane-1,2,3-triol and can also be called glycerol.

[0012] The textile composite material can have a dry peel strength in the range of about 5 to about 30 Newtons (N) as measured by DIN 54310.

[0013] The thermally reactive material can be applied to the fusible layer. The thermally reactive material can be applied to the additional layer. The thermally reactive material can be applied to both the fusible layer and the additional layer. The thermally reactive material can be applied in a continuous pattern. The thermally reactive material can be applied in a discontinuous pattern.

[0014] The thermally reactive material can be applied in a discontinuous pattern of dots.

[0015] The expandable graphite can expand by at least about 900 micrometers when heated to about 280 °C as measured by the TMA expansion test described herein.

[0016] At least one FR additive can include a nitrogen-based material and / or a phosphorus-based material. At least one FR additive can be melamine. At least one FR additive can be polyphosphate. At least one FR additive can be a combination of melamine and polyphosphate. At least one FR additive can be melamine polyphosphate.

[0017] The thermally reactive material can include a polyhydroxy compound in the range of about 3 to about 20 wt%, or about 3 to about 10 wt%, or about 3 to about 5 wt% based on the total mass of the thermally reactive material. The polyhydroxy compound can be propane-1,2,3-triol.

[0018] The thermally reactive material can include an acrylic polymer and a mixture of expandable graphite and at least one polyhydroxy compound. The thermally reactive material can include an acrylic polymer in the range of about 40 to about 90 wt% based on the total mass of the thermally reactive material. The thermally reactive material can include a mixture of expandable graphite and a polyhydroxy compound in the range of about 10 to about 60 wt% based on the total mass of the thermally reactive material. The thermally reactive material can include about 40 to about 90 wt% of an acrylic polymer and about 10 to about 60 wt% of a mixture of expandable graphite and a polyhydroxy compound based on the total mass of the thermally reactive material. The weight percentages used above are based on the total mass of the thermally reactive material minus any volatile substances that may be present, such as water or other organic molecules that can evaporate during drying and curing processes.

[0019] The additional layer can be a textile layer. The additional layer can be a thermally stable textile layer. The additional layer can be a combination of a textile layer and a thermally stable textile layer.

[0020] The additional layer can include one or more of aramid, flame-retardant cotton, cotton, linen, cuprammonium rayon (cupra), acetate, triacetate, wool, viscose, polybenzimidazole (PBI), polybenzoxazole (PBO), FR rayon, modacrylic, modacrylic / cotton blend, polyamine, glass fiber, polyacrylonitrile, polytetrafluoroethylene, or combinations thereof. The additional layer can include cotton, cupra, viscose, or combinations thereof.

[0021] The additional layer can include at least one meltable material. The meltable material can be flammable. Examples of textiles that are considered meltable include, but are not limited to, polyamides such as nylon 6 or nylon 6,6, polyester, and polypropylene.

[0022] The aqueous acrylic resin can contain acrylamide repeating units.

[0023] The aqueous acrylic resin can contain N-methylolacrylamide repeating units.

[0024] The polymer resin can be an aqueous acrylic resin.

[0025] The polymer resin contains at least 25 wt% of an aqueous acrylic resin based on the total mass of the polymer resin, and at least one polymer resin including vinyl acetate, styrene, polyether, polyester, polyurethane, polyether polyurethane, polyester polyurethane, polycarbonate polyurethane, or a copolymer or blend thereof.

[0026] The thermally reactive material can cover a range of about 25% to about 100% of the surface area of the meltable layer. The thermally reactive material can cover a range of about 25% to about 100% of the surface area of the additional layer.

[0027] The textile composite material can have a weight in the range of about 80 to about 240 grams per square meter (gsm) as measured by DIN EN 12127 (1997 / 12).

[0028] The textile composite material can have an air permeability of at least about 50 liters / m 2 s as measured according to DIN ISO 9237 (1995). The textile composite material can have an air permeability of more than about 50 liters / m 2 s. The textile composite material can have an air permeability in the range of about 50 liters / m 2 s to about 500 liters / m 2 s as measured according to DIN ISO 9237 (1995). The textile composite material can have an air permeability in the range of about 75 liters / m 2 s to about 500 liters / m 2 s, or about 100 liters / m2 s ~ about 500 liters / m 2 s, or about 125 liters / m 2 s ~ about 500 liters / m 2 s, or about 150 liters / m 2 s ~ about 500 liters / m 2 s, or about 175 liters / m 2 s ~ about 500 liters / m 2 s, or about 50 liters / m 2 s ~ about 100 liters / m 2 s, or about 75 liters / m 2 s ~ about 100 liters / m 2 s, or about 120 liters / m 2 s ~ about 150 liters / m 2 s, or about 130 liters / m 2 s ~ about 170 liters / m 2 s, or about 140 liters / m 2 s ~ about 180 liters / m 2 s, or about 150 liters / m 2 s ~ about 190 liters / m 2 s can have an air permeability. Optionally, the textile composite material, when measured according to DIN ISO 9237 (1995), can have an air permeability of more than about 150 liters / m 2 s.

[0029] The meltable layer and the additional layer can be adhered to each other by a thermally reactive material.

[0030] In a second aspect, there is provided a garment comprising the textile composite material described herein.

[0031] In a third aspect, there is provided a thermally reactive composition comprising: i) a polymeric resin comprising an aqueous acrylic resin, ii) an expandable graphite that expands at least about 900 micrometers when heated to about 280 °C as measured by the TMA expansion test described herein, iii) at least one flame retardant additive, iv) a polyhydroxy compound, and v) water.

[0032] The thermoreactive composition can contain a polyhydroxy compound in the range of about 3 to about 10 wt%, or about 3 to about 8 wt%, or about 3 to about 7 wt% based on the total mass of the thermoreactive materials.

[0033] The thermoreactive composition can contain an aqueous acrylic resin in the range of about 60 to about 80 wt%, expandable graphite in the range of about 5 to about 10 wt%, a flame retardant additive in the range of about 5 to about 10 wt%, a polyhydroxy compound in the range of about 5 to about 10 wt% and water in the range of about 5 to about 10 wt% based on the total mass of the thermoreactive composition.

[0034] The polyhydroxy compound can be propane-1,2,3-triol and the aqueous acrylic resin can contain acrylamide repeating units.

[0035] The terms "thermoreactive material" and "thermoreactive composition" are used to describe the same material components but under different conditions. The thermoreactive composition is a wet or aqueous combination of a polymer resin containing an aqueous acrylic resin, and a mixture of expandable graphite, at least one FR additive and at least one polyhydroxy compound, before application to the meltable layer and / or additional layer. The thermoreactive material is a dry combination of a polymer resin containing an aqueous acrylic resin, and a mixture of expandable graphite, at least one FR additive and at least one polyhydroxy compound after the heating step during the manufacture of the textile composite material. The thermoreactive material is a dried combination of an aqueous acrylic resin, expandable graphite and a mixture with at least one FR additive within the textile composite material of the present disclosure.

[0036] In a fourth aspect, a method of forming or manufacturing a textile composite material described herein is provided, the method comprising: a) providing a meltable layer and an additional layer; b) applying a thermally reactive composition onto the meltable layer, the additional layer, or both, wherein the thermally reactive composition comprises an aqueous acrylic resin, expandable graphite, at least one flame retardant additive, at least one polyhydroxy compound, and water; c) bonding the meltable layer and the additional layer together with the thermally reactive composition sandwiched therebetween to form a laminate; and d) heating the laminate to a temperature sufficient to remove at least a portion of the water from the aqueous acrylic resin.

[0037] The applying step can include applying the thermally reactive composition in a discontinuous pattern.

[0038] The laminate formed can have a length of about 400 meters or more, or about 500 meters or more, or about 1000 meters or more.

[0039] The method can include applying a durable water repellent coating onto the meltable layer.

[0040] The fusible layer can be a textile layer. The fusible layer can include one or more of woven fabric, knitted fabric, non-woven material, or combinations thereof. The fusible layer can be a multilayer textile including one or more of woven fabric, knitted fabric, and / or non-woven textile. The textile used for the fusible layer can include one or more of polyamide, such as nylon, nylon 6, nylon 6.6, polyester, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyurethane, polyolefin, polyethylene, polypropylene, and elastane. The fusible layer can be polyamide or polyester. The fusible material can be a blend or combination of polyamide, such as nylon, nylon 6, nylon 6.6, polyester, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyurethane, polyolefin, polyethylene, polypropylene, and / or elastane.

[0041] The fusible layer can include more than one fusible textile. For example, the fusible layer can include a combination of two or more of nylon, nylon 6, nylon 6.6, polyester, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyurethane, polyolefin, polyethylene, elastane, and polypropylene.

[0042] The fusible layer can be a fusible film, and this fusible film can be a microporous film or a non-porous film. The fusible film can be a non-porous and gas-impermeable film, for example, a fusible continuous film covering the whole or part of an article or clothing. The fusible continuous film does not permit chemicals or biological materials to penetrate from the surface of the composite article to the wearer. The fusible film can be a single-layer film or a multilayer film. In a flame-retardant composite article, the fusible film can be a microporous polyolefin, microporous polyester, or microporous polyurethane.

[0043] The meltable film can include polyolefin, polyethylene, polypropylene, ethyl vinyl alcohol (EVOH), ethyl vinyl acetate (EVAc), polyvinyl chloride (PVC), polyvinylidene chloride (PVdC), polyvinyl fluoride, polyvinylidene fluoride, fluoropolymer, polyurethane, polyester, polyamide, polyether, polyacrylate and polymethacrylate, copolyether ester, or their copolymers or multilayer laminates.

[0044] The meltable layer can be lightweight. The meltable layer can have a weight of about 120 grams per square meter (g / m 2 ) or less, about 110 g / m 2 or less, about 100 g / m 2 or less, about 90 g / m 2 or less, about 80 g / m 2 or less, 70 g / m 2 or less, about 60 g / m 2 or less, about 50 g / m 2 or less, about 45 g / m 2 or less, 40 g / m 2 or less, about 35 g / m 2 or less, about 30 g / m 2 or less, about 25 g / m 2 or less, or about 20 g / m 2 or less. In other embodiments, the meltable layer can be about 10 g / m 2 or more, or 15 g / m 2 or more. All weight measurements are carried out in accordance with DIN EN 12127 (1997 / 12).

[0045] The fusible layer can be a fusible and nonflammable textile. The fusible layer can include a phosphonate-modified polyester (e.g., materials sold under the trade names TREVIRA® CS and AVORA® FR). The fusible layer can include a fusible and nonflammable textile that is typically not intended for use in flame-retardant laminates for clothing applications. The textile composite material can typically include a fusible and nonflammable textile that is not intended for use in flame-retardant laminates for clothing applications, and can further include a thermally reactive material and an additional layer disposed on the thermally reactive material such that the thermally reactive material is between the fusible layer and the additional layer. The textile composite material can be used for flame-retardant laminate applications.

[0046] The fusible layer can be a multilayer textile. The fusible layer can be a multilayer textile including two or more layers. The fusible layer can be a multilayer textile including two or more textile layers. The fusible layer can be a multilayer textile including two or more layers selected from knitted textile layers, woven textile layers, and / or nonwoven textile layers. The fusible layer can include a multilayer textile including two or more layers, with at least one of the layers being a fusible textile. The fusible layer can include a multilayer textile including two or more layers, with each layer being a fusible textile. The textile layers in the multilayer textile can be stacked on top of each other in a layered manner.

[0047] Clothing can include the textile composite material described herein, and the fusible layer is the outer layer. The fusible outer layer can include a multilayer textile. When the multilayer textile is used as the fusible outer layer, the individual fusible layers can be selected independently of each other.

[0048] The use of fusible textiles can be beneficial because such materials can be lightweight, inexpensive, easy to dye and print, and can have suitable abrasion resistance. "Suitable abrasion resistance" means that the fusible textile has abrasion resistance measured according to DIN EN ISO 12 947-2 (2006) that is equal to or greater than that of polyester or polycotton of the same weight and structure.

[0049] The fusible layer can be the outer layer that faces the environment during use (e.g., when wearing clothing) or faces away from the user.

[0050] The fusible layer can include one or more treatments to improve the properties of the textile composite. Such treatments can be applied to the fusible layer before the formation of the textile composite or can be applied after the formation of the textile composite.

[0051] The meltable layer can include a flame retardant (FR) treatment. Suitable flame retardant treatments include, but are not limited to, applying a flame retardant chemical finish to the meltable layer or adding a chemical treatment agent to the fibers before weaving or knitting into a meltable textile or fabric. The flame retardant treatment can be such that it does not affect the melting properties of the meltable layer. The flame retardant treatment can include treatment with nanoclay. The flame retardant treatment can include treatment with montmorillonite. The flame retardant treatment can include treatment with one or more of aluminum oxide, aluminum hydroxide (ATH), magnesium hydroxide (MDH), hydrotalcite, hydromagnesite, red phosphorus, boron borate, organochlorine, organobromine, antimony trioxide, antimony pentoxide, sodium antimonate, organic phosphate, tris(2,3-dibromopropyl) phosphate, tetrabromobisphenol A (TBBPA), 2,2-bis(bromomethyl)-1,3-propanediol (BBMP), triphenyl phosphate (TPP), tris(1,3-dichloro-2-propyl) phosphate (TDCPP), tris(2-chloroethyl) phosphate (TCEP), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (TBB), bis(2-ethylhexyl) 3,4,5,6-tetrabromophthalate (TBPH), hexabromocyclododecane (HBCD), ammonium phosphate, ammonium sulfate, triisopropyl phosphate, diethyl ethyl phosphate, tris-(chloroethyl) phosphate, triphenyl phosphate, tris-(2-chloroethylhexyl) phosphate, tricresyl phosphate, mono-, bis- and tris-(isopropylphenyl) phosphate, triisopropylphenyl phosphate, resorcinol-bis-(diphenyl phosphate), bisphenol-A-bis-(diphenyl) phosphate, melamine, melamine phosphate, melamine cyanurate, melamine polyzinc, aluminum phosphate, melamine-based hindered amine light stabilizer, ethylenediamine phosphate, cyclic phosphonate, aromatic phosphonate, aliphatic phosphate ester, chlorinated paraffin, hexabromobenzole, tetrabromophthalic anhydride or a combination thereof.The flame-retardant treatment can provide FR protection to avoid and / or reduce flammability and afterglow.

[0052] The fusible layer can include a treatment for providing a resist finish. The fusible layer can be resist-dyed in any suitable color and / or pattern. The fusible layer can be resist-dyed with any suitable dye. For example, a camouflage pattern can be resist-dyed on the fusible layer. A light-reflective material can be resist-dyed on the fusible layer.

[0053] The fusible layer can include a treatment for adjusting near-infrared reflection or absorption characteristics. The fusible layer can include a treatment with a phthalocyanine pigment precursor. The fusible layer can be resist-dyed with a phthalocyanine dye. The fusible layer resist-dyed with a phthalocyanine dye can provide infrared (IR) camouflage (for military applications, etc.). Without being bound by theory, the phthalocyanine pigment precursor can absorb light in the near-infrared (NIR) region.

[0054] The fusible layer can be subjected to a hydrophobic treatment that helps reduce the water absorbency of the textile composite material. Suitable hydrophobic treatments can include fluorochemical treatments and / or silicone-based treatments.

[0055] The fusible layer can be subjected to an insecticidal or insect-repellent treatment such as permethrin or DEET, for example.

[0056] The fusible layer can include a hydrophilic or oleophobic treatment to impart water absorbency or stain resistance to the textile composite material.

[0057] The thermally reactive material can include a polymer resin containing an aqueous acrylic resin. The thermally reactive material can contain an aqueous acrylic resin. The thermally reactive material can include expandable graphite. The thermally reactive material can contain a flame retardant (FR) additive. The thermally reactive material can include a polyhydroxy compound. The thermally reactive material can contain a polymer resin containing an aqueous acrylic resin, expandable graphite, a flame retardant (FR) additive, and a polyhydroxy compound. The thermally reactive material can consist essentially of an aqueous acrylic resin, expandable graphite, a flame retardant (FR) additive, and a polyhydroxy compound. When used in this context, "consist essentially of" means that the thermally reactive material contains the recited materials and contains other materials that can potentially have a substantial effect on the composition at about 10 wt% or less (or about 5 wt% or less, or about 4 wt% or less, or about 3 wt% or less, or about 2 wt% or less, or about 1 wt% or less). The weight percent is based on the total weight of the thermally reactive material minus any volatile substances that may be present, such as water or other organic molecules that can evaporate during drying and curing processes.

[0058] Examples of the aqueous acrylic resin can include an aqueous acrylic polymer resin. The aqueous acrylic resin can contain acrylamide repeating units. The aqueous acrylic resin can contain N-methylolacrylamide repeating units. The aqueous acrylic resin can be an aqueous acrylic polymer resin and can contain N-methylolacrylamide repeating units, such as EDOLAN® AM available from Tanatex Chemicals B.V. of Ede, the Netherlands. The aqueous acrylic resin can be an acrylic copolymer containing different amounts of styrene. The aqueous acrylic resin can be an acrylic copolymer containing different amounts of acrylamide monomer. The aqueous acrylic resin can further contain acrylonitrile, vinyl acetate, styrene, or combinations thereof.

[0059] The aqueous acrylic resin can be thermoplastic. The aqueous acrylic resin can be self-crosslinking. The acrylic polymer can be a crosslinkable acrylic polymer. As is known in the art, the term "self-crosslinkable" means that the aqueous acrylic resin contains functional groups that can react with each other under specific conditions, such as high temperature, hydrolysis conditions, etc., to form a crosslinked polymer. In some embodiments, self-crosslinking can be initiated by applying a high temperature of, for example, about 120 °C or higher without using additional chemicals. The aqueous acrylic resin can contain a crosslinking agent. The aqueous acrylic resin can be uncrosslinked. The aqueous acrylic resin may be self-crosslinked and may further contain a crosslinking agent. The addition of a crosslinking agent can improve the binding to the textile. The thermoreactive composition can contain a crosslinking agent to produce a crosslinked aqueous acrylic resin.

[0060] The thermoreactive composition can comprise, or consist essentially of, an aqueous acrylic resin, expandable graphite, at least one FR additive, at least one polyhydroxy compound, and a crosslinking agent. Suitable crosslinking agents can include, for example, one or more of polyisocyanate-based crosslinking agents, blocked polyisocyanate-based crosslinking agents. Other suitable crosslinking agents are the following materials: N-methoxymethylmelamine, methylolmelamine, carbodiimide, polycarbodiimide, isocyanate, polyisocyanate, diaminocarbamate, propyleneimine crosslinking agent according to the chemical structure, propyleneimine, aliphatic propyleneimine, aromatic propyleneimine derivative, reaction product between a polyfunctional acrylate and propyleneimine, (cyclic) aliphatic bisamide crosslinking agent, or a combination thereof.

[0061] Based on the total mass of the aqueous acrylic resin and the crosslinking agent, the thermoreactive composition can contain about 10% by mass or less, or about 9% by mass or less, or about 8% by mass or less, or about 7% by mass or less, or about 6% by mass or less, or about 5% by mass or less, or about 4% by mass or less, or about 3% by mass or less, or about 2% by mass or less, or about 1% by mass or less of the crosslinking agent.

[0062] An aqueous acrylic resin having a melting temperature or softening temperature of less than about 280 °C can be used. This aqueous acrylic resin can expand expandable graphite by at least about 900 micrometers when heated to about 280 °C as measured by a TMA expansion test.

[0063] A suitable aqueous acrylic resin in the thermally reactive material can expand expandable graphite at a temperature lower than the thermal decomposition temperature of the fusible layer. The viscoelastic properties of the aqueous acrylic resin when exposed to heat enable the expansion of the expandable graphite and can maintain the structural integrity of the thermally reactive material after the expansion of the expandable graphite.

[0064] The thermally reactive material may not contain silicone or a silicone-containing compound. The thermally reactive material can be free of or substantially free of silicone. As used herein, "substantially free of silicone" means that the thermally reactive material can contain a silicone-containing compound of about 5 wt% or less, or about 4 wt% or less, or about 3 wt% or less, about 2 wt% or less, or about 1 wt% or less. All weight percentages are based on the total weight of the thermally reactive material.

[0065] One advantage of using an aqueous acrylic resin in the thermally reactive material is that print-through of the textile composite material can be reduced, for example, when compared to a textile composite material formed of a silicone-based thermally reactive material. This reduction in print-through can improve visual optics and color durability, such as in camouflage printing. Furthermore, a composite textile formed of an aqueous acrylic resin-based thermally reactive material may provide more suitable conditions for post-treatment, such as water repellency treatment, because acrylic chemicals react well with water repellency treatment agents compared to hydrophobic silicone.

[0066] The thermally reactive material may not contain, or may not substantially contain, glass fibers. It is known to use glass fibers in combination with a phosphorus-containing compound to form a relatively hard and stable char after thermal decomposition of the polymer resin. It is not necessary to use glass fibers to assist in the stabilization of the char formed by the thermally reactive materials described herein. As used herein, "essentially free of glass fibers" means that the thermally reactive material can contain about 5 wt% or less of glass fibers, or about 4 wt% or less, or about 3 wt% or less, or about 2 wt% or less, or about 1 wt% or less of glass fibers. All weight percentages are based on the total weight of the thermally reactive material.

[0067] A polymer resin containing an aqueous acrylic resin can contain, for example, an adhesive for laminating or attaching a meltable layer to an additional layer and / or can function as an adhesive.

[0068] The expandable graphite can expand at least about 400 microns in the TMA expansion test described herein when heated to about 240°C. The expandable graphite can expand at least about 500 microns in the TMA expansion test described herein when heated to about 240°C. The expandable graphite can expand at least about 600 microns in the TMA expansion test described herein when heated to about 240°C. The expandable graphite can expand at least about 700 microns in the TMA expansion test described herein when heated to about 240°C. The expandable graphite can expand at least about 800 microns in the TMA expansion test described herein when heated to about 240°C. The expandable graphite can expand at least about 900 microns in the TMA expansion test described herein when heated to about 280°C.

[0069] The expandable graphite can have an endotherm of about 50 joules / gram (J / g) or more, or about 75 J / g or more, or about 100 J / g or more, about 125 J / g or more, or about 150 J / g or more, or about 175 J / g or more, or about 200 J / g or more, or about 225 J / g or more, or about 250 J / g or more. The endotherm value of the expandable graphite material can be determined using differential scanning calorimetry (DSC).

[0070] The expandable graphite can also have both good expansion as described above and an endotherm of at least about 100 J / g when tested according to the DSC endotherm test method as described herein. The expandable graphite can have an expansion of more than about 900 μm at about 280 °C when measured in the TMA expansion test as described herein, and an endotherm of about 100 J / g or more when tested according to the DSC endotherm test method as described herein.

[0071] The size of the expandable graphite particles incorporated into the thermally reactive material can be selected such that the thermally reactive material is applied by the selected application method. For example, when the thermally reactive material is applied by gravure printing or screen printing techniques, the expandable graphite particle size can be made small enough to fit into the openings of the gravure cell or screen printing or spray nozzle (carpet printing). The expandable graphite can be Asbury 3626 expandable graphite available from Asbury Carbons, Asbury, New Jersey, USA.

[0072] The thermally reactive material can also include at least one flame retardant (FR) additive. The thermally reactive material can include one or more flame retardant (FR) additives selected from melamine, polyphosphate, or combinations thereof. The FR additive can be melamine polyphosphate. The thermally reactive material can include at least one of AFLAMMIT® PMN500 melamine, AFLAMMIT® PMN200 melamine polyphosphate, and AFLAMMIT® PCO962 additive, all of which are available from Thor GmbH, Spyer, Germany.

[0073] The thermally reactive material can also include at least one polyhydroxy compound. The polyhydroxy compound can have a molecular weight of less than about 1000 g / mol, less than about 500 g / mol, less than about 250 g / mol, or less than about 100 g / mol. For example, in some embodiments, the polyhydroxy compound can be propane-1,2,3-triol. In some embodiments, the polyhydroxy compound can be propane-1,2,3-triol, butane-1,2,3,4-tetrol (erythritol), 2,2-(bishydroxymethyl)propane-1,3-diol (pentaerythritol), ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, or combinations thereof.

[0074] The thermoreactive composition comprises from about 50 to about 90 weight percent (wt%) of an aqueous acrylic resin, or from about 50 to about 80 wt% of an aqueous acrylic resin, or from about 50 to about 76 wt% of an aqueous acrylic resin, or from about 60 to about 80 wt% of an aqueous acrylic resin, or from about 55 to about 90 wt% of an aqueous acrylic resin, or from about 55 to about 85 wt% of an aqueous acrylic resin, or from about 55 to about 80 wt% of an aqueous acrylic resin, or from about 55 to about 76 wt% of an aqueous acrylic resin, or from about 60 to 90 wt% of an aqueous acrylic resin, or from about 60 to about 85 wt% of an aqueous acrylic resin, or from about 60 to about 80 wt% of an aqueous acrylic resin, or from about 60 to about 76 wt% of an aqueous acrylic resin. All weight percents are based on the total weight of the thermoreactive composition.

[0075] Based on the total weight of the thermoreactive composition, the thermoreactive composition can contain expandable graphite in the range of from about 5 to about 45 weight percent (wt%), where the weight percent is based on the total weight of the thermoreactive composition. The expandable graphite can be present in the thermoreactive composition in the range of from about 5 to about 40 wt%, or from about 5 to about 35 wt%, or from about 5 to about 30 wt%, or from about 5 to 25 wt%, or from about 10 to 45 wt%, or from about 10 to 40 wt%, or from about 10 to about 35 wt%, or from about 10 to about 30 wt%, or from about 10 to about 25 wt%, where the weight percent is based on the total weight of the wet thermoreactive composition.

[0076] Based on the total weight of the thermoreactive composition, the thermoreactive composition can contain at least one FR additive in the range of from about 5 to about 45 weight percent (wt%), or in the range of from about 5 to about 40 wt%. The at least one FR additive can be present in the thermoreactive composition in the range of from about 5 to about 35 wt%, or from about 5 to about 30 wt%, or from about 5 to about 25 wt%, from about 10 to about 45 wt%, or from about 10 to about 40 wt%, or from about 10 to about 35 wt%, or from about 10 to about 30 wt%, or from about 10 to about 25 wt%, where the weight percent is based on the total weight of the thermoreactive composition.

[0077] Based on the total mass of the thermally reactive composition, the thermally reactive composition contains at least one polyhydroxy compound in the range of about 3 to about 10 wt%, or about 3 to about 8 wt%, or about 3 to about 7 wt%.

[0078] A mixture of expandable graphite and at least one FR additive can be present in the thermally reactive composition in the range of about 5 to about 45 wt% of expandable graphite and about 5 to about 45 wt% of the FR additive, based on the total mass of the thermally reactive composition. The mixture of expandable graphite and at least one FR additive can be present in the thermally reactive composition in the range of about 10 to about 40 wt% of expandable graphite and about 10 to about 40 wt% of the FR additive, or in the range of about 10 to about 30 wt% of expandable graphite and about 10 to about 25 wt% of the FR additive, and all mass percentages are based on the total mass of the thermally reactive composition.

[0079] The thermally reactive composition can contain about 50 to about 90 wt% of an aqueous acrylic resin and about 10 to about 50 wt% of a mixture of expandable graphite and an FR additive, based on the total mass of the thermally reactive composition. The thermally reactive composition can contain about 50 to about 80 wt% of an aqueous acrylic resin and about 20 to about 50 wt% of a mixture of expandable graphite and an FR additive, based on the total mass of the thermally reactive composition. The thermally reactive composition can contain about 50 to about 75 wt% of an aqueous acrylic resin and about 25 to about 50 wt% of a mixture of expandable graphite and an FR additive, based on the total mass of the thermally reactive composition. The thermally reactive composition can contain about 50 to about 70 wt% of an aqueous acrylic resin, about 5 to about 15 wt% of expandable graphite, about 5 to about 15 wt% of an FR additive, and about 3 to about 10 wt% of a polyhydroxy compound, based on the total mass of the thermally reactive composition.

[0080] The thermally reactive composition can contain about 50 to about 80 wt% of an aqueous acrylic resin, about 5 to about 15 wt% of expandable graphite, about 5 to about 15 wt% of a flame retardant additive, about 5 to about 20 wt% of a polyhydroxy compound, and about 5 to about 50 wt% of water, based on the total mass of the thermally reactive composition.

[0081] The thermoreactive composition can include additional additives such as pigments, fillers, antimicrobial agents, processing aids, crosslinking agents, thickeners, emulsifiers, defoamers, and stabilizers. The thermoreactive composition can include optional additives of about 10 wt% or less, or about 5 wt% or less, or about 4 wt% or less, or about 3 wt% or less, less than about 2 wt%, or about 1 wt% or less. In some embodiments, the thermoreactive composition may not include an emulsifier. All weight percentages are based on the total weight of the thermoreactive composition.

[0082] The thermoreactive composition can be produced by a method that provides a tight blend of a polymer resin including an aqueous acrylic resin, expandable graphite, an FR additive, and a polyhydroxy compound without causing substantial expansion of the expandable graphite. The aqueous acrylic resin can be an aqueous acrylic polymer. The expandable graphite, the FR additive, the polyhydroxy compound, and optional additives such as crosslinking agents can be mixed or blended separately from or simultaneously with each other with the aqueous acrylic resin to form the thermoreactive composition. Examples of mixing methods include, but are not limited to, paddle mixers, blending, and other low-shear mixing techniques. A tight blend of the aqueous acrylic resin, expandable graphite particles, FR additive, and polyhydroxy compound can be achieved by mixing the monomer mixture and / or prepolymer with the expandable graphite, FR additive, and polyhydroxy compound prior to polymerization of the aqueous acrylic resin. The monomer mixture and / or prepolymer can then be polymerized to produce the thermoreactive composition. In a method for providing a tight blend of the aqueous acrylic resin, FR additive, polyhydroxy compound, and expandable graphite particles or expandable graphite aggregates, the expandable graphite can be coated or encapsulated with the aqueous acrylic resin prior to expansion of the graphite.

[0083] The thermoreactive composition can be applied as a continuous layer.

[0084] The thermoreactive composition can be applied as a discontinuous layer. The discontinuous layer of the thermoreactive composition can have a surface coverage of less than 100%. Applying the thermoreactive composition as a discontinuous layer can improve air permeability, water vapor permeability, and / or the feel.

[0085] The discontinuous pattern of the thermoreactive composition can include any suitable shape or form. For example, the pattern can include one or more of dots, shapes, circles, squares, triangles, stars, diamonds, pentagons, hexagons, heptagons, octagons, polygons, ellipses, grids, lines, waveforms, zigzag lines, etc. Applying the thermoreactive material discontinuously can provide a surface coverage of less than 100% by forms including, but not limited to, dots, grids, lines, and combinations thereof. As used herein, the term "dot" means one or more of any discrete shape, such as a circle, square, rectangle, triangle, diamond, pentagon, hexagon, heptagon, octagon, ellipse, polygon, star, heart shape, etc. The line can have a straight shape, a waveform shape, a curved shape, or a mixed shape thereof. Depending on the pattern, the dots and lines can be arranged close to or spread out from each other. The lines can be arranged in a grid pattern.

[0086] The average distance between adjacent regions of the discontinuous pattern can be about 10 millimeters (mm) or less, or about 9 mm or less, or about 8 mm or less, or about 7 mm or less, or about 6 mm or less, or about 5 mm or less, or about 4 mm or less, or about 3.5 mm or less, or about 3 mm or less, or about 2.5 mm or less, or about 2 mm or less, or about 1.5 mm or less, or about 1 mm or less, or about 0.5 mm or less, or about 0.4 mm or less, about 0.3 mm or less, or about 0.2 mm or less. The average distance between adjacent regions of the discontinuous pattern can be about 40 microns or more, or about 50 microns or more, or about 100 microns or more, or about 200 microns or more, depending on the application. The average dot spacing measured to be about 200 microns or more and about 500 microns or less is useful in some of the patterns described herein. As used herein, "average distance between adjacent regions" means the distance between the edges of adjacent dots.

[0087] Pitch can be used in combination with surface coverage, for example, as a way to describe the laydown of a resist pattern. Generally, pitch is defined as the average center-to-center distance between adjacent shapes such as dots, lines, or grid lines of a resist pattern. The average is used, for example, to account for a resist pattern with irregular spacing. The thermally reactive composition can be applied discontinuously in a pattern having a pitch and surface coverage that provides excellent flame retardant performance as compared to continuous application of the thermally reactive composition having an equal weight laydown of the thermally reactive composition. Pitch can be defined as the average of the center-to-center distances between adjacent shapes of the thermally reactive composition. For example, pitch can be defined as the average of the center-to-center distances between adjacent dots or grid lines of the thermally reactive composition. Pitch can be about 500 microns or more, about 600 microns or more, about 700 microns or more, about 800 microns or more, about 900 microns or more, about 1000 microns or more, about 1200 microns or more, about 1500 microns or more, about 1700 microns or more, about 1800 microns or more, about 2000 microns or more, about 3000 microns or more, about 4000 microns or more, about 5000 microns or more, about 6000 microns or more, or any value therebetween. Preferred patterns of the thermally reactive composition can have a pitch of about 500 microns to about 6000 microns.

[0088] In embodiments where properties such as hand feel, breathability, and / or textile weight are important, a surface coverage of about 25% or more and about 90% or less, or less than about 80%, or less than about 70%, or less than about 60%, or less than about 50%, or less than about 40%, or less than about 30% can be used. When exposed to heat, the meltable layer can be exposed to sufficient energy to burn. In certain embodiments, when higher flame retardancy is required, it may be desirable to have a surface coverage of about 30% to about 100% of the heat-reactive material on the surface of the inner textile or intermediate layer. When higher flame retardancy is required, it may be desirable to have a surface coverage of the heat-reactive material at a pitch of about 500 microns to about 6000 microns. For example, the surface coverage of the heat-reactive material can be about 30% to about 80% of the heat-reactive material on the surface of the inner textile or intermediate layer at a pitch of about 500 microns to about 6000 microns.

[0089] The heat-reactive composition can be applied in a discontinuous dot pattern. The dots can have a diameter in the range of about 0.8 mm or more to about 5 mm. The dots can have a diameter in the range of about 0.9 mm to about 4.5 mm. The dots have a diameter in the range of about 1.0 mm to about 4.0 mm. The dots can have a diameter in the range of about 1.0 mm to about 3.5 mm. The dots can have a diameter in the range of about 1.0 to about 3.0 mm. The dots can have a diameter in the range of about 1.0 mm to about 2.5 mm. The dots can have a diameter in the range of about 1.0 mm to about 2.25 mm. The dots can have a diameter in the range of about 1.0 mm to about 2.2 mm. The dots can have a diameter in the range of about 1.0 mm to about 2.1 mm. The dots can have a diameter in the range of about 1.0 mm to about 2.0 mm.

[0090] The thermally reactive material can cover from about 20% or more to about 100% of the surface area of the fusible layer and / or additional layer. The thermally reactive material can cover from about 25% to about 80% of the surface area of the fusible layer and / or additional layer. The thermally reactive material can cover from about 25% to about 75% of the surface area of the fusible layer and / or additional layer. The thermally reactive material can cover from about 25% to about 55% of the surface area of the fusible layer and / or additional layer. The thermally reactive material can cover from about 25% to about 40% of the surface area of the fusible layer and / or additional layer. The thermally reactive material can cover from about 25% to about 35% of the surface area of the fusible layer and / or additional layer.

[0091] The thermally reactive material can cover from about 30% to about 100% of the surface area of the fusible layer and / or additional layer. The thermally reactive material can cover from about 45% to about 100% of the surface area of the fusible layer and / or additional layer. The thermally reactive material can cover from about 55% to about 100% of the surface area of the fusible layer. The thermally reactive material can cover from about 65% to about 100% of the surface area of the fusible layer. The thermally reactive material can cover from about 70% to about 100% of the surface area of the fusible layer and / or additional layer. The thermally reactive material can cover from about 95% to about 100% of the surface area of the fusible layer and / or additional layer.

[0092] The thermally reactive material can cover from about 30% to about 70% of the surface area of the fusible layer and / or additional layer. The thermally reactive material can cover from about 45% to about 65% of the surface area of the fusible layer and / or additional layer. The thermally reactive material can cover from about 25% to about 50% of the surface area of the fusible layer and / or additional layer. The thermally reactive material can cover from about 65% to about 90% of the surface area of the fusible layer. The thermally reactive material can cover from about 70% to about 80% of the surface area of the fusible layer and / or additional layer.

[0093] These ranges of the coverage rate of the layer with less than 100% heat-reactive material can improve the properties of textile composite materials such as air permeability, hand feel, breathability, and / or textile weight. For example, when the heat-reactive material is applied to the meltable layer and / or additional layer with a deposition of about 20% to about 95%, compared with a textile composite material in which the heat-reactive material is applied as a continuous layer with a 100% coverage rate to the meltable layer and / or additional layer, the air permeability and breathability of the textile composite material can be improved, the hand feel can be improved, and the weight can be reduced.

[0094] Methods for achieving a coverage rate of less than 100% can include applying or printing the heat-reactive composition onto the surface of the meltable layer, additional layer, or both. Suitable application, printing, or deposition methods for the heat-reactive composition include, but are not limited to, screen printing, rotary screen printing, gravure printing, spray or spread coating, or knife coating. In screen printing or rotary screen printing of the heat-reactive material, higher laydown (compared to the laydown achievable with a gravure roll) and lower area coverage are possible, enabling relatively high air permeability of the textile composite. Using this method, since the heat-reactive composition can contain water, the thickness of the screen may increase. However, after printing, a heat source, such as an oven or a heating roll, can be used to remove (e.g., evaporate) at least a portion of the water from the heat-reactive composition. When water is removed from the heat-reactive composition during heating, the mass of the heat-reactive material decreases, and a lighter textile composite material can be obtained. When at least a portion of the water in the heat-reactive composition is removed, the mass of the heat-reactive material can decrease by about 20%, or about 25%, or about 30%, or about 35%, or about 40%, or about 45% compared to the mass of the heat-reactive composition before water removal.

[0095] When the textile composite material is exposed to flame and / or heat, such as a temperature of about 280 °C or higher, the fusible layer begins to melt, and the melt can be mixed with the thermally reactive material, in particular, expandable graphite. In this process, a char containing the fusible layer and the thermally reactive material can also be formed. The char resulting from exposing the fusible layer and the thermally reactive material to heat and / or a high temperature of, for example, about 280 °C or higher can be a heterogeneous molten mixture containing at least the fusible layer and the expanded expandable graphite after expansion. According to the present disclosure, the char is intended to refer to the carbonaceous material remaining after exposing the fusible layer and the thermally reactive material to a temperature of about 280 °C or higher. At a temperature of about 280 °C or higher, one or both of the fusible layer and the aqueous acrylic resin can also oxidize or participate in the combustion process to form additional carbonaceous material that becomes part of the char. The formation of the char can help insulate the layer below the char from exposure to heat.

[0096] When the thermally reactive material expands, it can form a plurality of whiskers containing expanded graphite. During the expansion process, the total volume of the thermally reactive material can increase significantly when compared to the same mixture before expansion. The volume of the thermally reactive material can increase by at least about 5 times after expansion. The volume of the thermally reactive material can increase by at least about 6 times after expansion. The volume of the thermally reactive material can increase by at least about 7 times after expansion. The volume of the thermally reactive material can increase by at least about 8 times after expansion. The volume of the thermally reactive material can increase by at least about 9 times after expansion. The volume of the thermally reactive material can increase by at least about 10 times after expansion.

[0097] When a textile composite material includes a fusible layer, an additional layer, and a thermally reactive material applied in a discontinuous pattern, the thermally reactive material expands to form frills, is loosely packed after expansion, voids are formed between the frills, and spaces are formed between the patterns of the expanded thermally reactive material. When exposed to a flame, the fusible layer can melt and generally move away from the open areas between the discontinuous forms of the thermally reactive material. The additional layer can support the thermally reactive material during expansion, and the melt of the fusible layer can be absorbed and retained by the thermally reactive material that is expanding during melting. By absorbing and retaining the melt, the textile composite material described herein can be shown not to exhibit dripping of the melt. By absorbing and retaining the melt, the textile composite material described herein can be nonflammable as measured by the horizontal burn test described herein. Thermal stability When the thermally stable additional layer supports the thermally reactive material that is expanding during melt absorption, the thermally stable additional layer can be protected from tearing and forming holes. When the surface area of the thermally reactive material increases during expansion, absorption of the melt from the fusible layer by the expanded thermally reactive material when exposed to a flame can be enabled.

[0098] The textile composite material described herein can exhibit improved properties by a combination of a fusible layer, a thermally reactive material including an aqueous acrylic resin, expandable graphite, and an FR additive, and an additional layer. For example, the textile composite material can have a afterflame of about 2 seconds or less when tested for flame retardancy using the horizontal burn test described herein. Further, in some embodiments, the textile composite material may not exhibit dripping of the melt, formation of holes, and spread of the flame or glowing at the edges.

[0099] Since the thermoreactive composition contains an aqueous acrylic resin that can later remove water, the textile composite can have a dry peel strength in the range of about 5 to about 30 Newtons (N). The textile composite material can have a dry peel strength in the range of about 6 to about 30 N. The textile composite material can have a dry peel strength in the range of about 7 to about 30 N. The textile composite material can have a dry peel strength in the range of about 7 to about 24 N. The textile composite material can have a dry peel strength in the range of about 7 to about 23 N. The textile composite material can have a dry peel strength in the range of about 7 to about 22 N. The textile composite material can have a dry peel strength in the range of about 7 to about 21 N. The textile composite material can have a dry peel strength in the range of about 8 to about 22 N. The textile composite can have a dry peel strength in the range of about 8 to about 23 N. The textile composite material can have a dry peel strength in the range of about 8 to about 24 N. The textile composite material can have a dry peel strength in the range of about 8 to about 25 N. The value of the dry peel strength is as measured by DIN 54310.

[0100] The additional layer can be made of a heat-stable material. When exposed to fire, the fusible layer can melt towards the thermoreactive material. When the expandable graphite in the thermoreactive material expands, the heat-stable additional layer can hold the expanding thermoreactive material in place and facilitate the absorption of the melt of the fusible layer.

[0101] The additional layer can be a textile layer, a heat-stable textile layer, or a combination thereof. As disclosed above, the textile can be a woven fabric, a knitted fabric, a non-woven textile, or a multi-layer combination thereof. Examples of heat-stable textiles include, but are not limited to, aramid, flame-retardant cotton, cotton, linen, cupra, acetate, triacetate, wool, viscose, polybenzimidazole (PBI), polybenzoxazole (PBO), FR rayon, modacrylic, modacrylic / cotton blend, polyamine, glass fiber, polyacrylonitrile, polytetrafluoroethylene, or a combination thereof.

[0102] The additional layer can be a fusible layer. The fusible additional layer can be a fusible textile comprising one or more of a woven fabric, a knitted fabric, a non-woven material, or a combination thereof. The additional layer can be a fusible multi-layer textile comprising one or more of a woven fabric, a knitted fabric, and / or a non-woven textile. The textile used for the fusible additional layer can comprise one or more of polyamide, such as nylon, nylon 6, nylon 6.6, polyester, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyurethane, polyolefin, polyethylene, polypropylene, and elastane. The fusible additional layer can be polyamide or polyester. The fusible additional layer can be a blend or combination of polyamide, such as nylon, nylon 6, nylon 6.6, polyester, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyurethane, polyolefin, polyethylene, polypropylene, and / or elastane.

[0103] The fusible additional layer can include more than one fusible textile. For example, the fusible additional layer can include a combination of two or more of nylon, nylon 6, nylon 6.6, polyester, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyurethane, polyolefin, polyethylene, elastane, and polypropylene.

[0104] The additional layer can be a non-fusible textile such as cotton. The additional layer can be a non-fusible textile that includes fusible fibers. For example, the additional layer can be a textile that includes cotton and polyethylene terephthalate (PET). The additional layer can be a textile that includes cotton and polyamide (PA). The additional layer can be a textile that includes PET and viscose.

[0105] The additional layer can be a fusible film, and this fusible film can be a microporous or non-porous film. The fusible film can be a non-porous and gas-impermeable film, for example, a fusible continuous film that covers all or part of an article or clothing. The fusible continuous film can be such that it does not allow chemical or biological substances to penetrate from the surface of the composite article towards the wearer. The fusible film can be a single-layer film or a multi-layer film. In a flame-retardant composite article, the fusible film can be a microporous polyolefin, microporous polyester, or microporous polyurethane.

[0106] The fusible film can include polyolefin, polyethylene, polypropylene, ethyl vinyl alcohol (EVOH), ethyl vinyl acetate (EVAc), polyvinyl chloride (PVC), polyvinylidene chloride (PVdC), polyvinyl fluoride, polyvinylidene fluoride, fluoropolymer, polyurethane, polyester, polyamide, polyether, polyacrylate, and polymethacrylate, copolyether ester, or their copolymers or multi-layer laminates.

[0107] Textile composite materials can be used for clothing for workers in dangerous environments. The textile composite materials can exhibit one or more properties such as breathability, waterproofness, flame retardancy, light weight, flexibility, and a comfortable wearing feeling.

[0108] The textile composite materials can have a weight in the range of about 80 to about 240 grams per square meter (g / m 2 )). The textile composite materials can have a weight in the range of about 80 to about 200 g / m 2 ). The textile composite materials can have a weight in the range of about 80 to about 180 g / m 2 ). The textile composite materials can have a weight in the range of about 80 to about 165 g / m 2 ). The textile composite materials can have a weight in the range of about 80 to about 150 g / m 2 ). The textile composite materials can have a weight in the range of about 80 to about 125 g / m 2 ). The textile composite materials can have a weight in the range of about 80 to about 100 g / m 2 ). The textile composite materials can have a weight in the range of about 80 to about 90 g / m 2 ).

[0109] The textile composite materials can have a weight in the range of about 95 to about 240 g / m 2 ). The textile composite materials can have a weight in the range of about 110 to about 240 g / m 2 ). The textile composite materials can have a weight in the range of about 125 to about 240 g / m 2 ). The textile composite materials can have a weight in the range of about 140 to about 240 g / m 2 ). The textile composite materials can have a weight in the range of about 165 to about 240 g / m 2 ). The textile composite materials can have a weight in the range of about 180 to about 240 g / m 2 ).

[0110] The textile composite material can have a weight in the range of about 115 to about 160 g / m 2 The textile composite material can have a weight in the range of about 95 to about 150 g / m 2 The textile composite material can have a weight in the range of about 165 to about 190 g / m 2 The textile composite material can have a weight in the range of about 135 to about 175 g / m 2 The textile composite material can have a weight in the range of about 85 to about 100 g / m 2 The textile composite material can have a weight in the range of about 85 to about 100 g / m. All mass measurements are performed in accordance with DIN EN 12127 (1997 / 12).

[0111] The additional layer can be disposed on the thermally reactive material such that the thermally reactive material is disposed between the meltable layer and the additional layer. The additional layer can be attached or bonded inside the meltable layer of the textile composite material by the thermally reactive material. In use, the outside of the meltable layer can be oriented to contact a flame or heat source.

[0112] The combined meltable layer, thermally reactive material, and additional layer can be joined or adhered by the application of pressure. For example, pressure between the nip of two rollers can be applied to the combined meltable layer, thermally reactive material, and additional layer.

[0113] The combined fusible layer, heat-reactive material, and additional layer can be dried and cured by the application of heat. The temperature should be high enough to evaporate most of the water in the aqueous acrylic resin and at least a portion of any volatile compounds that may be present, but should be low enough so that the expandable graphite does not begin to expand. The heating temperature can be between 60°C and 180°C. The heating temperature for evaporating most of the moisture in the aqueous acrylic resin can be between about 80°C and about 100°C. The heating step can be carried out via one or more heating rolls, which can serve to provide heat to drive out water and / or volatile compounds and, optionally, can serve to provide pressure to cure or crosslink the aqueous acrylic resin and form better adhesion between the fusible layer and the additional layer.

[0114] This method can further include the step of applying pressure to the textile composite material to form a laminate.

[0115] The heat-reactive material can include an aqueous acrylic resin. Without being bound by theory, using an aqueous acrylic resin as the polymer resin can reduce the total mass of the textile composite material after the heating step in which at least a portion of the water is removed. However, reducing the amount of the heat-reactive material can limit the strength of the textile composite material. This solution is an improved mixture in which a polyhydroxy compound is added while reducing the amount of the heat-reactive material component, in particular, the amount of the FR additive and the amount of expandable graphite. Further advantages are an improvement in flame resistance (char performance) and an improvement in processability. Typically, a char is a relatively lightweight crust that forms after the textile composite material is exposed to a heat source or a flame source, i.e., after the thermal decomposition of the fusible layer and the expansion of the expandable graphite, and can function as a heat-insulating layer to protect the wearer from at least a portion of the heat. Since the char has little structural integrity, it can easily fall off the textile composite material when the textile is bent or moved. Surprisingly, adding a polyhydroxy compound, which is typically considered as a fuel source for a flame, to the heat-reactive material has been found to result in a char having a relatively high structural integrity when compared to the same heat-reactive composition without polyhydroxy. The improved structural integrity of the char allows the char to remain on the garment and can provide more time for the wearer to escape the effects of heat or flame. In one embodiment, a textile composite material having a afterflame of less than 2 seconds is described herein.

[0116] The textile composite material can have a afterflame of about 2 seconds or less when tested according to the DIN EN 15025A (April 2017) test standard. The textile composite material can have an afterflame of about 1.5 seconds or less when tested according to the DIN EN 15025A test standard. The textile composite material can have an afterflame of about 1 second or less when tested according to the DIN EN 15025A test standard. The textile composite material can have an afterflame of about 0.5 seconds or less when tested according to the DIN EN 15025A test standard. When exposed to a flame on the outside of the fusible layer with a layer of thermally reactive material when tested according to the DIN EN 15025A test standard, it can have an afterflame of about 2 seconds or less. During use, the fusible layer can shrink due to the flame.

[0117] Elongation can be incorporated into the textile composite material, thereby improving the comfort of clothing containing the textile composite material. Unidirectional stretch can be incorporated, for example, according to the disclosure of WO2018 / 067529 named "Stretchable laminate" filed in the name of W.L. Gore & Associates. As used herein, unidirectional stretch means that the textile composite material has recoverable elasticity in one of the machine direction or the cross direction, but typically not both. Other methods for incorporating elongation into the textile composite material, particularly methods involving one or more layers that are not inherently elastic, are known in the art. Suitable examples can include, for example, the teachings of EP1852253 named "Elongated composite film and composite fabric and method for producing the same" filed in the name of W.L. Gore and Associates.

[0118] The textile composite material can be used to manufacture clothing. When manufacturing clothing using the textile composite material, the textile composite material is oriented such that the fusible layer is exposed in the outer region of the clothing and the additional layer is disposed on the opposite side of the fusible layer, i.e., the additional layer faces the wearer.

[0119] The textile composite material provides an excellent lightweight protective clothing that can protect the wearer from burns. When the textile composite is exposed to a flame, the textile composite material can undergo a structural change to protect the wearer from harm. The heat-reactive material expands to prevent the meltable layer from burning and dripping onto the wearer, and while absorbing heat energy and molten textile, the meltable layer can melt. The combination of the melting of the meltable layer and the expansion of the heat-reactive material enables a lightweight textile composite material that can provide excellent comfort to the wearer and protection from burns.

[0120] It should be understood that the additional features disclosed in connection with each aspect or embodiment correspond to additional features of other aspects or embodiments of the present invention. For example, the method can include steps such as making a laminate material according to a first aspect, and thus can include any material preparation, coating, or manufacturing method disclosed in connection therewith. Further, the present invention extends to any laminate structure obtainable by the methods disclosed herein.

[0121] The above examples are merely examples and should not be construed as limiting or narrowing the scope of the concepts of the present invention provided separately by this disclosure. Although multiple examples are disclosed, further other embodiments will become apparent to those skilled in the art from the following detailed description which illustrates and describes exemplary examples. Therefore, the drawings and the detailed description are to be considered as being essentially non-limiting and essentially exemplary.

Brief Description of the Drawings

[0122] Brief Description of the Drawings The accompanying drawings are included to provide a further understanding of the present disclosure, are incorporated herein and constitute a part thereof, illustrate embodiments, and together with the description serve to explain the principles of the present disclosure.

[0123]

Figure 1

[0124]

Figure 2

[0125]

Figure 3

[0126]

Figure 4

[0127]

Figure 5

[0128]

Figure 6

DETAILED DESCRIPTION OF THE INVENTION

[0129] Definitions and Terms This disclosure is not intended to be read restrictively. For example, the terms used in this application should be read broadly in the sense relationships that a person skilled in the art would ascribe to those terms.

[0130] Regarding the term of inaccuracy, the terms "about" and "approximately" can be used interchangeably to refer to a measured value that includes the recited measured value and a measured value that also includes any measured value reasonably close to the recited measured value. A measured value reasonably close to the recited measured value deviates from the recited measured value by a reasonably small amount as would be understood and readily ascertainable by a person of ordinary skill in the relevant art. Such deviations can be due to measurement errors, differences in calibration of measurement and / or manufacturing equipment, human error in reading and / or setting of measured values, fine adjustments made to optimize performance and / or structural parameters taking into account differences in measured values related to other components, particular implementation scenarios, inaccurate adjustment and / or operation of the subject by a person or machine, etc. If it is determined that a person of ordinary skill in the relevant art cannot readily ascertain such values of reasonably small differences, the terms "about" and "approximately" can be understood to mean plus or minus 10% of the recited value.

[0131] Description of various embodiments A person of ordinary skill in the art will readily understand that the various aspects of the present disclosure can be implemented by any number of methods and apparatuses configured to perform the intended functions. It should also be noted that the accompanying drawings referred to herein are not necessarily drawn to scale and may be exaggerated in order to illustrate the various aspects of the present disclosure, and in that regard, the drawings should not be construed as limiting.

[0132] For the purposes of the present disclosure, the term "flame retardant", when used herein, refers to a textile or textile composite material that exhibits a afterflame of less than about 2 seconds when subjected to the DIN EN 15025A test standard.

[0133] For the purposes of the present disclosure, the term "flammable", when used herein, refers to a textile that has an afterflame of more than 2 seconds when tested in accordance with the horizontal burning test (DIN EN ISO 15025A) for textiles as shown herein.

[0134] For the purposes of the present disclosure, the term "laminate", as used herein, refers to a material in which at least two individual layers are joined via an adhesive or another means.

[0135] For the purposes of the present disclosure, the term "fusible", as used herein, refers to a textile or textile composite material that melts when tested according to the melting and thermal stability tests as set forth herein.

[0136] For the purposes of the present disclosure, the term "non-flammable", as used herein, refers to a textile that has a afterflame time of 2 seconds or less when tested according to the horizontal burning test (DIN EN ISO 15025A) for textiles as set forth herein.

[0137] For the purposes of the present disclosure, the term "textile", as used herein, refers to a fabric material made from fibers, filaments, yarns containing fibers and / or filaments, or combinations thereof. In particular, the term "textile", as used herein, refers to a manufactured sheet-like structure (e.g., a knitted fabric, a woven fabric, or a non-woven fabric) that contains fibers, filaments, and / or yarns.

[0138] For the purposes of the present disclosure, the term "void", as used herein, refers to the empty space / volume between the whiskers of expanded graphite.

[0139] A textile composite material having a fusible layer, a thermally reactive material, and an additional layer can be used as a protective garment. Examples of protective garments include clothing such as jackets, trousers, shirts, vests, overalls, gloves, gaiters, hoods, and boots.

[0140] The protective garment needs to be lightweight for widespread use, particularly in situations where there is a risk of flash fire, although the likelihood is low. To reduce the weight of the textile composite material, it is necessary to reduce the weight of the individual layers without losing protective properties or reducing breathability.

[0141] As described herein, the layer that can reduce weight is a thermally reactive material layer. When an aqueous acrylic resin is used as the polymer resin, the total mass of the textile composite material after the heating step in which at least a part of the water is removed decreases. However, when the amount of the thermally reactive material decreases, the strength of the textile composite material may be limited. Further, the stability of the process is limited by the thermally reactive material, and the production yard may be shortened.

[0142] The solution is an improved mixture in which a polyhydroxy compound is added while reducing the amount of the thermally reactive material component, in particular, the amount of the FR additive and the amount of expandable graphite. Additional advantages are improved flame retardancy (char performance), improved processability, and improved printing suitability. In one embodiment, a textile composite material with a afterflame of less than 2 seconds is described herein.

[0143] Referring to FIGS. 1-2, the textile composite material 10 includes a fusible layer 100, a thermally reactive material 102 including an aqueous acrylic resin, expandable graphite, at least one flame retardant additive, and at least one polyhydroxy compound, and an additional layer 108 on or adjacent to the thermally reactive material 102. In one embodiment, the thermally reactive material 102 is disposed on the inner side 104 of the fusible layer 100. When the outer side 106 of the fusible layer 100 is exposed to a flame, the afterflame of the textile composite material is less than 2 seconds when tested according to the DIN EN 15025A test standard.

[0144] FIG. 3 shows the textile composite material of FIGS. 1-2 in which the textile composite material includes a second additional layer 120. The second additional layer 120 can be a textile layer or a film layer.

[0145] The present disclosure relates to a textile composite material comprising: a) a fusible layer; b) a polymeric resin comprising an aqueous acrylic resin, expandable graphite, at least one flame retardant (FR) additive, and at least one polyhydroxy compound; and c) an additional layer disposed on the thermally reactive material such that the thermally reactive material is disposed between the fusible layer and the additional layer, wherein the afterflame of the textile composite material is less than 2 seconds. When manufacturing clothing using the textile composite material, the textile composite material is oriented such that the fusible layer is exposed in the outer region of the clothing and the additional layer is disposed on the opposite side of the fusible layer. That is, the additional layer is oriented towards the wearer of the clothing. The present disclosure also relates to embodiments in which, when the fusible layer is exposed to a flame, the combination of the fusible layer and the thermally reactive material forms a char. In some embodiments, the char comprises a carbonaceous layer formed after the polymeric materials of the fusible layer and the thermally reactive material have burned. The carbonaceous char has a very high melting point and provides thermal insulation to the material beneath the char.

[0146] The textile composite material includes a fusible layer, where the fusible layer can be a textile layer. The fusible layer can be a woven fabric, a knitted fabric, a tricot knit, a non-woven material, a multi-layer non-woven material, or a combination thereof. Suitable textiles for the fusible layer include, for example, polyamides such as nylon, nylon 6, nylon 6.6, polyesters, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyurethanes, polyolefins, polyethylene, polypropylene, elastane, or combinations thereof. The present disclosure also relates to any one of the above embodiments where the fusible layer is a polyamide or a polyester. In some embodiments, the fusible layer can be a single layer or two or more layers. In some embodiments, the fusible layer can be lightweight. For example, the fusible layer according to any of the above embodiments can be about 120 grams per square meter (g / m 2 ) or less, about 110 g / m 2 or less, about 100 g / m 2 or less, about 90 g / m2 The following can have a weight of about 80 g / m 2 The following can have a weight of 70 g / m 2 The following can have a weight of 60 g / m 2 The following can have a weight of 50 g / m 2 The following can have a weight of about 45 g / m 2 The following can have a weight of about 40 g / m 2 The following can have a weight of about 35 g / m 2 The following can have a weight of about 30 g / m 2 The following can have a weight of about 25 g / m 2 The following can have a weight of, or about 20 g / m 2 All weight measurements are carried out in accordance with DIN EN 12127 (1997 / 12).

[0147] In some embodiments, the fusible layer 100 can include one or more of a woven fabric, a knitted fabric, a non-woven material, or combinations thereof. The fusible layer can be a multi-layer textile including one or more of a woven fabric, a knitted fabric, and / or a non-woven fabric. The textile used for the fusible layer can include one or more of a polyamide, such as nylon, nylon 6, nylon 6.6, polyester, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyurethane, polyolefin, polyethylene, polypropylene, elastane, or combinations thereof. The fusible layer can be a polyamide or a polyester. The fusible material can be a blend or combination of a polyamide, such as nylon, nylon 6, nylon 6.6, polyester, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyurethane, polyolefin, polyethylene, polypropylene, and / or elastane. In some embodiments, the fusible layer 100 can be a fusible and non-flammable textile. Examples of fusible and non-flammable textiles include, for example, phosphonate-modified polyesters (materials sold under the trade names TREVIRA® CS and AVORA® FR, etc.). Some fusible and non-flammable textiles are not typically intended for use in flame-resistant laminates for clothing purposes because when constrained in a conventional laminate form, the textile cannot easily shrink away from the flame and will continue to burn. However, it has been found that the textile composite material can be used for flame-retardant laminate applications when the textile composite material further includes an additional layer 108 and an interlayer thermally reactive material 102.

[0148] In some embodiments, the fusible layer 100 includes more than one fusible textile. For example, in some embodiments, the fusible layer 100 includes a combination of two or more of nylon, nylon 6, nylon 6.6, polyester, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyurethane, polyolefin, polyethylene, polypropylene, elastane. In yet another embodiment, the fusible layer is a multilayer textile including two or more knitted fabrics, woven fabrics or non-woven fabrics. Each layer of the multilayer textile can be a fusible textile, and the textiles are stacked on top of each other in layers. If the multilayer textile is used as a fusible outer layer, the individual fusible layers can be selected independently of each other.

[0149] In some embodiments, the fusible layer can include one or more treatments to improve the properties of the textile composite. For example, the fusible outer layer can have a hydrophobic treatment that helps reduce the water absorption rate of the textile composite. Suitable hydrophobic treatments can include fluorochemical treatments and / or silicone-based treatments. The fusible outer layer can be treated with an insecticidal or insect repellent treatment such as permethrin or DEET, for example. In other embodiments, the fusible outer layer can include a hydrophilic or oleophobic treatment to impart desired water absorption or stain resistance to the textile composite. Such treatments can be applied to the fusible outer layer before the formation of the textile composite, or can be applied after the formation of the textile composite.

[0150] The textile composite material also includes a thermally reactive material, which comprises, or consists essentially of, an aqueous acrylic resin, expandable graphite, a flame retardant (FR) additive, and at least one polyhydroxy compound. When used in this context, "consisting essentially of" means that the thermally reactive material includes the recited materials and contains, on a mass basis, no more than 10% (or no more than 5%, or no more than 4%, or no more than 3%, or no more than 2%, or no more than 1%) of other materials that could substantially affect the composition. The mass percent is based on the total mass of the thermally reactive material minus any volatile substances that may be present, such as water or other organic molecules that can evaporate during the drying and curing processes.

[0151] In some embodiments, the acrylic polymer is an aqueous acrylic resin. In some embodiments, the aqueous acrylic resin includes acrylamide repeating units. In some embodiments, the aqueous acrylic resin includes N-methylolacrylamide repeating units. For example, in some embodiments, the aqueous acrylic resin is an aqueous acrylic polymer resin and includes N-methylolacrylamide repeating units, such as, for example, EDOLAN® AM available from Tanatex Chemicals B.V. of Ede, the Netherlands.

[0152] The water-based acrylic resin can be a thermoplastic resin. In one embodiment, it is a self-crosslinking water-based acrylic resin, and in another embodiment, it is a non-crosslinked water-based acrylic resin. In other embodiments, the thermoreactive material further includes a crosslinking agent to form a crosslinked water-based acrylic resin. In other embodiments, the thermoreactive material includes a self-crosslinking water-based acrylic resin and a crosslinking agent. The additional crosslinking agent can help improve the bonding to the fusible layer and the additional layer. Thus, in some embodiments, the thermoreactive material comprises or consists essentially of a water-based acrylic resin, expandable graphite, at least one FR additive, at least one polyhydroxy compound, and a crosslinking agent. Suitable crosslinking agents can include, for example, one or more of polyisocyanate-based crosslinking agents, blocked polyisocyanate-based crosslinking agents. Other suitable crosslinking agents are the following materials: N-methoxymethylmelamine, methylolmelamine, carbodiimide, polycarbodiimide, isocyanate, polyisocyanate, diaminocarbamate, propyleneimine crosslinking agent according to the chemical structure, propyleneimine, aliphatic propyleneimine, aromatic propyleneimine derivative, reaction product between a polyfunctional acrylate and propyleneimine, (cyclic) aliphatic bisamide crosslinking agent, or a combination thereof. If used, the crosslinking agent is typically used at about 10% by mass or less based on the total mass of the water-based acrylic resin and the crosslinking agent. In other embodiments, the crosslinking agent is present at about 8% by mass or less, or about 6% by mass or less, or about 5% by mass or less, or about 4% by mass or less, about 3% by mass or less, or about 2% by mass or less, or about 1% by mass or less, where all mass percentages are based on the total mass of the water-based acrylic resin and the crosslinking agent.

[0153] An aqueous acrylic resin having a melting temperature or softening temperature of less than 280 °C can be used in the disclosed embodiments. In some embodiments, the aqueous acrylic resin is deformable when exposed to heat of 300 °C or less, or 280 °C or less, and the expandable graphite can expand substantially. With an appropriate aqueous acrylic resin in the thermally reactive material, the expandable graphite can expand sufficiently at a temperature lower than the thermal decomposition temperature of the meltable outer textile. In some embodiments, the viscoelastic properties of the aqueous acrylic resin upon exposure to heat enable the expansion of the expandable graphite and can maintain the structural integrity of the thermally reactive material after the expansion of the expandable graphite.

[0154] In some embodiments, the thermally reactive material does not contain silicone or a silicone-containing compound. In other embodiments, the thermally reactive material does not contain silicone or is essentially free of silicone. As used herein, "essentially free of silicone" means that the thermally reactive material contains 5 wt% or less of a silicone-containing compound, or 4 wt% or less, or 3 wt% or less, or 2 wt% or less, or 1 wt% or less of a silicone-containing compound. All weight percentages are based on the total weight of the thermally reactive material.

[0155] The thermally reactive material can be free of or essentially free of glass fibers. It is known to use a combination of a phosphorus-containing compound and glass fibers to form a relatively hard and stable char after thermal decomposition of a polymer resin. There is no need to use glass fibers to assist in stabilizing the char formed by the thermally reactive material described herein. Polyhydroxy stabilizes the char equally well as glass fibers. As used herein, "essentially free of glass fibers" means that the thermally reactive material can contain about 5 wt% or less of glass fibers, or about 4 wt% or less, or about 3 wt% or less, or about 2 wt% or less, or about 1 wt% or less of glass fibers. All weight percentages are based on the total weight of the thermally reactive material.

[0156] One advantage of using an aqueous acrylic resin in the thermally reactive material 102 is that the print-through of the textile composite material 10 is reduced when compared, for example, to a textile composite material formed from a silicone-based thermally reactive material. This reduction in print-through improves the visual optics and color durability, such as in camouflage printing. Further, the composite textile 10 formed from an aqueous acrylic resin-based thermally reactive material provides better conditions for post-treatment with such treatment agents, etc., because acrylic chemicals react better with, for example, a water repellent treatment agent, etc., when compared to hydrophobic silicone. In embodiments, the aqueous acrylic resin can contain and / or function as an adhesive for laminating or attaching a meltable layer to an additional layer.

[0157] The thermally reactive material also includes expandable graphite. In some embodiments, the expandable graphite expands at least 900 micrometers when heated to about 280 °C using the TMA expansion test described herein. Other useful grades of expandable graphite expand at least 400 micrometers when heated to about 240 °C.

[0158] Also, the expandable graphite can have both good expandability as described above and an endothermic property of at least 100 joules / gram (J / g) when tested according to the DSC endothermic test method as described herein. In other embodiments, it can be desirable to use expandable graphite having an endotherm of 150 J / g or more, or 200 J / g or more, or 250 J / g or more. In some embodiments, suitable expandable graphite has an expansion exceeding 900 μm at 280 °C and an endotherm of 100 J / g or more.

[0159] The size of the expandable graphite particles incorporated into the thermally reactive material can be selected such that the thermally reactive material is applied in the selected application method. For example, when the thermally reactive material is applied by gravure printing or screen printing techniques, the particle size of the expandable graphite should be small enough to fit into the gravure cell or screen printing openings. In some embodiments, the expandable graphite is Asbury 3626 expandable graphite available from Asbury Carbons of Asbury, New Jersey, USA.

[0160] As described above, the thermally reactive material 102 also includes at least one flame retardant (FR) additive. Exemplary FR additives that can be incorporated into the thermally reactive material 102 include, but are not limited to, melamine, polyphosphate, or combinations thereof. In some embodiments, the FR additive is melamine polyphosphate. For example, in some embodiments, the thermally reactive material 102 includes at least one of AFLAMMIT® PMN500 melamine, AFLAMMIT® PMN200 melamine polyphosphate, and AFLAMMIT® PCO962 additive, all of which are available from Thor GmbH of Schopfheim, Germany.

[0161] Furthermore, the thermally reactive material 102 also includes at least one polyhydroxy compound. The polyhydroxy compound can have a molecular weight of less than about 1000 g / mol, less than about 500 g / mol, less than about 250 g / mol, or less than about 100 g / mol. For example, in some embodiments, the polyhydroxy compound can be propane-1,2,3-triol. In other embodiments, the polyhydroxy compound can be propane-1,2,3-triol, butane-1,2,3,4-tetrol (erythritol), 2,2-(bishydroxymethyl)propane-1,3-diol (pentaerythritol), ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, or combinations thereof.

[0162] In some embodiments, the thermoreactive composition comprises from about 50 to about 90 weight percent (wt%) of an aqueous acrylic resin, based on the total mass of the thermoreactive composition. In other embodiments, the thermoreactive composition comprises from about 50 to about 80 wt% of an aqueous acrylic resin, or from about 50 to about 76 wt% of an aqueous acrylic resin, or from about 60 to about 80 wt% of an aqueous acrylic resin, or from about 55 to about 90 wt% of an aqueous acrylic resin, or from about 55 to about 85 wt% of an aqueous acrylic resin, or from about 55 to about 80 wt% of an aqueous acrylic resin, or from about 55 to about 76 wt% of an aqueous acrylic resin, or from about 60 to about 90 wt% of an aqueous acrylic resin, or from about 60 to about 85 wt% of an aqueous acrylic resin, or from about 60 to about 80 wt% of an aqueous acrylic resin, or from about 60 to about 76 wt% of an aqueous acrylic resin. All weight percents are based on the total mass of the thermoreactive composition.

[0163] Based on the total mass of the thermoreactive composition, the thermoreactive composition can comprise a mixture of expandable graphite and at least one FR additive, with expandable graphite in the range of about 5 to about 45 wt% and the FR additive in the range of about 5 to about 45 wt%. The mixture of expandable graphite and at least one FR additive can be present in the thermoreactive composition in the range of about 10 to about 40 wt% of expandable graphite and about 10 to about 40 wt% of the FR additive, or in the range of about 10 to about 30 wt% of expandable graphite and about 10 to about 25 wt% of the FR additive, and all weight percents are based on the total mass of the thermoreactive composition.

[0164] Based on the total mass of the thermoreactive composition, the thermoreactive composition can comprise from about 3 to about 20 wt%, or from about 3 to about 10 wt%, or from about 3 to about 7 wt% of a polyhydroxy compound.

[0165] In some embodiments, the thermoreactive composition can include, based on the total mass of the thermoreactive composition, from about 50 to about 90 wt% of an aqueous acrylic resin and from about 10 to about 50 wt% of a mixture of expandable graphite, a FR additive, and a polyhydroxy compound. The thermoreactive composition can include, based on the total mass of the thermoreactive composition, from about 50 to about 80 wt% of an aqueous acrylic resin and from about 20 to about 50 wt% of a mixture of expandable graphite, a FR additive, and a polyhydroxy compound. The thermoreactive composition can include, based on the total mass of the thermoreactive composition, from about 50 to about 75 wt% of an aqueous acrylic resin and from about 25 to about 50 wt% of a mixture of expandable graphite, a FR additive, and a polyhydroxy compound. The thermoreactive composition can include, based on the total mass of the thermoreactive composition, from about 60 to about 80 wt% of an aqueous acrylic resin, from about 5 to about 10 wt% of expandable graphite, from about 5 to about 10 wt% of a flame retardant additive, from about 5 to about 10 wt% of a polyhydroxy compound, and from about 5 to about 10 wt% of water.

[0166] In some embodiments, the thermoreactive composition can include additional additives such as pigments, fillers, antimicrobial agents, processing aids, crosslinking agents, thickeners, emulsifiers, defoamers, and stabilizers. The thermoreactive composition can include any optional additive in an amount of about 10 mass% or less, or about 5 mass% or less, or about 4 wt% or less, or about 3 wt% or less, less than about 2 wt%, or about 1 wt% or less. In some embodiments, the thermoreactive composition may not include an emulsifier. All mass percentages are based on the total mass of the thermoreactive composition.

[0167] A thermally reactive composition can be produced by a method that provides a tight blend of an aqueous acrylic resin, expandable graphite, an FR additive, and a polyhydroxy compound without causing substantial expansion of the expandable graphite. In some embodiments, the expandable graphite, the FR additive, the polyhydroxy compound, and any optional additives, such as a crosslinking agent, can be mixed or blended separately from or simultaneously with each other and with the aqueous acrylic resin to form the thermally reactive composition. Mixing methods include, but are not limited to, paddle mixers, blending, and other low-shear mixing techniques. In other methods, a tight blend of the aqueous acrylic resin, expandable graphite particles, FR additive, and polyhydroxy compound is achieved by mixing the expandable graphite, the FR additive, and the polyhydroxy compound with the monomer mixture and / or prepolymer of the aqueous acrylic resin prior to polymerization. The monomer mixture and / or prepolymer can then be polymerized to produce the thermally reactive composition. In a method for providing a tight blend of an aqueous acrylic resin, at least one FR additive, at least one polyhydroxy compound, expandable graphite particles or aggregates, the expandable graphite can be coated or encapsulated by the aqueous acrylic resin prior to expansion of the graphite.

[0168] The textile composite material also includes an additional layer 108. The additional layer 108 is disposed on the thermally reactive material such that the thermally reactive material is disposed between the meltable layer and the additional layer. In some embodiments, the additional layer 108 is attached or bonded to the inner 104 of the meltable layer 100 of the textile composite material 10 by the thermally reactive material 102 (as shown in FIG. 1), and when used, the outer 104 of the meltable layer 100 is oriented to contact a flame or heat source. In some embodiments, the additional layer 108 can be made of a thermally stable material. When exposed to a flame, the meltable layer 100 melts towards the thermally reactive material 102. When the expandable graphite within the thermally reactive material 102 expands, the thermally stable additional layer 108 can hold the expanding thermally reactive material 102 in place and facilitate absorption of the melt of the meltable layer 100.

[0169] The additional layer 108 can be a textile layer, a heat-stable textile layer, or a combination thereof. As disclosed above, a textile can be a woven fabric, a knitted fabric, a non-woven fabric, or a multi-layer combination thereof. Examples of heat-stable textiles include, but are not limited to, aramid, flame-retardant (FR) cotton, cotton, PBI, PBO, FR rayon, modacrylic blend, polyamine, carbon, glass fiber, PAN, and blends and combinations thereof.

[0170] The textile composite material according to the present disclosure can be manufactured by providing a meltable layer 100 and applying a heat-reactive composition to one side 104 of the meltable layer 100, as illustrated in FIGS. 1 and 2. Next, the additional layer 108 can be applied to the heat-reactive composition. Then, the combined meltable layer, heat-reactive composition, and additional layer can be dried and cured, optionally by applying heat. The temperature should be high enough to evaporate at least a portion of the aqueous phase of the aqueous acrylic resin and at least a portion of any volatile compounds that may be present, but low enough so that the expandable graphite does not begin to expand. In some embodiments, the heating step can be via one or more heating rolls, which can provide heat to drive out water, optionally cure or crosslink the aqueous acrylic resin, and provide pressure, thereby creating a better bond between the meltable layer and the additional layer.

[0171] In other embodiments, a method of forming a textile composite material 10 includes: a) providing a meltable layer 100 and an additional layer 108; b) applying a thermally reactive composition to the meltable layer, the additional layer, or both, where the thermally reactive composition includes a polymer resin including an aqueous acrylic resin, expandable graphite, and a FR additive; c) adhering the meltable layer and the additional layer together with the thermally reactive composition sandwiched therebetween to form a laminate; and d) removing at least a portion of the water from the aqueous acrylic resin and heating the laminate to a temperature sufficient to crosslink the aqueous acrylic resin, optionally.

[0172] The thermally reactive composition can be applied as a continuous layer as shown in FIG. 2, or discontinuously as shown in FIG. 1 to form a layer of the thermally reactive composition having a surface coverage of less than 100% if improvement in air permeability, water vapor permeability, and / or handle is desired.

[0173] In other embodiments, a method of forming a textile composite material 10 includes: a) providing a meltable layer 100 and an additional layer 108; b) applying a thermally reactive composition in a discontinuous pattern to the meltable layer, the additional layer, or both, wherein the thermally reactive composition includes a polymeric resin including an aqueous acrylic resin, expandable graphite, a FR additive, and a polyhydroxy compound; c) adhering the meltable layer and the additional layer together with the thermally reactive composition sandwiched therebetween to form a laminate; and d) removing at least a portion of the water from the aqueous acrylic resin and heating the laminate to a temperature sufficient to crosslink the aqueous acrylic resin, optionally. In a discontinuous application, the surface coverage can be less than 100% by forms including, but not limited to, dots, grids, lines, and combinations thereof. FIGS. 4 and 5 show an example where a layer of the thermally reactive composition is provided in a pattern of dots 122 and lines 124 when the thermally reactive composition is applied discontinuously, for example, inside 104 of the meltable layer 100. As used herein, the term "dot" means any discrete shape, for example, any shape that can be circular, square, rectangular, polygonal, or combinations thereof. A line can have a straight shape, a wavy shape, a curved shape, or a mixed shape thereof. Depending on the pattern, the dots and lines can be arranged to be closer to or spread from each other. In one embodiment as shown in FIG. 4, the lines 124 are arranged in the form of a continuous grid.

[0174] In some embodiments having a discontinuous coating, the average distance between adjacent regions of the discontinuous pattern is smaller than the size of the impinging flame. In other embodiments, the average distance between adjacent dots or lines of the discontinuous pattern can be from 200 micrometers to 10 millimeters (mm). In other embodiments, the average distance between adjacent dots or lines of the discontinuous pattern can be from 0.25 mm to 10 mm. In other embodiments, the average distance between adjacent dots or lines of the discontinuous pattern can be from 1 mm to 10 mm. In other embodiments, the average distance between adjacent dots or lines of the discontinuous pattern can be from 4 mm to 10 mm. As used herein, the distance between adjacent dots or lines means the average distance between the adjacent edges of two adjacent dots or lines. The average distance also means an average based on the distances between the edges of at least 10 different pairs of dots or lines.

[0175] In some embodiments, the average distance between adjacent regions of the discontinuous pattern can be from 600 micrometers to 7.5 mm. In other embodiments, the average distance between adjacent regions of the discontinuous pattern can be from 600 micrometers to 4.5 mm. In other embodiments, the average distance between adjacent regions of the discontinuous pattern can be from 600 micrometers to 1 mm. In other embodiments, the average distance between adjacent regions of the discontinuous pattern can be from 600 micrometers to 0.75 mm. In some embodiments, the average distance between adjacent regions of the discontinuous pattern can be from 600 micrometers to 2.5 mm. In other embodiments, the average distance between adjacent regions of the discontinuous pattern can be from 600 micrometers to 1.2 mm. In other embodiments, the average distance between adjacent regions of the discontinuous pattern can be from 600 micrometers to 600 micrometers. In other embodiments, the average distance between adjacent regions of the discontinuous pattern can be from 1 mm to 2 mm.

[0176] In an exemplary embodiment where a discontinuous dot pattern is used, the dots have a diameter in the range of 0.8 mm or more to 5 mm. In other embodiments, the dots have a diameter in the range of 0.9 mm to 4.5 mm. In other embodiments, the dots have a diameter in the range of 1.0 mm to 4.0 mm. In other embodiments, the dots have a diameter in the range of 1.0 mm to 3.5 mm. In other embodiments, the dots have a diameter in the range of 1.0 to 3.0 mm. In other embodiments, the dots have a diameter in the range of 1.0 mm to 2.5 mm.

[0177] In embodiments where properties such as feel, breathability and / or textile weight are important, the thermally reactive material 102 covers a range of 20% or more to 100% of the surface area of the fusible layer 100. In other embodiments, the thermally reactive material 102 covers a range of 25% to 80% of the surface area of the fusible layer 100. In other embodiments, the thermally reactive material 102 covers a range of 25% to 75% of the surface area of the fusible layer 100. In other embodiments, the thermally reactive material 102 covers a range of 25% to 55% of the surface area of the fusible layer 100. In other embodiments, the thermally reactive material 102 covers a range of 25% to 40% of the surface area of the fusible layer 100. In other embodiments, the thermally reactive material 102 covers a range of 25% to 35% of the surface area of the fusible layer 100.

[0178] In some embodiments, the thermally reactive material 102 covers a range of 30% to 100% of the surface area of the fusible layer 100. In other embodiments, the thermally reactive material 102 covers a range of 45% to 100% of the surface area of the fusible layer 100. In other embodiments, the thermally reactive material 102 covers a range of 55% to 100% of the surface area of the fusible layer 100. In other embodiments, the thermally reactive material 102 covers a range of 65% to 100% of the surface area of the fusible layer 100. In other embodiments, the thermally reactive material 102 covers a range of 70% to 100% of the surface area of the fusible layer 100. In other embodiments, the thermally reactive material 102 covers a range of 95% to 100% of the surface area of the fusible layer 100.

[0179] In some embodiments, the thermally reactive material 102 covers a range of 30% to 70% of the surface area of the fusible layer 100. In other embodiments, the thermally reactive material 102 covers a range of 45% to 65% of the surface area of the fusible layer 100. In other embodiments, the thermally reactive material 102 covers a range of 25% to 50% of the surface area of the fusible layer 100. In other embodiments, the thermally reactive material 102 covers a range of 65% to 90% of the surface area of the fusible layer 100. In other embodiments, the thermally reactive material 102 covers a range of 70% to 80% of the surface area of the fusible layer 100.

[0180] Methods for achieving a coverage rate of less than 100% include, for example, applying or printing the thermally reactive composition by screen printing, rotary screen printing, gravure printing, spray or spread coating, or knife coating onto the surface of the fusible layer or an additional layer or both. In some embodiments, screen printing or rotary screen printing of the thermally reactive composition can allow for a relatively high laydown (compared to the laydown achievable by a gravure roll) and a low areal coverage, thereby allowing for a relatively high air permeability of the textile composite material. Using this method, since the thermally reactive composition contains water, the thickness of the screen may increase. However, after printing, a heat source, such as an oven or a heated roll, is used to remove at least a portion of the water from the thermally reactive material (e.g., evaporated). Since water is removed from the thermally reactive material 102 during heating, the mass of the thermally reactive material 102 decreases, and as a result, in some embodiments, the textile composite material 10 becomes lighter. In some embodiments, to remove at least a portion of the water, the mass of the thermally reactive material can be reduced by 20% or 25% or 30% or 35% or 40% or 45% compared to the mass of the thermally reactive composition before water removal.

[0181] The thermoreactive composition can be applied in other forms in addition to dots, lines or grids. Other methods for applying the thermoreactive composition include gravure printing, or spray or spread coating or knife coating, provided that the thermoreactive composition can be applied in a manner such that the desired properties are achieved when exposed to heat or flame.

[0182] In some embodiments, when the textile composite material is exposed to flame and / or heat, such as a temperature of 280 °C or higher, the fusible layer begins to melt and the melt mixes with the thermoreactive material, particularly the expanding graphite. In this process, it is also possible to form a char comprising the fusible layer and the thermoreactive material. In some embodiments, the char resulting from exposing the fusible layer and the thermoreactive material to heat and / or high temperature, such as 280 °C or higher, is a non-uniform molten mixture comprising at least the fusible layer and the expanded exfoliated graphite. According to the present disclosure, char means a carbonaceous material remaining after exposing the fusible layer and the thermoreactive material to a temperature of 280 °C or higher. At a temperature of 280 °C or higher, one or both of the fusible layer and the aqueous acrylic resin can oxidize or participate in the combustion process to form additional carbonaceous material that becomes part of the char. The formation of the char can serve to insulate the layer below the char from exposure to heat.

[0183] In some embodiments, when the thermally reactive material 102 expands, it forms a plurality of curls including expanded graphite. During the expansion process, the total volume of the thermally reactive material 102 significantly increases when compared to the same mixture before expansion. In one embodiment, the volume of the thermally reactive material 102 increases by at least 5 times after expansion. In another embodiment, the volume of the thermally reactive material 102 increases by at least 6 times after expansion. In another embodiment, the volume of the thermally reactive material 102 increases by at least 7 times after expansion. In another embodiment, the volume of the thermally reactive material 102 increases by at least 8 times after expansion. In another embodiment, the volume of the thermally reactive material 102 increases by at least 9 times after expansion. In another embodiment, the volume of the thermally reactive material 102 increases by at least 10 times after expansion.

[0184] In an embodiment where the textile composite material 10 includes a meltable layer 100 and an additional layer 108, and the thermally reactive material 102 is applied in a discontinuous pattern, the thermally reactive material 102 expands to form loosely packed curls after expansion, creating voids between the curls and also creating spaces between the patterns of the expanded thermally reactive material 102. When exposed to a flame, the meltable layer 100 melts and generally moves away from the open areas between the discontinuous shapes of the thermally reactive material 102. The thermally stable additional layer 108 supports the thermally reactive material 102 during expansion, and the melt of the meltable layer 100 is absorbed and retained by the thermally reactive material 102 that is expanding during melting. By absorbing and retaining the melt, a textile composite material 10 can be formed that does not show dripping of the melt and has suppressed flammability. When the thermally stable additional layer 108 supports the thermally reactive material 102 that is expanding during melt absorption, the thermally stable additional layer 108 can be protected from tearing and forming holes. The increase in the surface area of the thermally reactive material 102 during expansion enables the absorption of the melt from the meltable layer 100 by the thermally reactive material 102 that has expanded when exposed to a flame.

[0185] The textile composite material 10 described in this specification exhibits improved properties by a combination of a fusible layer 100, an aqueous acrylic resin, a heat-reactive material containing expandable graphite and an FR additive, and an additional layer 108. For example, in some embodiments, the textile composite material 10 has a residual flame of less than 2 seconds when tested for flame retardancy using the horizontal combustion test described herein. Further, in some embodiments, the textile composite material 10 does not exhibit melt dripping, hole formation, and flame spread or glowing at the edges.

[0186] Since the heat-reactive material contains an aqueous acrylic resin from which water is later removed, in some embodiments, the textile composite material can have a dry peel strength in the range of about 5 to about 30 Newtons (N). The textile composite material can have a dry peel strength in the range of about 6 to about 30 N. The textile composite material can have a dry peel strength in the range of about 7 to about 30 N. The textile composite material can have a dry peel strength in the range of about 7 to about 22 N. The textile composite material can have a dry peel strength in the range of about 7 to about 25 N. The textile composite material can have a dry peel strength in the range of about 7 to about 22 N. The textile composite material can have a dry peel strength in the range of about 7 to about 21 N. The textile composite material can have a dry peel strength in the range of about 8 to about 22 N. The textile composite material can have a dry peel strength in the range of about 8 to about 23 N. The textile composite material can have a dry peel strength in the range of about 8 to about 24 N. The textile composite material can have a dry peel strength in the range of about 8 to about 25 N. The value of the dry peel strength is as measured by DIN 54310.

[0187] In some embodiments, the textile composite material 10 is used in clothing for use in hazardous environments, has breathability and flame retardancy, and at the same time is lightweight, flexible, and has a comfortable wearing feeling. For example, in some embodiments, the textile composite material 10 is 80 to 240 grams per square meter (g / m 2has a weight in the range of. In other embodiments, the textile composite material 10 is 80 - 200 g / m 2 has a weight in the range of. In other embodiments, the textile composite material 10 is 80 - 180 g / m 2 has a weight in the range of. In other embodiments, the textile composite material 10 is 80 - 165 g / m 2 has a weight in the range of. In other embodiments, the textile composite material 10 is 80 - 150 g / m 2 has a weight in the range of. In other embodiments, the textile composite material 10 is 80 - 125 g / m 2 has a weight in the range of. In other embodiments, the textile composite material 10 is 80 - 100 g / m 2 has a weight in the range of. In other embodiments, the textile composite material 10 is 80 - 90 g / m 2 has a weight in the range of.

[0188] In some embodiments, the textile composite material 10 has a weight in the range of 95 - 240 g / m 2 has a weight in the range of. In other embodiments, the textile composite material 10 is 110 - 240 g / m 2 has a weight in the range of. In other embodiments, the textile composite material 10 is 125 - 240 g / m 2 has a weight in the range of. In other embodiments, the textile composite material 10 is 140 - 240 g / m 2 has a weight in the range of. In other embodiments, the textile composite material 10 is 150 - 240 g / m 2 has a weight in the range of. In other embodiments, the textile composite material 10 is 165 - 240 g / m 2 has a weight in the range of. In other embodiments, the textile composite material 10 is 180 - 240 g / m 2 has a weight in the range of.

[0189] In some embodiments, the textile composite material 10 is 115 - 160 g / m 2has a weight in the range of. In other embodiments, the textile composite material 10 has a weight in the range of 95 - 150 g / m 2 has a weight in the range of. In other embodiments, the textile composite material 10 has a weight in the range of 165 - 190 g / m 2 has a weight in the range of. In other embodiments, the textile composite material 10 has a weight in the range of 135 - 175 g / m 2 has a weight in the range of. In other embodiments, the textile composite material 10 has a weight in the range of 85 - 100 g / m 2 has a weight in the range of. All weight measurements are carried out in accordance with DIN EN 12127 (1997 / 12).

[0190] Furthermore, in some embodiments, the textile composite material 10 has an air permeability of at least about 50 liters / m 2 s. In other embodiments, the textile composite material 10 has an air permeability in the range of about 50 - about 500 liters / m 2 s. In other embodiments, the textile composite material 10 has an air permeability in the range of about 100 - about 300 liters / m 2 s. In other embodiments, the textile composite material 10 has an air permeability in the range of about 130 - about 170 liters / m 2 s. In other embodiments, the textile composite material 10 has an air permeability in the range of about 140 - about 180 liters / m 2 s. In other embodiments, the textile composite material 10 has an air permeability in the range of about 150 - about 190 liters / m 2 s. In other embodiments, the textile composite material 10 has an air permeability in the range of about 120 - about 150 liters / m 2 s. In other embodiments, the textile composite material 10 has an air permeability in the range of about 75 - about 100 liters / m 2 s.

[0191] The disclosed textile composite material having a fusible outer layer, a heat-reactive material, and an additional inner layer can be used as a protective garment. Examples of protective garments include clothing such as jacket 20 shown in FIG. 6, trousers, shirts, vests, overalls, gloves, gaiters, hoods, and shoes. When used in clothing, the textile composite material is oriented such that the fusible layer is exposed or disposed in an outer region outside the clothing, and the additional layer is disposed on the opposite side of the fusible textile.

[0192] Without intending to limit the scope of the present disclosure, the following test methods and examples illustrate how the present disclosure can be made and used.

Examples

[0193] Test Methods Specific methods and apparatuses are described below, but it should be understood that other methods or apparatuses determined to be suitable by those skilled in the art can alternatively be utilized.

[0194] Horizontal Combustion Test

[0195] Textile material samples were tested according to the DIN EN ISO 15025A (April 2017) test standard. The fusible textile of the sample was exposed to a flame for 10 seconds. The afterflame time was averaged for three samples. Textiles with an afterflame exceeding 2 seconds were considered flammable. Textiles with an afterflame less than 2 seconds were considered non-flammable.

[0196] Samples of textiles and textile composites were tested for flame retardancy according to the DIN EN 15025A test standard. The samples were exposed to a flame for 10 seconds. Textiles and textile composites with an afterflame exceeding 2 seconds were not considered flame retardant. Textiles and textile composites with an afterflame less than 2 seconds were considered flame retardant.

[0197] Weight

[0198] The weight measurements of the textile composite materials, the fusible layer and the additional layer described in this specification were carried out as specified in DIN EN 12127 (December 1997).

[0199] Air permeability

[0200] The air permeability of the textile composite materials described in this specification was measured as specified in DIN EN ISO 9237 (December 1995).

[0201] Dry peel strength

[0202] The dry peel strength of the textile composite materials described in this specification was measured as specified in DIN 54310 1980-07.

[0203] Radar down

[0204] The dry radar down of the thermally reactive materials described in this specification was measured based on the weight of the textile composite materials, the fusible layer and the additional layer after drying and fixing the textile composite materials.

[0205] TMA expansion test

[0206] The expansion of the expandable graphite particles was measured using TMA (Thermomechanical Analysis). The expansion was tested using a TA Instruments TMA 2940 instrument. A ceramic (alumina) TGA pan with a diameter of about 8 mm and a height of 12 mm was used to hold the sample. A macro expansion probe with a diameter of about 6 mm was used to set the bottom of the pan to zero. Then, flakes (about 15 mg) of expandable graphite with a depth of about 0.1 - 0.3 mm were placed in the pan as measured by the TMA probe. The furnace was closed and the initial sample height was measured. The furnace was heated from about 25 °C to 600 °C at a heating rate of 10 °C / min. The displacement of the TMA probe was plotted against the temperature. The displacement was used as a measure of expansion.

[0207] Furnace expansion test

[0208] A nickel crucible was heated in a high-temperature furnace at 300 °C for 2 minutes. A sample of expandable graphite (about 0.5 grams) to be measured 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 taken out of the furnace and allowed to cool, and the expanded graphite was transferred to a graduated cylinder to measure the expanded volume. The expanded volume was divided by the original weight of the sample to obtain the expansion in cubic centimeters / gram.

[0209] DSC endothermic test

[0210] The test was carried out on a TA instruments Q2000 DSC using Tzero (trademark) airtight pans. For each sample, about 3 milligrams of expandable graphite was placed in the pan. The pan was vented by pushing the corner of a razor blade into the center to create a vent hole with a length of about 2 millimeters and a width of less than 1 millimeter. The DSC was equilibrated at 20 °C. Next, the sample was heated from 20 °C to 400 °C at 10 °C / min. The endothermic values were obtained from the DSC curve.

[0211] Example Examples were created using the following materials.

[0212] EDOLAN (registered trademark) AM50% aqueous acrylic resin containing N-methylolacrylamide repeating units, EDOLAN (registered trademark) XCI crosslinking agent, EDOLAN (registered trademark) XTP thickener, and emulsifier WN are all available from Tanatex Chemicals B.V., Ede, the Netherlands. AFLAMMIT (registered trademark) PMN 200 melamine polyphosphate is available from Thor GmbH (Speyer, Germany). Asbury 3626 expandable graphite is available from Asbury Carbons, Asbury, New Jersey, USA.

[0213] Preparation of Comparative Thermal Reactive Material 1

[0214] A mixture of 1000 parts by weight (pbw) of EDOALN® AM was mixed with 40 pbw of EDOLAN® XTP, 150 pbw of Asbury 3626 expandable graphite, 150 pbw of PMN 200 melamine flame retardant, and 100 pbw of glycerol. The mixture was then stirred for 1 minute to form a thermally reactive composition.

[0215] Preparation of Comparative Thermally Reactive Material 2

[0216] A mixture of 1000 parts by weight (pbw) of EDOALN® AM was mixed with 40 pbw of EDOLAN® XTP, 150 pbw of Asbury 3626 expandable graphite, 150 pbw of PMN 200 melamine flame retardant, 100 pbw of glycerol, and 100 pbw of water. The mixture was then stirred for 1 minute to form a thermally reactive composition.

[0217] Preparation of Comparative Thermally Reactive Material A

[0218] A mixture of 1000 parts by weight (pbw) of EDOALN® AM was mixed with 40 pbw of EDOLAN® XTP, 40 pbw of EDOLAN® XCI, 200 pbw of Asbury 3626 expandable graphite, 200 pbw of PMN200 melamine flame retardant, and 5 pbw of emulsifier WN. The mixture was then stirred for 1 minute to form a thermally reactive composition.

[0219] Preparation of Comparative Thermally Reactive Material B

[0220] A mixture of 1000 parts by weight (pbw) of EDOALN® AM was mixed with 40 pbw of EDOLAN® XTP, 150 pbw of Asbury 3626 expandable graphite, 150 pbw of PMN 200 melamine flame retardant, and 3 pbw of emulsifier WN. The mixture was then stirred for 1 minute to form a thermally reactive composition.

[0221] Preparation of Comparative Thermally Reactive Material C

[0222] A mixture of 1000 parts by weight (pbw) of EDOALN® AM was mixed with 40 pbw of EDOLAN® XTP, 150 pbw of Asbury 3626 expandable graphite, 150 pbw of PMN 200 melamine flame retardant, and 60 pbw of emulsifier WN. The mixture was then stirred for 1 minute to form a thermally reactive composition.

[0223] [Table 1]

[0224] Fabrication of Laminate Samples

[0225] The meltable layer textile #1 is a 100% nylon 6,6 fabric having a textile weight of 78 ± 3 grams per square meter and is available from Toray Industries, Tokyo, Japan.

[0226] Textile #2 is a blend of 65% polyester and 35% cotton having a textile weight of 76 ± 5 grams per square meter and is available from Ames Europe, Enschede, the Netherlands.

[0227] Fabrication of Comparative Laminate C

[0228] The thermally reactive material C was screen-printed and dyed onto a 100% polyamide (nylon 6,6) plain weave substrate with a weight of 78 ± 3 grams per square meter using a screen with a depth of 250 μm, a dot size of 1.3 millimeters, and an area coverage rate of approximately 30.5%, achieving a wet laydown of the thermally reactive composition of approximately 70 - 80 grams per square meter (gsm). After dyeing the thermally reactive composition onto the substrate, the screen was removed, and a single knit jersey (65% polyester / 35% cotton) fabric with a weight of 76 ± 5 grams per square meter was applied to the dyed area. The two-layer textile composite material was dried at a temperature of 100 °C for 30 - 60 seconds. The textile composite material was dried for 60 seconds. Subsequently, the textile composite material was further placed in a hot press set at a temperature of 160 °C for another 60 seconds to crosslink the mixture. After aging for at least 24 hours, the flame retardancy of the textile composite material was tested using a horizontal combustion test in accordance with DIN EN ISO 15025A, and the results were reported in Table 2.

[0229] Fabrication of Laminate 1

[0230] The thermally reactive material #1 was screen-printed and dyed onto a 100% polyamide (nylon 6,6) plain weave substrate with a weight of 78 ± 3 grams per square meter using a screen with a depth of 250 μm, a dot size of 1.3 millimeters, and an area coverage rate of approximately 30.5%, achieving a wet laydown of the thermally reactive composition of approximately 70 - 80 grams per square meter (gsm). After dyeing the thermally reactive composition onto the substrate, the screen was removed, and a single knit jersey (65% polyester / 35% cotton) fabric with a weight of 76 ± 5 grams per square meter was applied to the dyed area. The two-layer textile composite material was dried at a temperature of 100 °C for 30 - 60 seconds. The textile composite material was dried for 60 seconds. Subsequently, the textile composite material was further placed in a hot press set at a temperature of 160 °C for another 60 seconds to crosslink the mixture. After aging for at least 24 hours, the flame retardancy of the textile composite material was tested using a horizontal combustion test in accordance with DIN EN ISO 15025A, and the results were reported in Table 2.

[0231] Preparation of Laminate 2

[0232] The thermally reactive material #2 was screen-printed and dyed onto a 100% polyamide (nylon 6,6) plain weave substrate having a weight of 78 ± 3 grams per square meter using a screen with a depth of 250 μm, a dot size of 1.3 millimeters, and an area coverage rate of approximately 30.5%, achieving a wet laydown of the thermally reactive composition of approximately 70 - 80 grams per square meter (gsm). After dyeing the thermally reactive composition onto the substrate, the screen was removed, and a single knit jersey (65% polyester / 35% cotton) fabric with a weight of 76 ± 5 grams per square meter was applied to the dyed area. The two-layer textile composite material was dried at a temperature of 100°C for 30 - 60 seconds. The textile composite material was dried for 60 seconds. Then, the textile composite material was further placed in a hot press set at a temperature of 160°C for another 60 seconds to crosslink the mixture. After aging for at least 24 hours, the flame retardancy of the textile composite material was tested using a horizontal combustion test in accordance with DIN EN ISO 15025A, and the results were reported in Table 2.

[0233] Preparation of Comparative Laminate A

[0234] The heat-reactive material A was screen-printed and dyed onto a 100% polyamide (nylon 6,6) plain-woven substrate having a weight of 78 ± 3 grams per square meter using a screen with a depth of 250 μm and a dot size of 1.6 millimeters, achieving a wet laydown of the heat-reactive composition of approximately 70 - 80 grams per square meter (gsm). After the heat-reactive composition was dyed onto the substrate, the screen was removed, and a single-knit jersey (65% polyester / 35% cotton) fabric with a weight of 76 ± 5 grams per square meter was applied to the dyed area. The two-layer textile composite material was dried at a temperature of 100 °C for 30 - 60 seconds. The textile composite material was dried for 60 seconds. Then, the textile composite material was further placed in a hot press set at a temperature of 160 °C for another 60 seconds to crosslink the mixture. After aging for at least 24 hours, the flame retardancy of the textile composite material was tested using a horizontal combustion test in accordance with DIN EN ISO 15025A, and the results were reported in Table 2.

[0235] Preparation of Comparative Laminate B

[0236] The heat-reactive material B was screen-printed and dyed onto a 100% polyamide (nylon 6,6) plain-woven substrate having a weight of 78 ± 3 grams per square meter using a screen with a depth of 250 μm, a dot size of 1.3 millimeters, and an area coverage rate of approximately 30.5%, achieving a wet laydown of the heat-reactive composition of approximately 70 - 80 grams per square meter (gsm). After the heat-reactive composition was dyed onto the substrate, the screen was removed, and a single-knit jersey (65% polyester / 35% cotton) fabric with a weight of 76 ± 5 grams per square meter was applied to the dyed area. The two-layer textile composite material was dried at a temperature of 100 °C for 30 - 60 seconds. The textile composite material was dried for 60 seconds. Then, the textile composite material was further placed in a hot press set at a temperature of 160 °C for another 60 seconds to crosslink the mixture. After aging for at least 24 hours, the flame retardancy of the textile composite material was tested using a horizontal combustion test in accordance with DIN EN ISO 15025A, and the results were reported in Table 2.

[0237]

Table 2

[0238] Laminates 1 and 2 show that glycerol is present in the thermally reactive material and that, despite having less exfoliated graphite compared to the comparative thermally reactive material, they were able to achieve passing points in the combustion test. Further, Laminates 1 and 2 formed a char that was more stable than the char from Comparative Laminates A, B, or C. The char did not break or fall off the sample even when the sample was bent or moved. This provides more protection because the char functions as a heat insulating layer.

[0239] Furthermore, the thermally reactive material according to embodiments of the present disclosure exhibits improved processability, and as a result, laminates having a length of 500 meters or more were formed.

[0240] The invention of the present application has been described above generally and with respect to specific embodiments. It will be apparent to those skilled in the art that various changes and modifications can be made to the embodiments without departing from the scope of the present disclosure. Accordingly, the embodiments are intended to cover changes and modifications of the present invention as long as they are within the scope of the appended claims and their equivalents.

Claims

1. a) a fusible layer, b) a polymer resin containing an aqueous acrylic resin, expandable graphite, at least one flame retardant (FR) additive, at least one polyhydroxy compound selected from the group consisting of propane-1,2,3-triol, butane-1,2,3,4-tetrol, 2,2-(bishydroxymethyl)propane-1,3-diol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, and combinations thereof a thermoreactive material comprising, and c) an additional layer disposed on the thermoreactive material, the thermoreactive material being between the fusible layer and the additional layer A textile composite material comprising: The textile composite material has a afterflame of less than about 2 seconds.

2. The textile composite material according to claim 1, wherein the polyhydroxy compound has a molecular weight of less than about 1000 g / mol.

3. The textile composite material according to claim 1 or 2, wherein the polyhydroxy compound is propane-1,2,3-triol.

4. The textile composite material according to any one of claims 1 to 3, having a dry peel strength in the range of about 5 to about 30 Newtons (N) as measured by DIN 54310.

5. The textile composite material according to any one of claims 1 to 4, wherein the thermoreactive material is applied to the fusible layer, the additional layer, or both in a continuous pattern or a discontinuous pattern.

6. The textile composite material according to any one of claims 1 to 5, wherein the thermoreactive material is applied in a discontinuous pattern of dots.

7. The expandable graphite expands at least about 900 micrometers when heated to about 280 °C as measured by a TMA expansion test, and the textile composite material according to any one of claims 1 to 6.

8. The FR additive is melamine, polyphosphate, or a combination thereof, and the textile composite material according to any one of claims 1 to 7.

9. The FR additive is melamine polyphosphate, and the textile composite material according to any one of claims 1 to 8.

10. The polyhydroxy compound is present in the thermally reactive material in an amount in the range of about 3 to 10 wt% of the polyhydroxy compound based on the total mass of the thermally reactive material, and the textile composite material according to any one of claims 1 to 9.

11. The thermally reactive material includes an acrylic polymer in the range of about 40 to about 90 wt% and a mixture of the expandable graphite and the polyhydroxy compound in the range of about 10 to about 60 wt% based on the total mass of the thermally reactive material, and the textile composite material according to any one of claims 1 to 10.

12. The additional layer is a textile layer, a thermally stable textile, or a combination thereof, and the textile composite material according to any one of claims 1 to 11.

13. The additional layer includes one or more of aramid, flame-retardant cotton, cotton, linen, cupra, acetate, triacetate, wool, viscose, polybenzimidazole (PBI), polybenzoxazole (PBO), FR rayon, modacrylic, modacrylic / cotton blend, polyamine, glass fiber, polyacrylonitrile, polytetrafluoroethylene, or a combination thereof, and the textile composite material according to any one of claims 1 to 12.

14. The textile composite material according to any one of claims 1 to 13, wherein the additional layer is a fusible layer including at least one of a fusible textile or a fusible film.

15. The textile composite material according to any one of claims 1 to 14, wherein the aqueous acrylic resin includes acrylamide repeating units.

16. The textile composite material according to any one of claims 1 to 15, wherein the aqueous acrylic resin includes N-methylolacrylamide repeating units.

17. The textile composite material according to any one of claims 1 to 16, wherein the polymer resin includes at least 25 wt% of an aqueous acrylic resin and at least one polymer resin selected from the group consisting of vinyl acetate, styrene, polyether, polyester, polyurethane, polyether polyurethane, polyester polyurethane, polycarbonate polyurethane, or copolymers or blends thereof.

18. The textile composite material according to any one of claims 1 to 17, wherein the thermally reactive material covers a surface area of the fusible layer in the range of about 25% to about 100%.

19. The textile composite material according to any one of claims 1 to 18, wherein the textile composite material has a weight in the range of about 80 to about 240 grams per square meter (gsm).

20. The textile composite material according to any one of claims 1 to 19, wherein the textile composite material has an air permeability of at least about 50 liters / m ２ s as measured by DIN ISO 9237 (1995).

21. The textile composite material according to any one of claims 1 to 20, wherein the fusible layer and the additional layer are adhered to each other by the thermally reactive material.

22. Clothing comprising the textile composite material according to any one of claims 1 to 21.

23. i) An aqueous acrylic resin, ii) Expansible graphite that expands at least about 900 micrometers when heated at about 280 °C as measured by a TMA expansion test, and iii) At least one flame retardant additive, iv) At least one polyhydroxy compound selected from the group consisting of propane-1,2,3-triol, butane-1,2,3,4-tetrol, 2,2-(bishydroxymethyl)propane-1,3-diol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, and combinations thereof, and v) Water, A thermoreactive composition comprising the same.

24. The thermoreactive composition according to claim 23, wherein the polyhydroxy compound has a molecular weight of less than 1000 g / mol.

25. The thermoreactive composition according to claim 23 or 24, wherein the thermoreactive composition comprises, based on the total mass of the thermoreactive composition, about 60 to about 80 wt% of an aqueous acrylic resin, about 5 to about 10 wt% of expansible graphite, about 5 to about 10 wt% of a flame retardant additive, about 5 to about 10 wt% of a polyhydroxy compound, and about 5 to about 10 wt% of water.

26. The thermoreactive composition according to any one of claims 23 to 25, wherein the polyhydroxy compound is propane-1,2,3-triol and the aqueous acrylic resin contains acrylamide repeating units.

27. a) Providing a meltable layer and an additional layer, b) applying the thermoreactive composition onto the meltable layer, the additional layer, or both, wherein the thermoreactive composition comprises an aqueous acrylic resin, expandable graphite, at least one flame retardant additive, propane-1,2,3-triol, butane-1,2,3,4-tetrol, 2,2-(bishydroxymethyl)propane-1,3-diol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, and at least one polyhydroxy compound selected from the group consisting of combinations thereof, and water, c) adhering the meltable layer and the additional layer together with the thermoreactive composition sandwiched therebetween to form a laminate, and, d) heating the laminate to a temperature sufficient to remove at least a portion of the water from the aqueous acrylic resin, A method comprising the steps of. **Claim 28** The method according to claim 27, wherein the thermoreactive composition is applied to the meltable layer in a discontinuous pattern. **Claim 29** The method according to claim 27 or 28, wherein the formed laminate has a length of 500 meters or more.

Images