Waterproof protective garment

Abstract

Protective garments made from a fabric treated with a durable waterproofing process are described. According to this description, this treatment is virtually fluorocarbon-free while offering excellent water resistance and durability.

Description

Waterproof protective garment BACKGROUND

[0001] There are various types of protective clothing designed to protect the wearer. In certain embodiments, for example, protective clothing is designed to protect against heat and flames in order to prevent burns. Such protective clothing is commonly worn by firefighters, other service providers, and military personnel. Military personnel, for example, use this clothing to protect themselves against incendiary devices and the like.

[0002] These garments must be fire-resistant and, at the same time, as light as possible, strong, resistant to abrasion, tearing and ripping, flexible and must hinder the user as little as possible.

[0003] Conventional firefighter clothing, for example, is usually made up of several discrete layers. These layers typically include an outer layer, a moisture barrier layer, a thermal barrier layer, and an inner lining. The layers are usually made of heat-resistant materials suitable for providing protection against heat and flames.

[0004] Previously, a challenge in designing protective clothing was preventing it from absorbing and retaining moisture. For example, protective clothing worn by firefighters often becomes wet during use due to exposure to firefighting water or rain. It can also become wet due to the absorption of the wearer's sweat. Unfortunately, when a garment absorbs moisture, its characteristics and properties can be negatively affected. For example, by retaining moisture, the garment can become significantly heavier.

[0005] In addition to increasing weight, the presence of moisture in a protective garment also negatively affects its thermal properties, reducing its effectiveness in protecting the wearer from the heat. In particular, since water is a much better conductor of heat than air, the rate of heat transfer through the garment increases. Furthermore, it has been found that when water in a protective garment heats up, it can turn into steam upon exposure to heat and actually burn the wearer.

[0006] In short, when the protective garments described above become wet or soaked with water or other liquids, they become hot and uncomfortable to work in due to their increased weight and the higher rate of heat transfer. Consequently, the wearer can only spend a limited time working or performing tasks while wearing the garment due to the possibility of heat stress.

[0007] Previously, to prevent protective garments from absorbing water, they were treated with a water-resistant composition. For example, water-resistant protective garments are described in U.S. Patents Nos. 6,192,520 and 7,581,260. These patents relate to inventions that have represented a major advance in the art.

[0008] However, in the past, water-resistant treatments applied to protective clothing, particularly garments containing inherently flame-resistant fibers, inevitably included fluorocarbon chemicals. These chemicals are durable and offer excellent water-resistant properties. Recently, however, various manufacturers, including fabric manufacturers, have faced increased pressure to reduce the amount of fluorocarbons incorporated into their products. Fluorocarbons, for example, do not readily biodegrade and can persist in landfills for many years. Furthermore, the manufacture and handling of fluorocarbons have been subject to increased government scrutiny and regulation.

[0009] US patent 8,793,814 B1 describes a flame-resistant fabric made from a blend of fibers. In all but one of the examples, a durable water-repellent treatment with a fluoropolymer is described. The only sample not treated with a fluoropolymer is a fabric coated with flame-retardant (FR) polyurethane.

[0010] Therefore, there is currently a need for an alternative water-repellent treatment that can be applied to protective garments and provides water-repellent properties without the use of fluorocarbons. In particular, a water-repellent treatment is needed that is virtually fluorocarbon-free and can be applied to all types of garments and layers, including firefighter, military, tactical, and industrial workwear, etc. SUMMARY

[0011] In general, this disclosure relates to a durable, virtually fluorocarbon-free water-repellent treatment for flame-resistant fabrics. For example, this treatment may contain virtually no fluoropolymers or be completely free of them, while still maintaining excellent water-repellent properties. This treatment is especially suitable for use on fabrics containing inherently flame-resistant fibers. Surprisingly, it was discovered that this treatment not only possesses excellent waterproofing properties, but also maintains them even after multiple washes.

[0012] The present invention relates to a protective garment according to claim 1. The protective garment includes at least one layer of fabric containing inherently fire-resistant fibers. This layer, for example, may be the outer layer of a protective garment, a lining for such a garment, or any layer of a multilayer composite. The inherently fire-resistant fibers may include, for example, para-aramid fibers, meta-aramid fibers, polybenzimidazole fibers, or mixtures thereof. In one embodiment, the outer layer material contains inherently fire-resistant fibers in an amount of at least approximately 80% by weight. According to the present disclosure, the fabric layer is treated with a durable water-repellent treatment. For example, the fabric layer may be impregnated with such a treatment.This treatment can be applied to the fabric layer using various techniques, such as immersing it in a bath, spraying it, or printing it.

[0013] The durable waterproof treatment is fluorocarbon-free. This treatment is incorporated into the fabric so that it maintains a spray resistance of at least 70, for example, 80 or 90, after ten wash cycles. In addition, the fabric can maintain a water absorption of less than 15%, 10%, 8%, 5%, 3%, or 2% after five or ten wash cycles.

[0014] The durable water-repellent treatment of this disclosure generally contains at least one polyurethane polymer. The polyurethane polymer, for example, may be a polyester / ether polyurethane polymer, such as an anionic aliphatic polyester / ether polyurethane. In one embodiment, the durable water-repellent treatment includes said polyurethane, according to claim 1, as a first polyurethane polymer, as described above, combined with a second polyurethane polymer. The second polyurethane polymer may comprise a blocked isocyanate. The weight ratio of the first polyurethane polymer to the second polyurethane polymer may be from approximately 5:1 to approximately 1:2, for example, from approximately 3:1 to approximately 1.5:1.The durable water-repellent treatment preferably contains the first polyurethane polymer in an amount of between 10% and 50% by weight, preferably the second polyurethane polymer in an amount of between 5% and 30% by weight, preferably a softener in an amount of between 5% and 25% by weight, and preferably a mixture of paraffin and acrylic polymer in an amount of between 20% and 70%; the weight percentages are based on the dry durable water-repellent treatment. The fabric layer treated in accordance with this disclosure may be practically free of fluorocarbons. For example, the fabric layers may contain fluorine in an amount of less than approximately 1000 ppm, for example, less than approximately 500 ppm, or less than approximately 100 ppm.In various embodiments, the fluoride content of the resulting fabric layer may be less than approximately 50 ppm, such as less than approximately 40 ppm, such as less than approximately 30 ppm, such as less than approximately 20 ppm.

[0015] In addition to at least one polyurethane polymer, a blocked isocyanate extender, and an acrylic polymer according to claim 1, the durable water-repellent treatment may contain other components and ingredients. In one embodiment, for example, the durable water-repellent treatment contains a softener. This softener may be a polyalkylene polymer, such as a polyethylene polymer. The durable water-repellent treatment may also contain a wax, such as paraffin.

[0016] As described above, textile material generally contains inherently fire-resistant fibers. Textile material, for example, may be made of spun yarns, multifilament yarns, monofilament yarns, broken elastic yarns, or mixtures thereof. In one embodiment, the outer layer material includes a combination of spun yarns and multifilament yarns.

[0017] Textile materials treated in accordance with this disclosure can exhibit an excellent balance of properties, in addition to excellent spray resistance. For example, when tested according to NFPA 19718.25, the textile material may exhibit water absorption of less than 10%, less than 7%, less than 5%, or less than 3%. The textile material can also provide protection against various chemical agents, such as acids, alkalis, and synthetic blood.When tested according to EN ISO 6530, for example, the fabric material may have a repellency index of more than approximately 85% and a penetration index of less than approximately 1% when tested against a 30% sulfuric acid solution, may show a repellency index of more than 90% and a penetration index of less than 1% when tested against a 10% sodium hydroxide solution, and may show a repellency index of more than approximately 85% and a penetration index of less than approximately 1.5% when tested against artificial blood.

[0018] Textile materials according to this disclosure also preferably exhibit greater abrasion resistance. For example, fabrics with a basis weight between 170 g / m² (5 osy) and 305 g / m² (9 osy) (e.g., outer layer materials) may exhibit abrasion resistance exceeding 90,000 cycles, for example, exceeding 95,000 cycles, according to the ASTM D4966 test method. Fabrics with a basis weight between 68 g / m² (2 osy) and 136 g / m² (4 osy) (e.g., lining materials) may exhibit abrasion resistance exceeding 40,000 cycles, according to the ASTM D4966 test method.

[0019] In one embodiment, the protective garment of this disclosure is a firefighter's garment. The garment may include an inner lining designed to cover at least a portion of the wearer's body. The inner lining is configured in the garment to face the wearer. The outer layer material may cover the inner lining. Any part of the protective garment may be treated in accordance with this disclosure, including the inner lining, the outer layer material, or any intermediate layer.

[0020] In alternative embodiments, the protective garment may comprise a fire-resistant hood, fire-resistant footwear, or fire-resistant gloves.

[0021] Other features and aspects of this disclosure are discussed in more detail below. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] A full and enabling disclosure of the present disclosure is set forth more particularly in the remainder of the specification, including reference to the accompanying figures, in which: Figure 1 is a perspective view of one embodiment of a protective garment made in accordance with this disclosure; Figure 2 is a cross-sectional view of an inner lining incorporated into the garment illustrated in Figure 1; Figures 3-3F are schematic views of illustrative examples of spray classifications for a standardized fabric spray test; and Figure 4 is a perspective view of one embodiment of a protective garment comprising trousers made in accordance with this disclosure.

[0023] The repeated use of reference characters in the present descriptive memorandum and drawings is intended to represent the same or analogous features or elements of the present invention. Definitions and standardized procedures

[0024] The following definitions and procedures are offered to better describe and quantify the performance of protective garments and fabrics manufactured according to the present invention compared to prior art constructions. Water repellency: AATCC TM2 spray test - 2017

[0025] As used herein, a fabric spray rating refers to a rating that a fabric or material receives according to AATCC TM2.-2017. In general, a spray test measures a material's resistance to being wetted by water.

[0026] According to the present invention, the following is the procedure used to determine the spray resistance of a material. 1. A 17.8 cm x 17.8 cm (7" x 7") sample of the material to be tested is conditioned to a relative humidity of 65 ± 2% and 21.1 ± 1.1 °C (70 ± 2 °F) for a minimum of four hours before testing. 2. The fabric sample is securely attached to a 15.2 cm (6") metal hoop to prevent creasing. The hoop is placed on a test stand with the fabric facing upward. Twills, gabardines, piqués, or similar ribbed fabrics are positioned on the stand so that the ribs run diagonally to the flow of water running down the fabric. A funnel connected to a nozzle to hold water is placed 15.2 cm (6") above the center of the fabric. 3. Pour 250 milliliters of water at 26.7 ± 1.1 °C (80 ± 2 °F) from a cup or other container into the funnel, allowing the water to be sprayed onto the cloth. 4. Once the water has passed through the funnel, hold one edge of the hoop and strike the opposite edge firmly once against a solid object with the cloth facing the object. Then, rotate the hoop 180° and strike it once more at the point previously held. 5. Next, the wet or stained fabric sample is compared to the standards shown in Figures 3A-3F. The fabric is assigned a spray rating that corresponds to the closest standard. As shown in Figures 3A-3F, the fabric can be rated from 0 to 100, where 0 indicates that the entire fabric is wet with water, while a rating of 100 indicates that no part of the fabric was wetted by water. Water-based liquid repellency: Water and alcohol solution resistance test (AATCC TM193-2017)

[0027] The following standardized water repellency test determines a material's resistance to wetting by aqueous liquids. Typically, drops of a water-alcohol mixture with varying surface tensions are placed on the material's surface, and the degree of wetting is visually assessed. A higher rating indicates resistance to staining by water-based substances. The composition of the standard test liquids is as follows: TABLE 1 Standard test liquids Water repellency composition Classification number Isopropanol, % Distilled water, % 1 2 98 23 10 90 4 20 80 5 30 70 6 40 60 7 50 50 8 60 40

[0028] The water repellency procedure is as follows: 1. A 20.3 cm x 20.3 cm (8" x 8") fabric sample is conditioned at a relative humidity of 65% ± 2% and 21.1 ± 1.1 °C (70 ± 2 °F) for a minimum of four hours. The fabric is placed horizontally face up on white blotting paper. 2. Starting with test liquid number 1, place one drop of the liquid on three points of the material. Each drop placed on the material should be separated by 5 cm. 3. The material is observed for 10 seconds from an approximate angle of 45º. 4. If two of the three drops have not wetted the fabric or seeped through, place drops of test liquid number 2 at an adjacent spot and repeat step 3. 5. This procedure is continued until two out of three drops have wetted or been absorbed by the fabric. The water repellency rating corresponds to the liquid with the highest number for which two out of three drops do not wet or be absorbed by the fabric. Oil repellency: Hydrocarbon resistance test (AATCC TM118-2013).

[0029] The following oil repellency test determines the resistance of finished fabrics to oil stains and moisture caused by organic liquids. In this test, drops of eight liquid hydrocarbons of varying surface tensions are placed on the surface of the material, and the degree of surface moisture is visually determined. The standard test liquids used are as follows: TABLE 2 Standard oil repellency test liquids Hydrocarbon Classification Number Refined mineral oil 1 Refined mineral oil / n-hexadecane 65 / 35% by volume at 22°C, 2 n-hexadecane 3 n-tetradecane 4 n-dodecane n-decan 6 n-octane 7 n-heptane 8 1. A sample of material measuring 20.3 cm x 20.3 cm (8" x 8") is conditioned at a relative humidity of 65 ± 2% and 21.1 ± 1.1 °C (70 ± 2 °F) for a minimum of four hours prior to testing. The fabric is placed horizontally face up on white blotting paper. 2. Starting with liquid number 1, drops of approximately 5 milliliters in diameter or 0.05 microliters in volume are placed on the test sample at various points. 3. Observe the droplets for 30 seconds from an approximate 45° angle. Fabric wetting is normally detected by the darkening of the liquid-fabric interface. On black or dark fabrics, wetting can be detected by a loss of gloss within the droplet. 4. If liquid number 1 does not penetrate or wet the fabric, nor does it show absorption around the drops, drops of liquid number 2 are placed on adjacent parts of the fabric and observed for 30 seconds. 5. This procedure is continued until the fabric shows wetting under or around the test liquid drops within 30 seconds. The AATCC oil repellency rating of a sample is the number of the highest-scoring test liquid that does not wet the fabric or show absorption within 30 seconds. Dimensional changes of fabrics after domestic washing AATCC TM135-2018

[0030] Washing is preferably done in a KENMORE automatic washing machine, followed by drying in a KENMORE automatic dryer. The following wash test is used to determine the fabric's wash resistance. Normally, after washing, the fabric is subjected to the spray, water repellency, and oleophobic tests described above. 1. Test samples of 20.3 cm x 25.4 cm (8" x 10") are combined with load fabrics (pieces of hemmed cotton sheets or 50:50 fabric sheets of 91.4 cm x 91.4 cm (36" x 36")) to obtain a total dry load of 1.8 kg (4 lbs). 2. The washing machine dials are adjusted as follows: High water level Normal wash cycle, 12 minutes Wash temperature with warm water, 40.6 ºC (105 ºF); rinse with cold water The test items and simulated load are placed in the washing machine, and the machine is started. 28.3 g (one ounce) of TIDE detergent (Proctor & Gamble) is added while the washing machine fills with soft water. If the water hardness is greater than 5 ppm, CALGON water softener (Nalco) is added in the amount specified by the manufacturer to soften the water. 3. Once the wash cycle is complete, the damp garment, including the dummy load, is placed in the automatic dryer. The dryer's temperature control is set to the appropriate high temperature setting to achieve a maximum fan temperature between 68.3°C (155°F) and 71.1°C (160°F). The timer is set to "Normal Cycle" for 45 minutes. The machine is started and allowed to dry until the cycle is complete. This represents one wash cycle. 4. The garments are washed and dried again until 10 cycles are completed. Optionally, the test fabrics may be ironed with a hand iron or equivalent at a temperature between 137.8°C (280°F) and approximately 160°C (320°F) for 30 seconds per side, ironing the front side last. The fabrics are then conditioned before testing for water resistance, oil repellency, or splash resistance. In this document, water resistance, oil repellency, and splash resistance are determined without ironing the fabric after washing, unless otherwise specified. Water absorption resistance test

[0031] The following water absorption test is used to determine the water absorption resistance of a fabric or material. This test is based on NFPA 1971-2018, 8-25. In particular, the water absorption test is performed according to the test method mentioned above after the fabric or material has been subjected to five wash cycles, in accordance with NFPA 1971, 8-1.2 (or AATCC TM135-201.- 1, V, Ai).

[0032] According to the present invention, the following is the procedure used to determine the water absorption capacity of a material. 1. Three 20.3 cm x 20.3 cm (8" x 8") samples of the material to be tested are subjected to five wash cycles in accordance with NFPA 1971, 81.2. The test method in NFPA 1972, 81.2 is substantially similar to the wash test described above. However, in this test, the samples are conditioned in an atmosphere of 21.1 ± 1.1 °C (70 ± 2 °F) and 65 ± 2% relative humidity before and after washing. Furthermore, the machine settings and parameters are as follows: normal water level normal wash cycle / heavy cotton 60 washing temperature 60 ± 2.8 ºC (140 + or - 5 ºF) dryer / heavy-duty cotton drying cycle Detergent 66 + or - 1 g of standard AATCC reference detergent of 1993 65 2. Each sample is securely attached, material-coated side up, to the embroidery frames with sufficient tension to ensure a uniformly smooth surface. The frame is placed on a test stand. The material is positioned so that the direction of water flow coincides with the warp direction of the sample when placed on the stand. A funnel with a water nozzle is positioned 61 cm (24") from the center of the material. The plane of the sample surface forms a 45° angle with the horizontal. 3. Quickly pour 500 ml of water at a temperature of 26.7 ± 1.1 °C (80 ± 2 °F) into the funnel and allow it to spray onto the sample. 4. As quickly as possible, the sample is removed from the rings and placed between two sheets of blotting paper on a flat, horizontal surface. A metal roller approximately 11.4 cm (4.5") long and weighing 1 kg (2.5 lb) is quickly rolled back and forth once over the paper without applying any pressure other than that of the roller's weight. 5. A 10.2 cm x 10.2 cm (4" x 4") square is cut from the center of the sample and weighed to the nearest 0.05 grams. No more than 30 seconds should elapse between the moment the water stops flowing from the spray nozzle and the start of weighing. 6. The same 10.2 cm x 10.2 cm (4" x 4") square sample is left in a conditioning room until it dries and reaches moisture equilibrium with the surrounding atmosphere. The sample is then reweighed. 7. The water absorbed is calculated as follows: W is the weight of the wet sample and O is the weight of the dry sample. The water absorption index of the sample is the average of the results obtained from the three samples analyzed. Water repellency: Dynamic absorption test in rotating cup.

[0033] The following test also measures the resistance of materials to moisture. It is especially suitable for measuring the water-repellent effectiveness of finishes applied to fabrics, as it subjects the treated fabrics to dynamic conditions similar to those typically encountered during actual use. The test complies with AATCC TM70-2015.

[0034] According to the present invention, the following is the procedure used to determine the dynamic water absorption capacity of a material. 1. During the test, two sets of samples are tested. Each set consists of five 20.3 cm x 20.3 cm (8" x 8") pieces of the material. The threads are removed from the corners of each cut piece, and if necessary, a drop of liquid latex or rubber cement is applied to the corners to prevent fraying. Before testing, each piece of material is conditioned at a relative humidity of 65 ± 2% and 21.1 ± 1.1 °C (70 ± 2 °F) for a minimum of four hours. The blotting paper to be used later is also conditioned. 2. The five pieces in each sample set are rolled up and weighed to an accuracy of 0.1 grams. 3. Two liters of distilled water at 26.7 ± 1.1 °C (80 ± 2 °F) are poured into the beaker of a dynamic absorption meter. This meter consists of a motor-driven, 6-liter cylindrical or hexagonal beaker approximately 15.2 cm (6") in diameter and 30.5 cm (12") long, mounted to rotate continuously at 55 ± 2 rpm with a constant tangential speed. The beaker may be made of glass, corrosion-resistant metal, or chemical ceramic. 4. Both sets of samples are placed in the beaker and it is rotated in the meter for 20 minutes. 5. Immediately afterward, one piece from a sample set is passed through a roller at a speed of 2.5 cm (1 in.) per second, with the edge of the piece parallel to the rollers. The piece is placed between two sheets of unused blotting paper and passed through the roller again. The piece is then left between the damp blotting paper. This process is repeated for the remaining four pieces in the sample set. The blotting paper is removed, the five pieces are rolled up, placed in a tared plastic container or a one-gallon resealable plastic bag, and the wet sample set is weighed to the nearest 0.1 gram. The mass of the wet sample set should not exceed twice its dry mass. 6. Step number five is repeated for the second set of samples. 7. The dynamic water absorption of each set of samples is calculated with an accuracy of 0.1% using the following equation: WA= (WC) / Cx100 where WA = water absorbed, percentage W = weight of the wet sample, C = weight of the conditioned sample, g. 8. The dynamic water absorption of the material is determined by averaging the water absorbed by each of the two sets of samples. 9. According to the present invention, the dynamic water absorption capacity of the material can be determined after washing the samples, in accordance with NFPA 1971, 8-1.2. For example, the samples can be analyzed after 10 and 20 wash cycles to determine the durability of the water-resistant coating. DETAILED DESCRIPTION

[0035] Anyone with ordinary knowledge of the subject matter should understand that the present discussion is only a description of exemplary forms of embodiment and is not intended to limit the broader aspects of the present disclosure.

[0036] In general, this disclosure relates to protective garments that provide resistance to heat and flames. It also relates to a fabric that may be incorporated into a protective garment. For example, the fabric may comprise any suitable material, whether woven, knitted, or nonwoven. The fabric may also be placed anywhere suitable within a protective garment. For example, the fabric may comprise an outer layer material of the protective garment, including protective garments made from a single layer of fabric. Alternatively, the fabric may consist of a lining material for a protective garment or may consist of one or more inner layers of fabric contained within a multi-layered garment construction.

[0037] The fabric generally contains flame-resistant fibers, particularly inherently flame-resistant fibers. According to this disclosure, the fabric is treated with a durable water-repellent treatment. In one embodiment, the fabric may be impregnated with a durable water-repellent treatment. This treatment may be applied by any suitable method or technique. For example, it may be immersed in a bath containing the durable water-repellent treatment. Alternatively, it may be sprayed or printed onto the fabric.

[0038] The durable water-repellent treatment prevents the textile material from absorbing water and moisture. According to this disclosure, this treatment is free or virtually free of fluorocarbons. Although the durable water-repellent treatment described in this disclosure contains little or no fluorocarbons, fabrics treated with this treatment are exceptionally durable and able to withstand multiple wash cycles.

[0039] Various protective garments may be manufactured in accordance with this disclosure. In this document, "protective garment" refers to any article of clothing worn on the body and may include any part of a protective ensemble. Protective garments include, for example, footwear, trousers, jackets, coats, shirts, hats, gloves, and the like. The fabric may also be used to make one-piece coveralls, ideal for use in industrial settings. Protective garments manufactured in accordance with this disclosure include, for example, military garments, tactical garments, firefighter garments, industrial garments, and the like, whether multi-layered or single-layered.

[0040] Garments can be made to suit all kinds of environments and be used by people with different occupations. In one embodiment, the garment can be military, such as a combat uniform. It can also include other military garments, such as flight suits, military jackets, military parkas, etc.

[0041] In one embodiment, the fabric can be used to make a firefighter's garment. For example, Figure 1 illustrates an embodiment of a firefighter's jacket 10 made in accordance with this disclosure. The garment 10 includes a relatively tough outer layer 12 with a lining 14 inside. The outer layer 12 and the lining 14 together protect the wearer from heat and flames that may occur during firefighting activities.

[0042] In the illustrated embodiment, the lining assembly 14 is constructed as a separate unit that can be detached from the outer casing 12. A zipper 16 is included for removably attaching it to the outer casing 12. However, it should be noted that other suitable means of attachment, including more permanent attachment such as stitches, can also be used between the lining assembly 14 and the outer casing 12.

[0043] The construction of the protective garment 10 is illustrated in more detail in Figure 2. As shown, the lining assembly 14 includes several layers of padded material. The outermost layers, namely lining layers 20 and 22, are connected at their respective edges to form an inner cavity. A thermal barrier layer 24 and a moisture barrier layer 26 are located within the inner cavity, as shown. Typically, lining layer 20 will be next to the wearer's body during use, while lining layer 22 will be next to the outer layer 12.

[0044] The thermal barrier layer 24 can be made from various materials. For example, an aramid felt, such as that produced with DuPont NOMEX meta-aramid fibers, can be used. The felt acts as an insulator and inhibits heat transfer from the environment to the user.

[0045] The moisture barrier 26 is preferably a suitable polymeric membrane, impermeable to liquid water but permeable to water vapor. The moisture barrier layer 26 is designed to prevent water that comes into contact with the outer surface of garment 10 from reaching the wearer, while allowing perspiration to escape.

[0046] In the embodiment described above, the firefighter jacket 10 includes several layers. However, in other embodiments, it should be understood that a jacket or coat manufactured according to this disclosure may include a single layer or an outer layer bonded to a lining. For example, garments for forest firefighters typically have one or two layers.

[0047] Figure 3 shows a pair of trousers made according to this disclosure. The trousers 40, as shown in Figure 3, can be worn in conjunction with the protective coat 10 illustrated in Figure 1. The trousers 40 also include an outer layer 12 made of the fabric of this disclosure.

[0048] Any of the fabric layers illustrated in the figures may be treated in accordance with this disclosure. For example, outer layer 12, lining layer 20, lining layer 22, and / or thermal barrier layer 24, as shown in Figures 1 and 3, may be treated, in accordance with this disclosure, with a durable, fluorocarbon-free waterproof treatment. The fabric material may be woven or knitted and, in one embodiment, contains inherently flame-resistant fibers. For example, the fabric material may contain inherently flame-resistant fibers in an amount greater than 50% by weight, for example, greater than 60% by weight, for example, greater than 70% by weight, for example, greater than 80% by weight, for example, greater than 90% by weight, for example, greater than 95% by weight.In one embodiment, for example, the textile material is made exclusively from inherently fire-resistant fibers or contains inherently fire-resistant fibers in an amount of up to approximately 97% by weight, for example, approximately 98% by weight. The inherently fire-resistant fibers may include, for example, aramid fibers, such as para-aramid fibers and / or meta-aramid fibers. Other inherently fire-resistant fibers include polybenzimidazole (PBI) fibers or poly(p-phenylene-2,6-benzobisoxazole) fibers (PBO fibers) and the like. In one embodiment, for example, the textile material contains only aramid fibers, such as para-aramid fibers, alone or in combination with meta-aramid fibers. In another embodiment, the textile material contains only meta-aramid fibers. In yet another embodiment, the textile material contains aramid fibers in combination with PBI fibers.PBI fibers may be present in the fabric material, for example, in an amount greater than approximately 20% by weight, such as in an amount greater than approximately 25% by weight, such as in an amount greater than approximately 30% by weight, such as in an amount greater than approximately 35% by weight, such as in an amount greater than approximately 40% by weight, such as in an amount greater than approximately 45% by weight, such as in an amount greater than approximately 50% by weight, and generally in an amount less than approximately 70% by weight, such as in an amount less than approximately 60% by weight.

[0049] In addition to any of the inherently flame-resistant fibers described above, the textile material may contain other fibers. For example, it may also include fibers treated with a flame retardant, such as flame-retardant cellulose fibers, including flame-retardant viscose fibers and flame-retardant rayon fibers. Furthermore, it may include antistatic fibers, nylon fibers, and the like. For example, a textile material treated in accordance with this disclosure may contain nylon fibers in an amount of up to approximately 20% by weight. For example, nylon fibers may be present in an amount of between approximately 18% and approximately 2% by weight, or between approximately 15% and approximately 8% by weight.

[0050] The yarns used to produce the textile material may vary depending on the specific application and the desired result. In one embodiment, for example, the textile material may contain only spun yarns, only filament yarns, or both spun and filament yarns. The numerical ratio of spun to filament yarns, for example, may be from approximately 1:1 to approximately 10:1. For example, in one embodiment, the textile material may contain spun and filament yarns in a numerical ratio of approximately 2:1 to approximately 4:1. When the textile material is a woven fabric, it may have any type of weave, such as plain weave, twill weave, ripstop weave, etc.

[0051] In one embodiment, the filament yarns may be made of an inherently flame-retardant material. For example, they may be made of an aramid filament, such as a para-aramid or meta-aramid filament.

[0052] In other embodiments, the filament yarns can be made from other flame-retardant materials. For example, they can be made from poly-p-phenylenebenzobisoxazole fibers (PBO fibers) or flame-retardant cellulose fibers, such as flame-retardant viscose fibers.

[0053] Filament yarns may be combined with spun yarns. Alternatively, the textile material may be manufactured using only filament yarns or spun yarns. According to this disclosure, the spun yarns, in one embodiment, may contain polybenzimidazole fibers alone or in combination with other fibers. For example, in one embodiment, the spun yarns may contain polybenzimidazole fibers in combination with aramid fibers, such as para-aramid fibers, meta-aramid fibers, or mixtures thereof.

[0054] Instead of or in addition to containing polybenzimidazole fibers, spun yarns may contain aramid fibers as described above, modacrylic fibers, pre-oxidized carbon fibers, melamine fibers, polyamide imide fibers, polyimide fibers, or mixtures thereof.

[0055] In one particular embodiment, the spun yarns contain polybenzimidazole fibers in an amount greater than 30% by weight, for example, greater than 40% by weight. The polybenzimidazole fibers may be present in the spun yarns in an amount less than 60% by weight, for example, less than 55% by weight. The remainder of the fibers, on the other hand, may be composed of para-aramid fibers.

[0056] In one embodiment, the spun yarns may contain other fibers. When the fabric is used to manufacture firefighter coats, the spun yarns may be made exclusively of inherently flame-resistant fibers. However, when the fabric is used in other applications, they may contain other fibers. For example, the spun yarns may contain fibers treated with a flame retardant, such as flame-retardant cellulose fibers. These fibers may include flame-retardant cotton, flame-retardant rayon, flame-retardant acetate, flame-retardant triacetate, and flame-retardant lyocell, among others. The spun yarns may also contain nylon fibers, if desired, as antistatic fibers.

[0057] In one respect, the fabric treated with the waterproof treatment may comprise an outer material. The basis weight of this material may vary depending on the type of protective garment being manufactured. For example, the basis weight of the outer material is typically greater than approximately 136 g / m² (4 ounces per square yard), greater than approximately 170 g / m² (5 ounces per square yard), greater than approximately 186 g / m² (5.5 ounces per square yard), greater than approximately 203 g / m² (6 ounces per square yard), and generally less than approximately 288 g / m² (8.5 ounces per square yard), less than approximately 271 g / m² (8 ounces per square yard), less than approximately 254 g / m² (7.5 ounces per square yard).

[0058] In another respect, the textile material treated in accordance with this disclosure is a lining fabric. This fabric, for example, may be placed next to the wearer's body during use. The lining fabric may be made from a combination of spun yarns and filament yarns, as described above. The filament yarns may be larger than approximately 111 dtex (100 denier), for example, larger than approximately 222 dtex (200 denier), and smaller than approximately 555 dtex (500 denier), for example, smaller than approximately 444 dtex (400 denier). To increase the lubricity of the lining fabric, the spun yarns and filament yarns may be woven together such that the filament yarns comprise more than 50% of the surface area of ​​one side of the fabric. For example, filament yarns may comprise more than 60%, such as more than 70%, or more than 80% of one side of the fabric.The side of the fabric with more exposed filament yarns is used as the lining side of the garment. The filament yarns give the fabric high lubricity, which makes it easier to position. For example, lining fabric can be woven with a cross weave, such as a 2x1 or 3x1 weave. Lining fabric can have a basis weight of less than 170 g / m² (5 ounces per square yard), less than 136 g / m² (4 ounces per square yard), and generally greater than 85 g / m² (2.5 ounces per square yard), or greater than 102 g / m² (3 ounces per square yard).

[0059] In another respect, the textile material treated in accordance with this disclosure is barrier layer 24, as shown in Figure 2. Barrier layer 24, for example, may be composed of a filling material, such as felt. Once treated, layer 24 may have the same characteristics described above regarding spray resistance and water absorption.

[0060] According to this disclosure, the textile material is treated with a durable water-repellent treatment. This durable water-repellent treatment is free or practically free of fluorocarbons. The term "practically free," as used herein, indicates that the fabric contains fluorocarbons in an amount less than approximately 0.1% by weight. In one embodiment, the durable water-repellent treatment is free or practically free of perfluorinated carboxylic acids, such as perfluorooctanoic acid. For example, perfluorooctanoic acid or any perfluorinated carboxylic acid may be present in the durable water-repellent treatment or in a treated fabric in an amount less than approximately 0.1% by weight.

[0061] In another embodiment, the durable water-repellent treatment may be free or virtually free of polyfluoroalkyl compounds, including C6 compounds. For example, the durable water-repellent treatment and / or the treated fabric may contain one or more polyfluoroalkyl compounds in an amount less than approximately 0.1% by weight.

[0062] It was unexpectedly discovered that the durable water-resistant treatment of the present disclosure withstood multiple wash cycles and still provided the desired water-resistant properties.

[0063] It was also unexpectedly discovered that the durable water-resistant treatment of the present disclosure is resistant to hydrocarbon compounds, such as liquids, gels, and solids. For example, upon contact with a hydrocarbon compound, such as a polycyclic aromatic hydrocarbon like benzene, it will wash away from the fabric. This result is completely surprising and unexpected.

[0064] According to this disclosure, the durable water-repellent treatment contains a binder and extender combined with other ingredients and components. For example, the durable water-repellent treatment may also include a softener, a repellent agent, or both.

[0065] The binder for the durable water-repellent treatment comprises a polyurethane polymer. A special advantage is that this polymer can be water-based and can therefore be applied to the fabric in aqueous dispersion. In one embodiment, the polyurethane polymer is an anionic polyurethane. The polyurethane polymer can also be an aliphatic polyurethane. In a particular embodiment, the polyurethane polymer comprising the binder is a polyester / ether polyurethane polymer, such as an aliphatic polyester / ether polyurethane polymer.

[0066] The aforementioned binder is combined with an extender. This extender may also comprise a polyurethane polymer. Therefore, in one embodiment, the durable water-resistance treatment includes said polyurethane, according to claim 1, as a first polyurethane polymer combined with a second polyurethane polymer. The extender, for example, may comprise a modified polyurethane polymer. The extender is a blocked isocyanate, such as an oxime-blocked isocyanate. The extender may be cationic or nonionic. The extender further enhances water and oil resistance.

[0067] In addition to a binder and an extender, in one embodiment, the durable water-repellent treatment may include a softener. This softener, for example, may comprise an emulsion of a polyalkylene polymer. The softener is generally nonionic. In one embodiment, the softener is a polyethylene polymer, such as a low-molecular-weight polyethylene polymer.

[0068] In one embodiment, the durable waterproofing treatment may also contain a repellent agent. This agent may include an acrylic polymer alone or in combination with a wax, such as paraffin. In another embodiment, the repellent agent may include a polyacrylate that also acts as a binder.

[0069] Each of the above ingredients can be combined with water and, optionally, a wetting agent, such as isopropyl alcohol, for application to a fabric. The relative amounts of each component may vary depending on the formulation. In one embodiment, for example, the binder or first polyurethane polymer may be present relative to the extender or second polyurethane polymer in a weight ratio of approximately 5:1 to approximately 1:2, or, for example, in a weight ratio of approximately 4:1 to 1:1. In another embodiment, the binder or first polyurethane polymer and the extender or second polyurethane polymer are present in a weight ratio of approximately 3:1 to approximately 1.5:1, based on the dry weight of the finish. The repellent agent may be present in greater amounts than the binder (or first polyurethane polymer) or the extender (or second polyurethane polymer).For example, the weight ratio (based on the dry weight of the finish) between the binder (or first polyurethane polymer) or extender (or second polyurethane polymer) and the repellent agent can be from approximately 3:1 to approximately 1:8, such as from approximately 1:1 to approximately 1:5, such as from approximately 1:1.5 to approximately 1:3.

[0070] When included in the formulation, the softener may generally be present in smaller quantities than the binder (or first polyurethane polymer), the repellent, or the extender (or second first polyurethane polymer). For example, in one embodiment, the softener may be present relative to the binder or first polyurethane polymer in a weight ratio of approximately 1:1 to approximately 1:4, for example, from approximately 1:1.5 to approximately 1:3.

[0071] To produce a liquid-resistant fabric according to the present invention, a knitted or woven fabric suitable for use in protective garments is first constructed or obtained. As described above, the fabric must be made of flame-resistant fibers.

[0072] Before applying the durable waterproof treatment, the fabric can be degreased, although this may not be necessary in all applications. Once degreased, the material can be cleaned with an alkaline solution.

[0073] After scouring, the fabric is placed on a tensioning frame, dried, and heat-set. For example, after scouring, the fabric must be dried so that its moisture level is practically equivalent to the natural moisture level of the fibers used in its manufacture. For example, for most fibers, the moisture level must be less than 10%, and in particular, less than 7%.

[0074] After drying and heat-setting the fabric, a durable water-resistant composition, as described herein, is applied to at least one of its sides. While the composition may be sprayed or printed onto the fabric, preferably the fabric is immersed in a bath containing the durable water-resistant treatment in dispersion form.

[0075] The amount of water-resistant composition applied to the fabric will depend on the particular formulation and application.

[0076] After applying the durable water-repellent treatment to the fabric, it is heated to a temperature sufficient for the coating to dry or cure. Once the durable water-repellent treatment has cured and set, it can be used to make protective garments in accordance with this disclosure.

[0077] In one aspect, the dry finish may contain the binder or first polyurethane polymer in an amount greater than 10% by weight, for example, 15% or 20% by weight, and generally in an amount less than 50% by weight, for example, 40% or 30% by weight. The extender or second polyurethane polymer may be present in the dry finish in an amount greater than 5% by weight, for example, 8% or 10% by weight, and generally in an amount less than 30% by weight, for example, 25% or 20% by weight. The repellent agent may be present in the dry durable water-resistant treatment in an amount greater than 10% by weight, for example, 20% by weight, 25% by weight, 35% by weight, and generally in an amount less than 70% by weight, 65% by weight, or 55% by weight.If a fabric softener is used, it may be present in the dry treatment in an amount greater than 5% by weight, for example, 10% by weight, and generally in an amount less than 25% by weight, 20% by weight or 15% by weight, with respect to the weight of the dry water-resistant treatment.

[0078] Although the durable water-resistant treatment does not contain fluorocarbon chemicals, it was unexpectedly found that the treatment described in this disclosure has excellent water resistance. The durable water-resistant treatment is also able to withstand multiple wash cycles.

[0079] For example, textile materials treated in accordance with this disclosure may have a spray resistance of at least 70 or higher, such as at least 80 or higher, or at least 90 or higher, even after ten wash cycles. In one embodiment, for example, the fabric may maintain a spray resistance of 100 after ten wash cycles.

[0080] Similarly, the textile material also exhibits excellent resistance to water absorption. For example, according to the water absorption test (NFPA 19718.25), the fabric can have a water absorption of approximately 15%, as well as approximately 10%, as well as approximately 5%, as well as approximately 4%, as well as approximately 3%, as well as approximately 2%, as well as approximately 1% or less.

[0081] The above-mentioned water absorption properties can be retained in the fabric after five wash cycles or even after ten wash cycles.

[0082] In addition to water, the textile material treated according to this disclosure also provides protection against various chemical agents, such as acids, alkalis, and artificial blood, according to EN ISO 6530. For example, when tested against a 30% sulfuric acid solution, textile materials manufactured according to this disclosure may exhibit a repellency index greater than 85%, greater than 90%, greater than 92%, or greater than 94%. The textile material may exhibit a penetration index, when tested against a 30% sulfuric acid solution, of less than 5%, less than 2%, less than 1%, or less than 0.5%. When the textile material is incorporated into a composite, such as a three-layer composite, the penetration index may be 0%.

[0083] When tested with a 10% sodium hydroxide solution, textile materials manufactured according to this disclosure may exhibit a repellency index greater than 90%, for example, greater than 92%, for example, greater than 94%, for example, greater than 96%, for example, greater than 97%. The textile materials may exhibit a penetration index less than 2%, for example, less than 1.5%, for example, less than 1%, for example, less than 0.8%.

[0084] Textile materials manufactured according to this disclosure also exhibit excellent resistance to artificial blood. For example, when tested with artificial blood, they may show a repellency index greater than 85%, for example, greater than 87%, for example, greater than 90%, for example, greater than 92%, for example, greater than 94%. The textile materials may show an artificial blood penetration index of less than 4%, for example, less than 1.5%, for example, less than 1%, for example, less than 0.8%.

[0085] Textile materials manufactured in accordance with this disclosure may also exhibit excellent abrasion resistance. For example, a fabric with a basis weight between 170 g / m² (5 osy) and 305 g / m² (9 osy), for example, between 186 g / m² (5.5 osy) and 288 g / m² (8.5 osy), for example, between 203 g / m² (6 osy) and 254 g / m² (7.5 osy), may exhibit abrasion resistance exceeding 90,000 cycles, for example, exceeding 95,000 cycles, for example, exceeding 98,000 cycles, for example, exceeding 100,000 cycles, according to ASTM D4966 test method. Abrasion resistance is generally less than 150,000 cycles.

[0086] When testing lighter fabrics, such as linear materials, textile materials manufactured according to this disclosure may have an abrasion resistance of approximately 40,000 cycles, for example, approximately 42,000 cycles, approximately 44,000 cycles, approximately 46,000 cycles, approximately 48,000 cycles, and generally approximately 80,000 cycles. Lighter textile materials, for example, may have a basis weight of approximately 68 g / m² (2 osy) to approximately 179 g / m² (5 osy), approximately 68 g / m² (2 osy) to approximately 136 g / m² (4 osy), approximately 85 g / m² (2.5 osy) to approximately 129 g / m² (3.8 osy).

[0087] As described above, the durable water-repellent treatment of this disclosure may be water-based. For example, it may comprise an aqueous dispersion of the different ingredients or components. Furthermore, it is virtually free of fluorocarbons. Therefore, it is exceptionally safe to handle and use. In this respect, it can be applied to protective garments during their service life to further enhance their water-repellent properties. For example, in one embodiment, the durable water-repellent treatment can be added to a wash cycle for absorption by the garment. Subsequently, the garment can be placed in a dryer, which cures the treatment and further enhances its water-repellent properties. The fabric or fabric layers treated according to this disclosure may be fluorine-free or virtually fluorine-free.For example, the fabric or fabric layer treated in accordance with this disclosure may contain fluorine in an amount less than approximately 1000 ppm, such as in an amount less than approximately 500 ppm, such as in an amount less than approximately 100 ppm, such as in an amount less than approximately 50 ppm, such as in an amount less than approximately 40 ppm, such as in an amount less than approximately 30 ppm, such as in an amount less than approximately 20 ppm.

[0088] This disclosure will be better understood with reference to the following examples. Example No. 1

[0089] The following tests were performed in order to demonstrate some of the advantages and benefits of the treated tissues in accordance with this disclosure.

[0090] Three different fire-resistant fabrics suitable for use as outer layer material were impregnated with a durable water-resistant treatment in accordance with this disclosure and compared to the same fabric treated with a water-resistant treatment containing fluorocarbon chemicals.

[0091] The fabrics that were tested were the following: Fabric No. 1: Made from para-aramid filament yarns combined with spun yarns. The spun yarns contained an intimate blend of aramid polymer fibers and PBI fibers. The ratio of spun yarn to filament yarn was 2:1 and the fabric had a basis weight of 203 g / m2 (6 osy). Fabric No. 2: Made from para-aramid filament yarns combined with spun yarns. The spun yarns contained an intimate blend of aramid polymer fibers and PBI fibers. The ratio of spun yarn to filament yarn was 3:1 and the fabric had a basis weight of 203 g / m2 (6 osy). Fabric No. 3: Made from para-aramid filament yarns combined with spun yarns. The spun yarns contained an intimate blend of aramid polymer fibers and PBI fibers. The ratio of spun yarn to filament yarn was 4:1 and the fabric had a basis weight of 220 g / m² (6.5 oz).

[0092] Each of the fabrics mentioned was scoured and heat-set. A durable water-repellent treatment was applied by immersing them in said treatment and then drying them.

[0093] The following durable and water-resistant treatments were tested:

[0094] The previously treated fabrics were subjected to spray resistance testing according to AATCC TM22-2017 and water absorption testing according to NFPA 1971:20188.25, initially and after multiple wash cycles. The following results were obtained: Spray resistance

[0095] Water absorption (%)

[0096]

[0097] As shown above, fabrics treated in accordance with this disclosure exhibited excellent water repellency properties, even when compared to fabrics treated with a fluorocarbon. Example No. 2

[0098] In the following example, several fire-resistant fabrics were treated in accordance with this disclosure and tested for fluorine content compared to several commercial fabrics treated with a water-resistant treatment containing fluorocarbon chemicals.

[0099] The fabrics analyzed were the following: Samples C1 and C2: Manufactured with para-aramid filament yarns combined with spun yarns. The spun yarns contained an intimate blend of aramid polymer fibers and PBI fibers. The ratio of spun yarn to filament was 2:1 and the fabric had a basis weight of 203 g / m² (6 osy).

[0100] Samples No. C3, C4, 8, 9 and 10: Made from para-aramid filament yarns combined with spun yarns. The spun yarns contained meta-aramid polymer fibers. The ratio of spun yarns to filaments was 1:4 and the fabric had a basis weight of 220 g / m² (6.5 osy).

[0101] Samples No. 5, 6, and 7: Manufactured from para-aramid filament yarns combined with spun yarns. The spun yarns contained an intimate blend of aramid polymer fibers and PBI fibers. The ratio of spun yarn to filament was 2:1, and the fabric had a basis weight of 237 g / m² (7 osy).

[0102] Sample No. 11: Manufactured with 100% meta-aramid warp and weft yarns, with 80% meta-aramid fibers combined with 20% by weight of flame-retardant viscose fibers. The fabric is woven so that the face contains 93% meta-aramid fibers and 7% flame-retardant viscose fibers. The face of the fabric was analyzed for the sample.

[0103] Sample No. 12: Made with 100% meta-aramid warp and weft yarns, with 80% meta-aramid fibers combined with 20% by weight of flame-retardant viscose fibers. The reverse of the fabric contained 87% by weight of meta-aramid fibers and 13% by weight of flame-retardant viscose fibers. The reverse of the fabric was analyzed for the sample.

[0104] Samples C1, C2, C3 and C4 were commercial products treated with a water-resistant treatment containing fluorocarbon chemicals.

[0105] Samples No. 5-12 were treated with the same durable water-resistant treatment described in Example No. 1 above for Sample No. 2. The durable water-resistant treatment was substantially free of fluorocarbon chemicals.

[0106] The fluorine content in the resulting tissue was analyzed by particle-induced gamma emission (PIGE). PIGE is a type of nuclear reaction analysis that uses an ion beam with thin-film analytical techniques. A MeV proton beam is projected onto a sample, and the protons excite the target nuclei, emitting gamma rays that can produce a spectrum to determine the fluorine content.

[0107] The following results were obtained:

[0108] As shown above, fabrics manufactured according to this disclosure are virtually fluorine-free and contain fluorine in an amount less than 100 ppm. Example No. 3

[0109] In the following example, fabrics treated in accordance with this disclosure and an untreated fabric were tested for chemical resistance according to the EN ISO 6530 test. In particular, the fabrics were treated against a 30% sulfuric acid solution, a 10% sodium hydroxide solution, and artificial blood.

[0110] Three different fabrics were tested, as follows: Sample No. 13 was an untreated fabric. The fabric was made from para-aramid filament yarns combined with spun yarns. The latter contained an intimate mixture of aramid fibers. The ratio of spun yarns to filaments was 1:1. The fabric had a basis weight of 220 g / m² (6.5 osy).

[0111] Sample No. 14 was made from the same fabric as described with respect to Sample No. 13, only treated in accordance with this disclosure as described in Example No. 1 above.

[0112] Sample No. 15 was also treated in accordance with this disclosure and contained a fabric made from para-aramid filament yarns combined with spun yarns. The spun yarns contained an intimate mixture of aramid polymer fibers and PBI fibers. The ratio of spun yarn to filament was 2:1 and the fabric had a basis weight of 237 g / m² (7 osy).

[0113] Sample No. 16 contained the treated fabric from Sample No. 14, incorporated into a three-layer composite. This composite also included a face cloth and a moisture barrier placed between the face cloth and the treated fabric.

[0114] The repellency, absorption, and penetration indices of each fabric were analyzed. The following results were obtained: Example #4.

[0115] In this example, a coating material or a linear thermal material was treated in accordance with this disclosure and various properties were analyzed. An untreated sample was also analyzed.

[0116] Sample No. 17 in the table below was an untreated linear thermoplastic. This linear thermoplastic was made from meta-aramid fibers.

[0117] Sample No. 18 in the table below was made from the same fabric as sample No. 17, but was treated with the composition described in example No. 1.

[0118] The following results were obtained: Example No. 5

[0119] The following example demonstrates the ability of the fabric treatment in accordance with this disclosure to increase abrasion resistance.

[0120] In particular, the abrasion resistance of fabric samples No. 13 and 14, as well as samples No. 17 and 18, was evaluated according to ASTM D4966 test method. Samples No. 13 and 14 correspond to outer layer fabrics, while samples No. 17 and 18 correspond to inner lining fabrics. The following results were obtained:

[0121] These and other modifications and variations of the present invention may be implemented by those skilled in the art, without departing from the scope of the present invention, as set forth in the appended claims. Furthermore, it should be understood that aspects of the various embodiments may be interchangeable, in whole or in part. Likewise, those skilled in the art will understand that the foregoing description is by way of example only and is not intended to limit the invention described in more detail in the appended claims.

Claims

1. A protective garment comprising: a fabric material constituting at least a part of the protective garment, composed of inherently fire-resistant fibers, treated with a durable water-repellent treatment, said durable water-repellent treatment containing a polyurethane polymer, a blocked isocyanate as an extender, an acrylic polymer and, optionally, a wax, as well as, optionally, a softener, the durable water-repellent treatment being practically free of fluorocarbons, such that the fabric contains fluorocarbon chemicals in an amount of less than approximately 0.1% by weight, the durable water-repellent treatment being incorporated into the fabric such that it maintains a spray resistance of at least 70 after ten wash cycles. 2.A protective garment as defined in claim 1, wherein the fabric material maintains a sprayability index of at least 80, preferably 90, after ten wash cycles.

3. A protective garment as defined in claim 1 or 2, wherein the fabric material maintains a water absorption of less than approximately 15% after five wash cycles, preferably less than approximately 10% after ten wash cycles, and / or wherein the fabric material exhibits a water absorption of less than 5% when tested in accordance with NFPA 19718.

25.

4. A protective garment as defined in any of the preceding claims, wherein the polyurethane polymer comprises an aliphatic polyester / ether polyurethane polymer.

5. A protective garment as defined in any of the preceding claims, wherein the softener comprises a polyalkylene, such as a nonionic polyethylene polymer. 6.A protective garment as defined in any of the preceding claims, wherein the wax comprises a paraffin wax.

7. A protective garment as defined in any of claims 4 to 7, wherein the polyurethane polymer is a first polyurethane polymer and wherein the durable water-resistant treatment further contains a second polyurethane polymer.

8. A protective garment as defined in any of the preceding claims, wherein the first polyurethane polymer is present relative to the second polyurethane polymer in a weight ratio of between approximately 5:1 and approximately 1:2, such as in a weight ratio of between approximately 3:1 and approximately 1.5:

1.

9. A protective garment as defined in any of the preceding claims, wherein the fabric material comprises more than approximately 50% by weight of inherently flame-resistant fibers. 10.A protective garment as defined in any of the preceding claims, wherein the inherently fire-resistant fibers contained in the fabric material comprise: - para-aramid fibers, meta-aramid fibers, or mixtures thereof, and / or - polybenzimidazole fibers or poly(p-phenylene-2,6-benzobisoxazole) fibers, and / or - a mixture of aramid fibers and polybenzimidazole fibers.

11. A protective garment as defined in any of the preceding claims, wherein the fabric material comprises: - spun yarns and multifilament yarns, or - spun yarns only, or - multifilament yarns only, and wherein preferably: - the fabric material comprises an inner lining, and / or - the protective garment comprises a hood, footwear, or glove, and / or - the protective garment is a single-layer fabric garment, said layer being the fabric material. 12.A protective garment as defined in any of the preceding claims, wherein the fabric material contains fluorine in an amount of less than approximately 1,000 ppm, preferably less than approximately 500 ppm, such as less than approximately 100 ppm.

13. A protective garment as defined in any of the preceding claims, wherein the fabric material forms an outer surface of the protective garment and comprises an outer layer material. 14.A protective garment according to any of the preceding claims, wherein the textile material, when tested according to EN ISO 6530, exhibits a repellency index against a 30% sulfuric acid solution greater than 85% and a penetration index of less than 1%, a repellency index against a 10% saline hydroxide solution greater than 90% and a penetration index of less than 1%, and a repellency index against artificial blood greater than approximately 85% and a penetration index of less than approximately 1.5%.

15. A protective garment, as defined in any of the preceding claims, wherein the fabric has a basis weight of between approximately 170 g / m² (5 osy) and approximately 288 g / m² (8.5 osy) and exhibits an abrasion resistance greater than 90.000 cycles according to the ASTM D4966 test method; or in which the fabric has a basis weight of between approximately 68 g / m² (2 osy) and approximately 136 g / m² (4 osy) and exhibits an abrasion resistance greater than 40,000 cycles according to the ASTM D4966 test method.

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