Flame resistant, water repellent finished fabric and method of making same

Abstract

Described herein are fabrics exhibiting water repellency, abrasion resistance, and optionally, flame resistance. The fabrics include a plurality of fibers (e.g., flame resistant fibers) and a finish that imparts water repellency and abrasion resistance to the fibers. The fabrics are free or substantially free of alkyl fluoropolymers. Further, described herein are garments including the fabrics.

Description

[0001] Cross-reference to related applications

[0002] This application claims priority to U.S. Provisional Application No. 62 / 852,647, filed May 24, 2019, which is incorporated herein by reference in its entirety. Technical Field

[0003] This disclosure relates to flame-retardant fabrics exhibiting water repellency and other desired properties, including surface abrasion resistance and / or anti-pilling properties. This disclosure also relates to novel fabric finishing agents that impart water repellency and surface abrasion resistance, and methods for preparing flame-retardant finished fabrics exhibiting water repellency and surface abrasion resistance. Background of the Invention

[0005] Firefighters, emergency responders, search and rescue personnel, and military personnel may be exposed to intense heat and / or flames while on duty. Protective clothing is designed and constructed as a means of combating injury. Often referred to as firefighting suits (including jumpsuits, trousers, and jackets), these suits are made of specialized fire-resistant materials and are designed to protect workers from both heat and flames. These garments typically consist of several layers of material, such as an outer shell protecting the wearer from flames, a moisture-proof layer preventing water from entering the clothing, and an insulating layer that insulates the wearer from intense heat.

[0006] Individuals, including but not limited to emergency responders, such as firefighters and other first responders, are exposed not only to intense heat or flames but also to water. In those situations, it will be expected that fire-resistant fabrics also possess water-repellent properties. Therefore, firefighting suits and other protective clothing may comprise woven fabrics formed from one or more types of fire-resistant fibers, and this fabric may also possess water-repellent properties. These protective fabrics are expensive, so fabric durability is important. Abrasion refers to the wear and tear of any part of a material due to friction relative to another surface. Even as the fabric becomes abraded, the fire-resistant fibers will retain their fire resistance, but abraded protective fabrics are more susceptible to tearing or ripping. Abraded clothing may not provide the protection required by firefighters, emergency responders, or other individuals. Therefore, if protective clothing becomes abraded, it must be replaced. Clothing with improved abrasion resistance will require less frequent replacement compared to conventional protective clothing. The abrasion resistance of fabrics can be measured using various test methodologies and equipment, such as the test procedures described in ASTM standards D3886 and D3884.

[0007] Fabrics are known in the art to be treated with finishing agents that impart particularly useful properties. For example, many prior art finishing agents are water-repellent agents that include alkyl fluoropolymers. However, due to current perceptions that alkyl fluoropolymers and other fluorinated chemicals may be unsafe, alternative options for finishing agents that impart desired properties to fabrics are needed. There remains a need for water-repellent, abrasion-resistant, and flame-retardant fabrics and protective clothing that are fluorine-free due to industry requirements. Summary of the Invention

[0008] This article describes a water-repellent and flame-retardant fabric, along with its preparation method. The water-repellent and flame-retardant fabric described herein comprises multiple yarns containing multiple flame-retardant fibers and finishing agents that impart water repellency and abrasion resistance to the fabric. The finishing agents comprise a water-repellent agent selected from the group consisting of hydrocarbon-based polymers, silicone-based polymers, polyurethane-based polymers, and acrylic-based polymers, as well as a polymeric abrasion auxiliaries. The fabric, before washing and after five washes according to AATCC Test Method 135 (2018), exhibits abrasion resistance of at least approximately 500 cycles before the first breakage when tested according to ASTM Test Method D3884 (2017) (H-18, 500g per wheel), and a water absorption rate of less than or equal to 15.0% as determined by NFPA 1971, 8.26 (2018). In some instances, the finishing agents are substantially free of alkyl fluoropolymers.

[0009] In some instances, the polymer abrasion accelerator comprises an acrylic polymer. The finishing agent may also comprise at least one of alkoxylated fatty amines or derivatives thereof, melamine-formaldehyde resin, N-hydroxymethyl stearamide, or combinations thereof. Optionally, at least some of the plurality of flame-retardant fibers are inherently flame-retardant fibers, comprising at least one of meta-aramid fibers, para-aramid fibers, polybenzimidazole fibers, polybenzoxazole fibers, melamine fibers, polyimide fibers, polyimide amide fibers, modified polyacrylonitrile fibers, and FR rayon fibers.

[0010] The abrasion resistance of the fabrics described herein is at least about 700 cycles before the first breakage (e.g., at least about 800 cycles or at least about 1000 cycles before the first breakage). Optionally, the water absorption is less than or equal to 12.0% as determined by NFPA 1971,8.26 (2018) (e.g., less than or equal to 10.0% or less than or equal to 5.0% as determined by NFPA 1971,8.26 (2018)). In some instances, the fabric meets all flammability requirements of one or more of NFPA 1951 (2013), NFPA 1971 (2018), NFPA 1977 (2016), NFPA 2112 (2018), Military Specification MIL-C-83429B, or Military Specification GL-PD-07-12 before washing and after ten washes according to AATCC Test Method 135 (2018). For example, the fabric meets the vertical flammability requirements of NFPA 1951 (2013) after washing before washing and after ten washes according to AATCC Test Method 135 (2018). Optionally, the fabric meets the vertical flammability requirements of NFPA 1977 (2016) after washing before washing and after one hundred washes according to AATCC Test Method 135 (2018). Optionally, the fabric meets the vertical flammability requirements of NFPA 2112 (2018) before washing and after one hundred industrial washes. Optionally, the fabric meets the vertical flammability requirements of NFPA 1971 (2018) before washing and after five washes according to AATCC Test Method 135 (2018).

[0011] In some cases, the fabric meets all the water repellency requirements of one or both of NFPA 1951 (2013) or NFPA 1971 (2018) before washing and after five washes according to AATCC Test Method 135 (2018). Optionally, the fabric meets the Total Heat Loss (THL) requirements according to NFPA 1971 (2018). The fabric may comprise plain weave, nylon yarn reinforced fabric (rip-stop), twill weave, satin weave, or knitted fabric. Optionally, the fabric may be elastic or non-elastic. The fabric may have a weight of less than about 8.0 osy.

[0012] Water-repellent and flame-retardant garments containing the water-repellent and flame-retardant fabrics described herein are also provided.

[0013] Furthermore, this paper describes a water-repellent fabric comprising multiple spun yarns containing multiple fibers and finishing agents that impart water repellency and abrasion resistance to the fabric. The finishing agents comprise (a) water-repellent agents selected from the group consisting of hydrocarbon-based polymers, silicone-based polymers, urethane-based polymers, and acrylic-based polymers, and (b) polymeric abrasion auxiliaries. The fabric, before washing and after five washes according to AATCC Test Method 135 (2018), exhibits abrasion resistance of at least approximately 500 cycles before the first breakage when tested according to ASTM Test Method D3884 (2017) (H-18, 500g per wheel), and a water absorption rate of less than or equal to 15.0% as determined by NFPA 1971, 8.26 (2018).

[0014] Upon examination of the following figures and detailed description, other systems, methods, processes, apparatuses, features, and advantages associated with the fabrics and garments described herein will be apparent to or will become apparent to those skilled in the art. All such additional systems, methods, processes, apparatuses, features, and advantages are intended to be included within this specification and are intended to be contained within the scope of this disclosure. Brief description of the attached diagram

[0016] Figure 1 A partial cross-sectional view of the protective suit is shown. Invention Details

[0018] This article describes fabrics exhibiting water repellency, flame retardancy, and / or abrasion resistance. The fabrics comprise multiple fibers (e.g., flame-retardant fibers) and finishing agents that impart water repellency and abrasion resistance to the fibers. The fabrics contain little or no alkyl fluoropolymers but unexpectedly exhibit desired abrasion resistance and water absorption when tested according to industry-recognized standard tests, as further described below.

[0019] Finishing agent composition

[0020] This document describes novel finishing agent compositions that impart water repellency and abrasion resistance to fabrics when applied to them to form a finishing agent. The finishing agent compositions described herein comprise water repellents selected from the group consisting of hydrocarbon polymers, silicone polymers, urethane polymers, and acrylic polymers. The finishing agent compositions also include polymeric abrasion accelerants.

[0021] Examples of suitable water repellents include, but are not limited to: hydrocarbon polymers such as Altopel F3 and Altopel M-213-SP (available from Bolger & O'Hearn), Ruco Dry ECO Plus (cationic hyperbranched and linear polymers available from Rudolph Group), Repellan HY-N (a cationic blend of paraffin and melamine available from Pulcra Chemicals), Evo Protect DTE (a quaternary ammonium compound paraffin dispersion available from DyStar), and Fibropel NF-22 (a hydrocarbon available from FibroChem LLC); silicone polymers such as Wacker CT 303 (available from Wacker Silicones), Dowsil Z-6689 (available from Dow Consumer Group and HiTech Group), Barpel FF (available from Apollo Chemical), and NEOSEED NR-8000 (available from NICCA USA); and urethane polymers such as Zelan. R-3 (alkyl urethane, commercially available from Huntsman Chemical) and RucoPur SLR (cationic polyurethane, commercially available from Rudolph Group); and acrylic polymers such as Phobotex RSY (acrylic copolymer and paraffin dispersion, commercially available from Huntsman Chemical). Optionally, the urethane polymer used as a water repellent may have a relatively high elongation value (e.g., 300% or higher, such as 500% or higher).

[0022] Other water repellents applicable to this document include other non-fluorinated water repellents such as SmartRepel products (e.g., SmartRepel Hydro PM and SmartRepel Hydro AM) and Arkophob FFR, each commercially available from Archroma; other Repellan products (e.g., Repellan V5), commercially available from Pulcra Chemicals; NEOSEEDNR-7080, an acrylic product, commercially available from NICCA USA; and Nonax products (commercially available from Pulcra Chemicals).

[0023] The water repellent may be included in the finishing agent composition in an amount of 5% to 20% (%owb) of the bath weight (as used herein, by weight of the finishing agent composition bath). In some instances, the finishing agent composition may include water repellent in amounts of about 6% to about 18%, about 8% to about 17%, or about 9% to about 15% owb. For example, the finishing agent composition may include water repellent in amounts of about 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, or 20% owb.

[0024] The finishing agent compositions described herein also include polymeric abrasion accelerators. These polymeric abrasion accelerators may be, for example, acrylic polymers, urethane polymers, or combinations thereof. Optionally, the urethane polymer used as the polymeric abrasion accelerator may have a relatively low elongation value (e.g., less than or equal to 250%).

[0025] Examples of suitable polymer abrasion aids include, but are not limited to: urethane-based polymers such as EccorezFRU-33 (a hydrophobic urethane polymer, available from Organic Dyes & Pigment LLC) and Dicrylan PSF (a crosslinked polyurethane, available from Huntsman Chemical); and acrylic polymers such as FDP-61063 (a self-crosslinked acrylic copolymer with a Tg of +25°C, available from Omnova Solutions) and Dicrylan TA-GP (a self-crosslinked ethyl acrylate polymer with a Tg of -14°C, available from Huntsman Chemical).

[0026] The polymer abrasion accelerant may be included in the finishing agent composition in an amount of 5% to 20% (%owb) of the bath weight (as used herein, by weight of the finishing agent composition bath). In some instances, the finishing agent composition may include a water repellent in amounts of about 6% to about 18%, about 8% to about 17%, or about 9% to about 15% owb. For example, the finishing agent composition may include a polymer abrasion accelerant in amounts of about 5% owb, 6% owb, 7% owb, 8% owb, 9% owb, 10% owb, 11% owb, 12% owb, 13% owb, 14% owb, 15% owb, 16% owb, 17% owb, 18% owb, 19% owb, or 20% owb.

[0027] The finishing agent composition may also include one or more of the following additional components: polymer extenders and other crosslinking agents, silicone softeners, pH control agents, polyethylene, wetting agents, complexing agents, sewing / abrasion polymeric acids, alkoxylated fatty amines or derivatives thereof, melamine-formaldehyde resins, N-hydroxymethyl stearamide, and / or flame retardant additives. Suitable polymer extenders and crosslinking agents include, but are not limited to: Phobol Extender XAN (terminated isocyanate crosslinking agent, available from Huntsman), Evo Protect XL (modified polyisocyanate crosslinking agent, available from DyStar), NK ASSIST FU (aromatic terminated isocyanate crosslinking agent, available from NICCA USA), and RucoLink XCR (available from Rudolph Group). Suitable silicone softeners include, but are not limited to, Ultratex SI (available from Huntsman). Suitable pH control agents include, but are not limited to, acids, such as acetic acid. Suitable polyethylene includes, but is not limited to, medium-density and high-density polyethylene. Suitable wetting agents include, but are not limited to, Ridgewet NRW (formerly known as Genwet NRW and available from Blue Ridge Products) and Invadine PBN (available from Huntsman). Suitable complexing agents include Securon 540, a phosphonic acid complexing agent available from Pulcra Chemicals. Suitable sewing / abrasion polymer auxiliaries include, but are not limited to, medium to high density polyethylene emulsions such as Aquasoft 706 (available from Apollo Chemicals, Ware Shoals, SC). Suitable alkoxylated fatty amines or their derivatives include, but are not limited to, Cartafix U (an alkoxylated fatty amine derivative designed to inhibit finishing agent migration and minimize roll-up polymerization, available from Clariant). Suitable melamine-formaldehyde resins include, but are not limited to, Aerotex M3 (manufactured by Cytec Industries and available from Dystar LP, Charlotte, NC) and Eccoresin M300 (available from Organic Dyes & Pigment LLC). Suitable N-hydroxymethyl stearamides include, but are not limited to, Aurapel 330 (available from Star Chemicals). Suitable flame retardants include, but are not limited to, FlovanCGN01 (a phosphorus and nitrogen-containing flame retardant, available from Huntsman International).

[0028] One or more other

[0029] The total amount of components may be included in the finishing agent composition in an amount from 0.01% to 20% (%owb) of the bath weight (as used herein, by weight of the finishing agent composition bath). In some instances, the finishing agent composition may include water repellent in amounts of about 1% to about 18%, about 3% to about 17%, or about 5% to about 15%owb. For example, the finishing agent composition may include an amount of polymeric abrasion accelerator of about 0.01% owb, 0.02% owb, 0.03% owb, 0.04% owb, 0.05% owb, 0.1% owb, 0.5% owb, 1% owb, 2% owb, 3% owb, 4% owb, 5% owb, 6% owb, 7% owb, 8% owb, 9% owb, 10% owb, 11% owb, 12% owb, 13% owb, 14% owb, 15% owb, 16% owb, 17% owb, 18% owb, 19% owb, or 20% owb. The remaining amount of the finishing agent composition may include water or another aqueous solvent.

[0030] As further described below, the finishing agent compositions described herein impart desired properties to fibers, fabrics, and garments upon application, including water repellency, abrasion resistance, and / or pilling resistance. According to various embodiments, finishing agents prepared using the finishing agent compositions described herein can improve the water repellency of fibers, fabrics, or garments while simultaneously improving the surface abrasion resistance and / or pilling resistance of the fibers, fabrics, or garments. Preferably, the finishing agent can improve the water repellency and surface abrasion resistance and / or pilling resistance of flame-retardant and / or water-resistant fabrics without reducing the flame-retardant or water-resistant properties of the fabric. In some cases, the finishing agent compositions can improve the post-wash appearance of fabrics described herein (e.g., fabrics containing para-aramids) by reducing the amount of fibrillary structures that appear during washing. The application of finishing agents to fabrics can vary depending on the desired physical properties of the treated fabric, the composition of the fabric, and the type of fiber or bulk yarn selected for the fabric.

[0031] Alternatively, when the finishing agent composition described herein is added to another finishing agent composition applied to a fabric, the finishing agent composition described herein can impart water repellency, abrasion resistance, and / or pilling resistance to the fabric. For example, the finishing agent composition described herein can be added to known finishing agent compositions, such as, but not limited to, water-treated finishing agents, durable pressing finishing agents, or antimicrobial finishing agents. Depending on the finishing agent used, the combination of finishing agents imparts a variety of advantageous properties, including water repellency, abrasion resistance, and / or pilling resistance.

[0032] The finishing agent composition is free of or substantially free of alkyl fluoropolymers. As used herein, the term “substantially free of” refers to components (e.g., substantially free of alkyl fluoropolymers) meaning that the finishing agent composition may include less than 1%, less than 0.1%, less than 0.01%, less than 0.001%, or less than 0.0001% of components (e.g., alkyl fluoropolymers) based on the weight of the finishing agent composition.

[0033] The exemplary finishing agent compositions described herein may include combinations of alkyl urethane polymers, acrylic polymers, crosslinked polyurethanes, wetting agents, end-capped isocyanate crosslinking agents, and silicone softeners as water repellents.

[0034] In some instances, exemplary finishing agent compositions as described herein may include combinations of hydrocarbon polymers, acrylic polymers, crosslinked polyurethanes, wetting agents, end-capped isocyanate crosslinking agents, and silicone softeners as water repellents.

[0035] In other examples, exemplary finishing agent compositions as described herein may include combinations of cationic hyperbranched and linear alkyl polymers, acrylic polymers, crosslinked polyurethanes, wetting agents, end-capped isocyanate crosslinking agents, and silicone softeners as water repellents.

[0036] In other instances, exemplary finishing compositions as described herein may include combinations of fluorine-free water repellents, acrylic polymers, wetting agents, and silicone softeners.

[0037] In other instances, exemplary finishing agent compositions as described herein may include wetting agents, acrylic polymers, water repellents comprising acrylic copolymers and paraffin dispersions, and end-capped isocyanate crosslinking agents.

[0038] The finishing agent composition may optionally include a pH control agent such as acetic acid.

[0039] fabric

[0040] Furthermore, this document describes fabrics to which the above-described finishing agent composition is applied. The fabric may be a flame-retardant fabric. For example, the fabric may comprise multiple spun yarns containing multiple fibers (e.g., flame-retardant fibers). Before the finishing agent is applied, the fabric is also referred to herein as an untreated fabric (e.g., an untreated flame-retardant fabric). In one embodiment, the untreated fabric as described herein is formed from multiple flame-retardant fibers such as: aromatic polyamide fibers (e.g., meta-aramid fibers and para-aramid fibers), polybenzimidazole (PBI) fibers, polybenzoxazole (PBO) fibers, melamine fibers, polyimide fibers, polyimide amide fibers, modified polyacrylonitrile fibers, FR rayon fibers, and combinations thereof.

[0041] The specific commercially available fibers suitable for use alone or in combination with other fibers mentioned in this article include: (para-aramid), (meta-aramid) (para-aramid), (aromatic copolyamide), and (Polybenzoxazole). Other suitable fabrics include fabrics containing non-inherently flame-retardant fibers that have been made flame-retardant by treating such fibers with a suitable flame retardant. Such fibers include, but are not limited to, nylon, cellulosic fibers, such as rayon, cotton, acetate fibers, triacetate fibers, lyocell, and combinations thereof. Suitable fabrics may be plain-weave fabrics or fabrics with another construction, such as, but not limited to, nylon yarn reinforcement, twill weave, satin weave, or knit, and these constructions may be elastic or non-elastic. Flame-retardant fabrics may additionally have water-resistant properties and / or may be treated separately from the finishing agent compositions described herein with a water-resistant finishing agent to prevent or reduce water absorption from the external environment where garments made of the fabric may be used. Optionally, the fabric may include filament yarns and / or long-pile yarns.

[0042] As noted above, in some embodiments, the fabric is a flame-retardant fabric. The fabric preferably has flame-retardant properties that are maintained after the application of the finishing agent composition. The fabric may further have water-repellent properties that are also maintained after the application of the finishing agent composition. Where applicable, the fabric is expected to meet all the flame-retardant and / or water-repellent requirements of one or more of the following: NFPA 1951, NFPA 1971, NFPA 1977, NFPA 2112, NFPA 70E, and military specifications MIL-C-83429B and GL-PD-07-12. For example, according to NFPA 1971, the outer shell fabric of a firefighter must exhibit a char length of less than or equal to 4.0 inches after exposure to flame, and when tested according to ASTM D6413, the fabric must exhibit an afterflame of less than 2.0 seconds.

[0043] Methods for preparing finished fabrics

[0044] Untreated fabrics can be treated with finishing agent compositions as described herein to produce water-repellent and flame-retardant fabrics. A variety of methodologies and associated apparatuses can be used to apply finishing agents to untreated fabrics. These methodologies include, but are not limited to, spray application, pad dyeing, roller coating, application of foam finishing agents, and combinations thereof.

[0045] In some embodiments, the finishing agent can be cured by applying heat and / or pressure over time to the untreated fabric, finishing agent, or both until one or more components of the finishing agent are affected. In such cases, curing can activate specific finishing agent components to form crosslinks with the fabric, or otherwise cause the finishing agent to substantially adhere to the untreated protective fabric, while removing any excess moisture that may be present in the untreated fabric and / or the finishing agent. By way of example, and not limitation, a suitable curing process can be a drying process, applying heat between about 300 and about 400℉ to the initially treated fabric and finishing agent for about 1 to 5 minutes.

[0046] In other embodiments, a finishing process may be used to apply the finishing agent to fibers, yarns, fabrics, or garments. The following process is described by way of example, and other process embodiments may have fewer or more steps and may be practiced in an alternative order. An untreated fabric containing multiple flame-retardant fibers is received for treatment. The untreated fabric may be substantially untreated, or may be treated with flame-retardant, water-resistant, or other compositions, but is referred to herein as “untreated” to distinguish it from fabrics treated as described herein. A finishing agent composition as described above is applied to the untreated fabric. The finishing agent is cured by controlling at least one of heat, pressure, or time. Fabrics treated with this process have improved water repellency and surface abrasion resistance and / or pilling resistance.

[0047] Finishing fabric properties

[0048] Compared to untreated fabrics (i.e., fabrics not treated with finishing agents as described herein and including at least the aforementioned reagents and polymeric abrasion-resistant acids), the resulting finished fabrics exhibit improved water absorption and improved surface abrasion resistance and / or pilling resistance. Finished or treated fabrics, before washing and after five washes according to AATCC Test Method 135 (2018), have abrasion resistance of at least approximately 500 cycles before the first breakage when tested according to ASTM Test Method D3884 (2017) (H-18, 500g per wheel), and other properties of less than or equal to 15.0% as determined by NFPA 1971, 8.26 (2018). For example, the finished fabrics described herein meet the Total Heat Loss (THL) requirements according to NFPA 1971 (2018). Additionally, the fabric has a weight of less than about 8.0 osy (e.g., 7.9 osy or less, 7.8 osy or less, 7.7 osy or less, 7.6 osy or less, 7.5 osy or less, 7.4 osy or less, 7.3 osy or less, 7.2 osy or less, 7.1 osy or less, 7.0 osy or less, 6.9 osy or less, 6.8 osy or less, 6.7 osy or less, 6.6 osy or less, 6.5 osy or less, 6.4 osy or less, 6.3 osy or less, 6.2 osy or less, 6.1 osy or less, or 6.0 osy or less). Other advantageous properties exhibited by the finished fabric are further described below.

[0049] Flammability and flame resistance

[0050] The flammability of the finished fabrics described herein can be tested according to the standard test method (vertical test) of ASTM D6413, "Flame Resistance of Textiles". Prior to washing, the finished fabrics described herein exhibit a char length of no more than 0.8 inches in the warp direction (e.g., no more than 0.75 inches, 0.70 inches, 0.65 inches, 0.60 inches, or 0.55 inches) and no more than 0.9 inches in the weft direction (e.g., no more than 0.85 inches, 0.80 inches, 0.75 inches, 0.70 inches, 0.65 inches, 0.60 inches, or 0.55 inches). The finished fabrics described herein also exhibit an afterglow of 35 seconds or less before washing and after five washes. Additionally, when tested according to ASTM D6413, the finished fabrics described herein may exhibit an afterflame shorter than 2.0 seconds (e.g., 1.9 seconds or less, 1.8 seconds or less, 1.7 seconds or less, 1.6 seconds or less, 1.5 seconds or less, 1.4 seconds or less, 1.3 seconds or less, 1.2 seconds or less, 1.1 seconds or less, 1.0 seconds or less, 0.9 seconds or less, 0.8 seconds or less, 0.7 seconds or less, 0.6 seconds or less, 0.5 seconds or less, 0.4 seconds or less, 0.3 seconds or less, 0.2 seconds or less, 0.1 seconds or less, or 0.0 seconds).

[0051] In some instances, the finished fabric meets all flammability requirements of one or more of NFPA 1951 (2013), NFPA 1971 (2018), NFPA 1977 (2016), NFPA 2112 (2018), Military Specification MIL-C-83429B, or Military Specification GL-PD-07-12 before washing and after ten washes according to AATCC Test Method 135 (2018). For example, the fabric meets the vertical flammability requirements of NFPA 1951 (2013) after washing and ten washes according to AATCC Test Method 135 (2018). Optionally, the fabric meets the vertical flammability requirements of NFPA 1977 (2016) after washing and one hundred washes according to AATCC Test Method 135 (2018). Optionally, the fabric meets the vertical flammability requirements of NFPA 2112 (2018) before washing and after one hundred industrial washes. Optionally, the fabric meets the vertical flammability requirements of NFPA 1971 (2018) before washing and after five washes according to AATCC Test Method 135 (2018).

[0052] Water repellency

[0053] The water-repellent properties of the finished fabrics described herein can be determined according to AATCC Test Method 22 Water Repellency: Spray Test and NFPA 1971, 8.26 Water Absorption Resistance Test. In some instances, the finished fabrics described herein have a water spray rating of at least about 70 before washing and after five washes according to AATCC Test Method 135 (2018). In some instances, the finished fabrics described herein may have a water spray rating of 100 before washing.

[0054] As described above, the finished or treated fabric has a water absorption rate of less than or equal to 15.0% as determined by NFPA 1971, 8.26 (2018) before washing and after five washes according to AATCC test method 135 (2018). For example, before washing and after five washes as detailed above, the absorbency may be 14.5% or less, 14.0% or less, 13.5% or less, 13.0% or less, 12.5% ​​or less, 12.0% or less, 11.5% or less, 11.0% or less, 10.5% or less, 10.0% or less, 9.5% or less, 9.0% or less, 8.5% or less, 8.0% or less, 7.5% or less, 7.0% or less, 6.5% or less, 6.0% or less, 5.5% or less, 5.0% or less, 4.5% or less, 4.0% or less, 3.5% or less, 3.0% or less, 2.5% or less, 2.0% or less, 1.5% or less, or 1.0% or less.

[0055] In some instances, the finished fabrics met all the water repellency requirements of one or both of NFPA 1951 (2013) or NFPA 1971 (2018) before washing and after five washes according to AATCC Test Method 135 (2018). In some instances, the finished fabrics continued to meet the above water repellency requirements after ten washes according to AATCC Test Method 135 (2018).

[0056] Abrasion resistance and / or anti-pilling properties

[0057] The abrasion resistance of the finished fabrics described herein can be determined according to the standard test method (turntable, double-headed method) for abrasion resistance of textiles, ASTM D3884, using an H-18 wheel and a 500g load on each wheel. As described above, the finished or treated fabric, before washing and after five washes according to AATCC Test Method 135 (2018), has an abrasion resistance of at least approximately 500 cycles before the first breakage when tested according to ASTM Test Method D3884 (2017) (H-18, 500g per wheel), which means that the fabric withstands at least 500 cycles before the first breakage. For example, the abrasion resistance of the fabric before the first breakage can be at least about 550 cycles, at least about 600 cycles, at least about 650 cycles, at least about 700 cycles, at least about 750 cycles, at least about 800 cycles, at least about 850 cycles, at least about 900 cycles, at least about 950 cycles, at least about 1000 cycles, at least about 1050 cycles, at least about 1100 cycles, at least about 1200 cycles, at least about 1300 cycles, at least about 1400 cycles, at least about 1500 cycles, at least about 1600 cycles, at least about 1700 cycles, at least about 1800 cycles, at least about 1900 cycles, at least about 2000 cycles, at least about 2100 cycles, at least about 2200 cycles, at least about 2300 cycles, at least about 2400 cycles, or at least about 2500 cycles.

[0058] Alternatively or concurrently, according to the standard test method for anti-pilling and other related surface changes of textiles, ASTM D3512 Random Tumble Pilling Tester, the finished fabrics described herein may have a pilling performance rating of at least 4 after 60 minutes and at least 3 after 90 minutes. More preferably, the finished fabrics may have a rating of at least 4 after 90 minutes and at least 3 after 120 minutes.

[0059] clothing

[0060] Furthermore, this article describes garments made from fabrics treated with finishing agent compositions as described herein. As described above, the finishing agent compositions improve the water repellency, surface abrasion resistance, and / or pilling resistance of the fabrics. Therefore, garments made from fabrics treated or finished as described herein also exhibit improved water repellency, surface abrasion resistance, and / or pilling resistance compared to untreated garments. The garments also exhibit flame-retardant properties, which are maintained after the application of the finishing agent compositions.

[0061] Preferably, most of the fibers on the outer surface of the protective clothing of this disclosure are composed of flame-retardant materials such as meta-aramid, para-aramid, flame-retardant cellulose materials (e.g., flame-retardant cotton, rayon or acetate fiber), polybenzoxazole (PBO), or polybenzimidazole (PBI).

[0062] Figure 1 Examples of protective clothing 100, for which the fabric described herein is particularly suitable, are shown. Clothing 100 may be a firefighter's combat uniform top (…). Figure 1 (As shown herein) or any other garment or garment layer that is flame-retardant, water-repellent, and has an abrasion-resistant and / or pill-resistant surface as described herein. While firefighter combat jackets are used as examples and are explicitly discussed herein, jackets are identified for illustrative purposes only. Therefore, this disclosure is not limited to firefighter combat jackets, but generally relates to any garment that firefighters, rescuers, military personnel, electricians, petrochemical workers, or other individuals may wear to provide thermal or other type of protection. Such garments include, but are not limited to, shirts, trousers, jackets, jumpsuits, vests, T-shirts, underwear, gloves, glove linings, hats, helmets, boots, etc. This disclosure is not limited to garments and may also include other uses of flame-retardant, water-repellent, and pill-resistant and / or abrasion-resistant fabrics unrelated to their application.

[0063] Figure 1 The garment 100 shown includes a shell 102 forming the outer surface of the garment 100, a barrier layer 104 forming the middle layer of the garment, and a thermal lining 106 forming the inner surface of the garment 100. For general reference, the outer surface or shell 102 may be directly exposed to the environment in which the user or wearer operates, and the inner surface of the thermal lining 106 is a surface that comes into contact with the user or wearer, or with clothing that the user or wearer may wear. In some instances, some or all of the layers 102, 104, or 106 forming the garment 100 may comprise the flame-retardant, water-repellent, and anti-pilling and / or surface-abrasion resistant fabrics described herein.

[0064] The following examples will help to further illustrate this disclosure, but do not constitute any limitation thereof. Rather, it is to be clearly understood that, upon reading the description herein, one may resort to various embodiments, modifications, and equivalents that may occur to those skilled in the art without departing from the spirit of this disclosure. Example

[0065] In the embodiments described below, as further detailed below, the following methods were used to test the NPFA 1971 water absorption, abrasion resistance, and vertical flammability of finished fabric samples using char length and / or afterflame testing.

[0066] Water absorption resistance was measured according to NFPA 1971 for protective suits for structural fire protection and near-fire protection, 8.26 Water absorption test, the contents of which are hereby incorporated by reference.

[0067] Abrasion resistance was measured according to the standard test method (rotary double-head method) for abrasion resistance of textiles in ASTM D3884, using an H-18 wheel and a 500g load on each wheel, the contents of which are hereby incorporated by reference.

[0068] Vertical flammability is measured according to the standard test method (vertical test) of ASTM D6413 for flammability of textiles, the contents of which are hereby incorporated by reference.

[0069] Fabric samples were tested before washing (BW), after 5 washes (5×), or after 10 washes (10×). All washes were performed according to AATCC Test Method 135 for dimensional changes of fabric after household washing. Specifically, samples were subjected to washing and drying according to the following conditions: Machine cycle 1: normal / heavy cotton fabric cycle; washing temperature V: 60±3℃ (140±5℉); washing machine conditions: normal cycle, water level 18±1 gal, agitator speed 179±2 spm, washing time 12 min, spin speed 645±15 rpm and final spin time 6 min; and dryer settings: cotton / heavy garment cycle, high exhaust temperature (66±5℃, 150±10℉) and cooling time 10 min.

[0070] The flame retardancy standards referenced in this document are NFPA 1951, a standard for protective suits for technical rescue incidents; NFPA 1971, a standard for protective suits for structural fire fighting and near-fire fighting; NFPA 1977, a standard for protective clothing and equipment for wildland fire fighting; NFPA 2112, a standard for flame-retardant clothing for industrial workers to protect against flashovers; NFPA 70E, a standard for electrical safety requirements in the workplace; and military specifications MIL-C-83429B and GL-PD-07-12, the contents of which are hereby incorporated by reference.

[0071] Example 1:

[0072] Exemplary finishing agent compositions were prepared according to Tables 1-6. The finishing agent compositions were applied to PIONEER KHAKI fabric samples (60 / 40 para-aramid / meta-aramid twill fabric). The finishing agent compositions were applied to the fabric samples using pad-dyeing application (5 bar / 3 m / min). The fabrics were then pre-dried at 260℉ for three minutes in a Mathis Labdryer single-zone electric laboratory tenter, followed by curing at a temperature ranging from 310℉ to 338℉ for one to two minutes to provide finished fabric samples.

[0073] Table 1

[0074]

[0075] *All values ​​are based on percentages of bath weight; the remainder of the composition is water.

[0076] Table 2

[0077]

[0078] *All values ​​are based on percentages of bath weight; the remainder of the composition is water.

[0079] Table 3

[0080]

[0081]

[0082] *All values ​​are based on percentages of bath weight; the remainder of the composition is water.

[0083] Table 4

[0084]

[0085] *All values ​​are based on percentages of bath weight; the remainder of the composition is water.

[0086] Table 5

[0087] Components Component description 25 26 27* Ridgewet NRW wetting agent 0.50 0.50 0.50 Phobotex RSY Acrylic copolymers and paraffin dispersions 15.00 - - Repellan V5 Fluorine-free water repellent - 15.00 15.00 Phobol Extender XAN End-capped isocyanate crosslinking agent 6.00 6.00 6.00 Dicrylan TA-GP acrylic polymers 8.00 8.00 8.00 Securon 540 Phosphonic acid complexing agents - - 1.0

[0088] *All values ​​are based on percentages of bath weight; the remainder of the composition is water.

[0089] Table 6

[0090]

[0091] *All values ​​are based on percentages of bath weight; the remainder of the composition is water.

[0092] experiment

[0093] As further detailed below, the vertical flammability, abrasion resistance, and NPFA 1971 water absorption of the finished fabric samples were tested using the char length test. All tests were performed prior to any washing of the finished fabric samples.

[0094] The water resistance of fabrics was determined using NFPA 1971, 8.26. According to NFPA 1971, 8.26, the sample was fixed to a lace loop, and a volume of water was sprayed onto the sample. Excess water was removed using blotting paper, and a 4-inch × 4-inch square was cut from the sample. The wet sample was weighed, dried, and weighed again. The percentage water absorption (PWA) was determined based on the difference between the wet and dry weights. The results of this test are shown in Table 7 below.

[0095] According to ASTM D3884, each fabric sample is subjected to the standard Taber abrasion test using H-18 wheels and a 500g load on each wheel. This method involves abrading the specimen using a rotating friction motion under controlled pressure and abrasion action. The specimen, fixed to a platform, is connected to a longitudinal axis that slides relative to two abrasion wheels. One abrasion wheel rubs the specimen outwards towards the periphery, while the other rubs it inwards towards the center. The resulting abrasion marks are formed at approximately 30cm. 2 The intersecting arc pattern on the area.

[0096] Each fabric sample was subjected to 250 cycles, followed by inspection for thread breaks. If no thread breaks were observed, the fabric sample was subjected to another 250 cycles and inspected again. This process was repeated for each fabric sample until a thread break was observed. The results of the abrasion resistance test are shown in Table 7 below.

[0097] The flame retardancy of fabrics was tested according to ASTM D6413. According to this method, the fabric was suspended vertically and exposed to an open flame. The char length and afterglow of each fabric were determined. The char length of each fabric was determined in both the warp (w) and weft (f) directions. The test results for the fabrics described herein are shown in Table 7 below.

[0098] Table 7

[0099]

[0100]

[0101] *The value in parentheses indicates the retest value.

[0102] Based on these results, many of the finishing agent compositions presented in Table 7 do not affect the water-repellent properties of the fabrics, and the treated fabrics meet the water resistance requirements of NFPA 1971. In some cases, the finishing agent compositions described herein impart significant water-repellent properties to the fabric samples (see, for example, samples Y, B1, C1, D1, and E1). The samples exhibited absorbance values ​​significantly lower than the maximum allowable value of 15% according to NFPA 1971 requirements.

[0103] Compared to the untreated fabric samples, the test fabric samples presented in Table 7 withstood more cycles before breaking. Most of the finished fabric samples withstood at least 500 cycles before the first thread break and / or breakage. These data demonstrate that the finishing agent compositions described herein effectively impart abrasion resistance to the fabric samples.

[0104] Furthermore, the data in Table 7 indicate that the finishing agent composition according to this disclosure does not adversely affect the flame retardant properties of the fabric.

[0105] Example 2:

[0106] Exemplary finishing agent compositions were prepared according to Table 8. The finishing agent compositions were applied to PIONEER KHAKI fabric samples (60 / 40 para-aramid / meta-aramid twill fabric). The finishing agent compositions were applied to the fabric samples using pad-dyeing application (5 bar / 3 m / min). The fabrics were then pre-dried at 260℉ for three minutes in a Mathis Labdryer single-zone electric laboratory tenter, followed by curing at a temperature ranging from 300℉ to 338℉ for one to two minutes to provide finished fabric samples.

[0107] Table 8

[0108]

[0109]

[0110] *All values ​​are based on percentages of bath weight; the remainder of the composition is water.

[0111] Following the experimental procedure described in Example 1, the vertical flammability, abrasion resistance, and NPFA 1971 water absorption of the finished fabric samples were tested using the char length test. All tests were performed prior to any washing of the finished fabric samples. The data are shown in Table 9.

[0112] Table 9

[0113]

[0114] Based on these results, the finishing agent compositions described herein impart significant water-repellent properties to the fabric samples. The resulting samples F1, G1, H1, and I1 exhibited water absorption values ​​significantly lower than the maximum allowable value of 15% according to NFPA 1971. Furthermore, the finishing agent compositions described herein do not adversely affect the flame-retardant properties of the fabrics.

[0115] Example 3:

[0116] Exemplary finishing agent compositions were prepared according to Table 10. The finishing agent compositions were applied to two different fabrics. Both fabrics were woven protective fabrics containing ring-spun yarns. Fabric 1 was a PIONEER AIRO fabric, consisting of 60% T-970 Kevlar and 40% N303 Tan Nomex. Fabric 2 was a KOMBAT FLEX fabric, consisting of 54% T-970 Kevlar and 46% polybenzimidazole (PBI). Both Fabric 1 and Fabric 2 were fire-fighting shell fabrics. The finishing agent compositions were applied to the fabric samples using pad-dyeing with an impregnation finishing agent at a WPU (liquid absorbency) of 40% to 65%. The fabrics were then dried and cured using a 60°C oven with a zone set between 285°F and 330°F. The drying and curing speed was 15 yards per minute.

[0117] Table 10

[0118]

[0119]

[0120] *All values ​​are based on percentages of bath weight; the remainder of the composition is water.

[0121] Following the experimental procedure described in Example 1, the NPFA 1971 water absorption, abrasion resistance, and vertical flammability using the char length test were tested on the finished fabric samples. The vertical flammability test was performed before any washing of the finished fabric samples. Water absorption and abrasion resistance tests were performed before washing (indicated as “BW” in Table 11 below) and after five washes (5×) according to AATCC Test Method 135 described above. The data are shown in Table 11. Surface abrasion data show the number of Taber cycles before the first thread breakage of the sample was observed, as described above.

[0122] Table 11

[0123]

[0124] Based on these results, the finishing agent compositions described herein impart significant water-repellent properties to the fabric samples. The water repellency was observed in the finished fabric samples before washing and remained in the finished fabric samples after washing. All samples exhibited water absorption values ​​below the maximum allowable value of 15% according to NFPA 1971 requirements.

[0125] Compared to the untreated fabric samples, the test fabric samples presented in Table 11 withstood more cycles before breaking. All finished fabric samples withstood at least 500 cycles before the first breakage. These data demonstrate that the finishing agent compositions described herein effectively impart abrasion resistance to the fabric samples.

[0126] In addition, the finishing agent composition described herein does not adversely affect the flame retardant properties of the fabric.

[0127] Example 4:

[0128] Exemplary finishing agent compositions were prepared according to Table 12. The finishing agent compositions were applied to PIONEER KHAKI fabric samples (60 / 40 para-aramid / meta-aramid twill fabric) using pad-dyeing application (5 bar / 3 m / min). The fabric was then dried and cured in an oven at 340℉ for three minutes. The spin speed used for the drying and curing steps was 1800 rpm.

[0129] Table 12

[0130] Components Component description 36 37 38 39 Ridgewet NRW wetting agent 0.25 0.25 1.00 1.00 Acetic acid, 84% pH control agent 0.15 0.15 - - Fibropel NF-22 Fluorine-free water repellent 15.00 - - - Neoseed NR-7080 acrylic polymers 15.00 Phobol Extender XAN End-capped isocyanate crosslinking agent 2.00 2.00 - 1.00 Barpel FF New Silicone-based polymers - - - 12.00 NK Assist FU End-capped isocyanate crosslinking agent - - 1.00 - Neoseed NR-8000 Silicone-based polymers - - 12.50 -

[0131] *All values ​​are based on percentages of bath weight; the remainder of the composition is water.

[0132] Following the experimental procedure described in Example 1, the vertical flammability, abrasion resistance, and NPFA 1971 water absorption of the finished fabric samples were tested using the char length test. All tests were performed before any washing of the finished fabric samples. The data are shown in Table 13.

[0133] Table 13

[0134]

[0135] The resulting samples N1, O1, and P1 exhibited water absorption values ​​below the maximum allowable value of 15% according to NFPA 1971. Furthermore, the finishing agent compositions described herein do not adversely affect the flame retardant properties of the fabrics.

[0136] Example 5:

[0137] Exemplary finishing agent compositions 25 (see Table 5) and 30 (see Table 6) were prepared and applied to five different woven protective fabrics containing ring-spun yarns. Fabric 3 is a GEMINI XT natural fabric, consisting of 60% para-aramid and 40% polybenzimidazole. Fabric 4 is an ADVANCE fabric, consisting of 60% para-aramid and 40% meta-aramid. Fabric 5 is a PIONEER KHAKI fabric, a twill fabric consisting of 60% para-aramid and 40% meta-aramid. Fabric 6 is an AGILITY DARK GOLD fabric, an aramid blend. Fabric 7 is a KOMBAT FLEX fabric, consisting of 54% T-970 Kevlar and 46% polybenzimidazole (PBI). All fabrics are fire-fighting shell fabrics, commercially available from TenCate Protective Fabrics (Union City, Georgia). Apply the finishing agent composition to the fabric sample using padding with an impregnation finishing agent at a WPU (liquid absorbency) of 40% to 55%. Then, dry and cure the fabric using a 60°C oven set at 330°F for all areas. For both formulations, the drying and curing speed is 10 yards per minute.

[0138] The NPFA 1971 water absorption, abrasion resistance, and vertical flammability using the char length test were tested on the finished fabric samples according to the experimental procedures described in Example 1. The water repellency of the finished fabric samples was also tested using AATCC Test Method 22 by testing the water spray rating. All tests were performed before washing (indicated as “BW”) and after five washes (indicated as “5×”) or ten washes (indicated as “10×”) according to AATCC Test Method 135 described above. Surface abrasion data showed the number of Taber cycles before the first thread breakage of the sample was observed, as described above. Data for samples prepared by applying finishing agent composition 25 to each of fabrics 3, 4, 5, 6, and 7 are shown in Table 14.

[0139] Table 14

[0140]

[0141]

[0142] Data for samples prepared by applying finishing agent composition 30 to each of fabrics 3, 4, 5, 6 and 7 are shown in Table 15.

[0143] Table 15

[0144]

[0145] As a control, PIONEER KHAKI fabric (“Control 1”) and KOMBAT FLEX fabric (“Control 2”) treated with alkyl fluoropolymer finishing agents were tested using the same parameters described above. The alkyl fluoropolymer finishing agents included 2.50 g / L wetting agent, 2.50 g / L compatibilizer, 2.50 g / L defoamer, 60.0 g / L urethane anti-pilling / abrasion aid, 140.0 g / L acrylic abrasion aid, 120.0 g / L C6 alkyl fluoropolymer DWR agent, 60.0 g / L crosslinking agent, 60.0 g / L high-density polyethylene softener, and 10.0 g / L non-durable flame retardant. The results are shown in Table 16.

[0146] Table 16

[0147] Comparison 1 Comparison 2 Width (inches) 60.25 60.875 Weight (osy) 6.6 6.8 structure 45×42 47×45 Washing shrinkage rate (%) 0.5×1.2 0.9×0.7 Stretching [lbf]BW 381×364 254×333 Stretching [lbf]AW10× 339×361 303×312 Trapezoidal tear in BW[lbf] 47×45 53×52 Trapezoidal tear AW5×[lbf] 47×47 58×63 Vertical combustion charring length BW [inches] (warp x weft) 0.45×0.49 0.28×0.21 Vertical combustion charring length AW5 × [inches] (warp × weft) 0.51×0.59 0.38×0.46 Water absorption rate (BW) [%) 5.4 5.4 Water absorption rate AW5 × [%) 3.7 5.5 Water spray BW 90 70 Water spray AW5× 80 70 TaberBW 4750 3200 TaberAW5× 2500 650

[0148] Based on these results, finishing agent compositions 25 and 30 consistently imparted significant water-repellent properties to a variety of fabric samples. The water repellency was observed in the finished fabric samples before washing and remained after washing. All samples exhibited water absorption values ​​below the maximum allowed under NFPA 1971 requirements (15%), and water spray ratings equal to or higher than those of the untreated samples. Furthermore, the finishing agent compositions described herein did not adversely affect the flame-retardant properties of the fabrics.

[0149] Example 6:

[0150] Exemplary finishing agent compositions were prepared according to Tables 17 and 18. The finishing agent compositions were applied to PIONEER KHAKI fabric samples (60 / 40 para-aramid / meta-aramid twill fabric) using pad-dyeing application (5 bar / 3 m / min). The fabric was then dried in an oven at 260℉ for three minutes and cured at 330℉ for one minute. The spin speed used for the drying and curing steps was 1800 rpm.

[0151] Table 17

[0152] Components Component description 40 41 42 43 44 Ridgewet NRW wetting agent 0.50 0.50 0.50 0.50 0.50 Dicrylan TA-GP acrylic polymers 8.00 8.00 8.00 8.00 8.00 Dicrylan PGS Carbamate polymers - 10.00 10.00 - 10.00 Phobotex RSY Acrylic copolymers and paraffin dispersions 15.00 15.00 25.00 25.00 - Phobol Extender XAN End-capped isocyanate crosslinking agent 6.00 6.00 6.00 6.00 6.00 Repellan V5 Fluorine-free water repellent 15.00

[0153] *All values ​​are based on percentages of bath weight; the remainder of the composition is water.

[0154] Table 18

[0155] Components Component description 45 46 47 48 49 Ridgewet NRW wetting agent 0.50 0.50 0.50 0.50 0.50 Dicrylan TA-GP acrylic polymers 8.00 8.00 8.00 8.00 8.00 Dicrylan PGS Carbamate polymers - 10.00 10.00 - 10.00 Phobol Extender XAN End-capped isocyanate crosslinking agent 6.00 6.00 6.00 6.00 6.00 Repellan V5 Fluorine-free water repellent - - - 15.00 Acetic acid, 84% pH control agent 0.04 0.04 0.04 0.04 0.04 Smart Repel Hydro PM Liq Fluorine-free water repellent 15.00 15.00 25.00 25.00 - Ultratex SI Silicone softener 2.00 2.00 2.00 2.00 2.00

[0156] *All values ​​are based on percentages of bath weight; the remainder of the composition is water.

[0157] Following the experimental procedure described in Example 1, the NPFA 1971 water absorption, abrasion resistance, and vertical flammability using the char length test were tested on the finished fabric samples. Vertical flammability, water absorption, and abrasion resistance tests were performed before washing (indicated as “BW” in Table 19 below) and after five washes (5×) according to AATCC Test Method 135 described above. The data are shown in Table 19. Surface abrasion data show the number of Taber cycles before the first thread breakage of the sample was observed, as described above.

[0158] Table 19

[0159]

[0160]

[0161] Example 7:

[0162] Exemplary finishing agent compositions 41 (see Table 17), 47 (see Table 18), and 48 (see Table 18) were prepared and applied to PIONEER KHAKI fabric (a 60% para-aramid and 40% meta-aramid twill fabric). The finishing agent compositions were applied to the fabric samples using pad-dyeing with an immersion finishing agent at 50% to 60% WPU (liquid absorbance). The fabrics were then dried and cured in an oven at a temperature set at 330℉ for all areas. The drying and curing speed was 10 yards per minute.

[0163] The NPFA 1971 water absorption, abrasion resistance, and vertical flammability using the char length test were tested on the finished fabric samples according to the experimental procedure described in Example 1. All tests were performed before washing (indicated as "BW") and after five washes according to AATCC Test Method 135 described above (indicated as "5×"). Surface abrasion data showed the number of Taber cycles prior to the first observed thread breakage of the sample, as described above. Data for samples prepared by applying finishing agent compositions 41, 47, and 48 to the fabric are shown in Table 20.

[0164] Table 20

[0165] Finishing agent 41 Finishing agent 47 Finishing agent 48 Vertical combustion charring length BW [inches] (warp x weft) 0.6×0.5 0.6×0.6 0.5×0.5 Vertical combustion charring length AW 5 × [inches] (warp × weft) 0.6×0.6 0.5×0.5 0.5×0.6 Water absorption rate (BW) [%) 7.2 16.5 9.9 Water absorption rate AW 5 × [%) 5.2 8.8 7.5 Taber BW 5000 5000 1000 Taber AW 5× 5000 4000 1000

[0166] Based on these results, finishing agent compositions 41, 47, and 48 consistently imparted the desired water-repellent properties to the various fabric samples. Water repellency was exhibited in the finished fabric samples prior to washing and remained in the finished fabric samples after washing. All samples showed water absorption values ​​below the maximum allowed under NFPA 1971 requirements of 15%.

[0167] Furthermore, the finishing agent compositions described herein do not adversely affect the flame retardancy of the fabrics. The test-treated fabric samples presented in Table 20 exhibit the desired abrasion resistance, as shown by the Taber results.

[0168] All patents, publications, and abstracts cited above are incorporated herein by reference in their entirety. Various embodiments of the invention have been described to achieve various objects of the invention. It should be understood that these embodiments are merely illustrative of the principles of the invention. Numerous modifications and adjustments to these embodiments will be apparent to those skilled in the art without departing from the spirit and scope of the invention as defined in the following claims.

Claims

1. A water repellent and flame resistant fabric comprising: a plurality of spun yarns comprising a plurality of flame resistant fibers; and a finish that imparts water repellency and abrasion resistance to the fabric, the finish comprising: (a) a water repellent that is a urethane-based polymer, and (b) a polymeric abrasion aid, wherein the fabric has: an abrasion resistance of at least 500 cycles to first break when tested according to ASTM Test Method D3884 (2017) (H-18, 500 g on each wheel), and a water absorption of less than or equal to 15.0% as determined by NFPA 1971, 8.26 (2018), wherein the finish comprises less than 1% of an alkyl fluoropolymer based on the weight of the finish.

2. The water repellent and flame resistant fabric of claim 1, wherein the finish further comprises a water repellent that is a hydrocarbon-based polymer.

3. The water repellent and flame resistant fabric of claim 1, wherein the finish further comprises a water repellent that is a silicone-based polymer.

4. The water repellent and flame resistant fabric of claim 1, wherein the finish further comprises a water repellent that is an acrylic-based polymer.

5. The water repellent and flame resistant fabric of claim 1, wherein the polymeric abrasion aid further comprises an acrylic polymer.

6. The water repellent and flame resistant fabric of any one of claims 1-5, wherein the finish further comprises at least one of an alkoxylated fatty amine or derivative thereof, a melamine formaldehyde resin, an N-methylol stearamide, or a combination thereof.

7. The water repellent and flame resistant fabric of any one of claims 1-5, wherein at least some of the plurality of flame resistant fibers are inherently flame resistant fibers comprising at least one of meta-aramid fibers, para-aramid fibers, polybenzimidazole fibers, polybenzoxazole fibers, melamine fibers, polyimide fibers, polyimide amide fibers, modacrylic fibers, and FR rayon fibers.

8. The water repellent and flame resistant fabric of any one of claims 1-5, wherein the abrasion resistance is at least 700 cycles to first break.

9. The water repellent and flame resistant fabric of any one of claims 1-5, wherein the abrasion resistance is at least 1000 cycles to first break.

10. The water repellent and flame resistant fabric of any one of claims 1-5, wherein the water absorption is less than or equal to 12.0% as determined by NFPA 1971, 8.26 (2018).

11. The water repellent and flame resistant fabric of any one of claims 1-5, wherein the water absorption is less than or equal to 10.0% as determined by NFPA 1971, 8.26 (2018).

12. The water repellent and flame resistant fabric of any one of claims 1-5, wherein the water absorption is less than or equal to 5.0% as determined by NFPA 1971, 8.26 (2018).

13. The water repellent and flame resistant fabric of any of claims 1-5, wherein the fabric meets the flammability requirements of NFPA 1971 (2018) before washing and after five washes according to AATCC Test Method 135 (2018).

14. The water repellent and flame resistant fabric of any of claims 1-5, wherein the fabric meets all of the water repellency requirements of one or both of NFPA 1951 (2013) or NFPA 1971 (2018) before washing and after five washes according to AATCC Test Method 135 (2018).

15. The water repellent and flame resistant fabric of any of claims 1-5, wherein the fabric meets the total heat loss requirement according to NFPA 1971 (2018).

16. The water repellent and flame resistant fabric of any of claims 1-5, wherein the fabric comprises a plain weave, a nylon thread reinforced fabric, a twill weave, a satin weave, or a knit fabric, and wherein the fabric is elastic or inelastic.

17. The water repellent and flame resistant fabric of any of claims 1-5, wherein the fabric has a weight of less than 8.0 osy.

18. A water repellent and flame resistant garment comprising the water repellent and flame resistant fabric of any of claims 1-17.

19. A water repellent fabric comprising: a plurality of spun yarns comprising a plurality of fibers; and a finish that imparts water repellency and abrasion resistance to the fabric, the finish comprising: (a) a water repellent that is a urethane-based polymer, and (b) a polymeric abrasion aid, wherein the fabric has: an abrasion resistance of at least 500 cycles before first break when tested according to ASTM Test Method D3884 (2017) (H-18, 500 g on each wheel), and a water absorption of less than or equal to 15.0% as determined by NFPA 1971, 8.26 (2018), wherein the finish comprises less than 1% of an alkyl fluoropolymer based on the weight of the finish.

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