Protective fabric displaying water, oil and fuel repellency

Abstract

Protective garments are disclosed having a fabric material treated with a durable water resistant treatment. In accordance with the present disclosure, the durable water resistant treatment contains primarily non-fluorinated chemistries or components in combination with a very minor amount of a fluorocarbon compound. The resulting treated fabric not only displays excellent water resistance but is also resistant to many chemicals including fuels and oils.

Description

BACKGROUND

[0001] Various different types of protective garments exist that are intended to provide protection to the wearer. In certain embodiments, for instance, the protective garments are designed to provide protection from liquids, such as water and / or oil. Such protective garments, for instance, are typically worn by first responders, medical personnel, public service providers, and military personnel.

[0002] Notably, the absorbing and retaining of moisture and / or oil may result in detrimental effects to both the garment and the wearer. For instance, if the garment retains moisture, the protective garment can become significantly heavier and / or affect the thermal properties of the garment making the garment less effective in shielding its wearer from thermal heat. Additionally, for instance, if the garment absorbs and / or retains oil, the protective garment may have reduced breathability, reduced chemical resistance, and / or may be subject to staining. Thus, water repellency and oil repellency are important considerations in garment and fabric material treatments.

[0003] In the past, treatments utilized to provide water repellency and / or oil repellency have contained fluorocarbon chemicals. In general, fluorocarbon chemicals are durable and provide for adequate water resistance and oil resistance. Recently, however, various manufacturers, including fabric makers, have been placed under increased pressure to reduce the amount of fluorocarbons incorporated into products. For instance, the manufacture and handling of fluorocarbons has been subject to greater scrutiny and governmental regulation.

[0004] Thus, a need currently exists for a treatment for fabrics that not only provides water resistance but is also resistant to oils, fuels, and the like. In particular, a need exists for a treatment for fabrics that provides resistance to all different types of liquids and contains a reduced level of fluorocarbon chemistries. Further, a need exists for fire resistant fabrics that are capable of accepting a fabric treatment as described above.SUMMARY

[0005] In general, the present disclosure is directed to a fabric material that is not only water resistant but is also resistant to oils, fuels, and the like. In one aspect, the fabric material can also be fire resistant. In this regard, the present disclosure is also directed to protective garments made from the fabric. The present disclosure is further directed to a fabric treatment containing reduced fluorine levels that, once applied to a fabric, makes the fabric water and chemical resistant.

[0006] In one aspect, for instance, the present disclosure is directed to a fabric for producing protective garments. The fabric comprises a fabric material containing inherently flame resistant fibers. The inherently flame resistant fibers can comprise para-aramid fibers, meta-aramid fibers, modacrylic fibers, polybenzimidazole fibers, polybenzoxazole fibers, metacrylic fibers, wool fibers, or mixtures thereof. The inherently flame resistant fibers can comprise greater than about 50% by weight, such as greater than about 60% by weight, such as greater than about 70% by weight, such as greater than about 80% by weight, such as greater than about 90% by weight, such as greater than about 95% by weight of the fabric material. The fabric material further comprises a durable water resistant treatment. The durable water resistant treatment comprises a non-fluorinated binder in combination with a fluorocarbon compound.

[0007] In accordance with the present disclosure, the treated fabric material of the present disclosure contains fluorine in reduced amounts while still displaying excellent water and fuel resistance. For instance, the treated fabric material can contain fluorine in an amount less than about 3,500 ppm, such as in an amount less than about 3,300 ppm, such as in an amount less than about 3,000 ppm, such as in an amount less than about 2,800 ppm, such as in an amount less than about 2,500 ppm, such as in an amount less than about 2,300 ppm, such as in an amount less than about 2,200 ppm, such as in an amount less than about 2,000 ppm, such as in an amount less than about 900 ppm, such as in an amount less than about 700 ppm. The resulting fabric material, for instance, can contain fluorine in an amount greater than about 100 ppm, such as in an amount greater than about 150 ppm, such as in an amount greater than about 200 ppm, such as in an amount greater than about 250 ppm, such as in an amount greater than about 300 ppm.

[0008] In one aspect, the fluorocarbon compound incorporated into the durable water resistant treatment comprises a fluoropolymer or oligomer containing relatively short carbon chains. For instance, in one aspect, the durable water resistant treatment and the fabric material can be free of any C8 or longer chain perfluoroalkyl and polyfluoroalkyl substances such as perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorooctane sulfonate (PFOS), and long chain fluorotelomer alcohols within the chemistry (8:2 FTOH) and / or does not contain an alkylphenol ethoxylate.

[0009] The fabric material of the present disclosure can display excellent water resistance in combination with oil and fuel resistance. For instance, the fabric material can maintain a water absorption of less than about 10%, such as less than about 8%, such as less than about 6%, such as less than about 4% after 10 laundry cycles. The fabric material can also maintain a spray rating of at least 70, such as at least 80, such as at least 90 after 10 laundry cycles. In addition, when tested according to ISO Test 6530 against O-xylene, the fabric material can display an index of repellency of greater than about 80%, such as greater than about 85%, such as greater than about 87%, and can display an index of repellency after 10 laundry cycles of greater than about 80%, such as greater than about 82%. The fabric material can display an index of penetration against O-xylene of less than about 10%, such as less than about 5%, and after 10 laundry cycles, of less than about 10%, such as less than about 6%. The fabric material can display an index of absorption against O-xylene of less than about 10%, such as less than about 9%, such as less than about 8%. After 10 laundry cycles, the fabric material can display an index of absorption of less than about 20%, such as less than about 15%.

[0010] When tested against hydraulic fluid according to ISO Test 6530, the fabric material can display an index of repellency initially and after 10 laundry cycles of greater than about 80%, such as greater than about 85%, such as greater than about 87%, can display an index of penetration initially and after 10 laundry cycles of less than about 3%, such as less than about 2%, and can display an index of absorption initially and after 10 laundry cycles of less than about 10%, such as less than about 8%.

[0011] When tested against 30% sulfuric acid according to ISO Test 6530, the fabric material can display an index of repellency initially and after 10 laundry cycles of greater than about 95%, such as greater than about 96%, such as greater than about 97%, can display an index of penetration initially and after 10 laundry cycles of less than about 2%, such as less than about 1%, and can display an index of absorption initially and after 10 laundry cycles of less than about 1%, such as less than about 0.8%.

[0012] In one aspect, the fluorocarbon compound contained in the durable water resistant treatment comprises a smaller chain fluorocarbon polymer or oligomer. For instance, the carbon chain length of the fluorocarbon compound can be a C2 to a C6 chain length, such as a C6 chain length. In one aspect, the fluorocarbon compound comprises a fluoroalkyl acrylate.

[0013] The non-fluorinated binder contained in the durable water resistant treatment can comprise an acrylic polymer, a polyurethane polymer, a silicone polymer, or mixtures thereof. The durable water resistant treatment can also contain various other components. For instance, the durable water resistant treatment can contain a wax, such as a paraffin and / or a polyethylene wax. The durable water resistant treatment can also contain a repelling agent which may comprise an acrylic polymer. In one embodiment, for instance, the durable water resistant treatment contains a non-fluorinated binder comprising an acrylic polymer, a polyurethane polymer, a silicone polymer, or mixtures thereof in combination with an acrylic polymer repelling agent and a wax, such as a paraffin. The durable water resistant treatment can also contain a latent crosslinking agent, such as a blocked isocyanate.

[0014] As described above, the fabric material can contain inherently flame resistant fibers. The fabric material can comprise a woven fabric that contains only spun yarns or spun yarns in combination with multifilament yarns. In one aspect, the fabric material contains spun yarns comprised of aramid fibers blended with PBI fibers and filament yarns comprised of aramid fibers, such as para-aramid or meta-aramid filaments or stretched broken filaments. The spun yarns and the multifilament yarns can both extend in the warp direction and the weft direction and can be present in the fabric material, for instance, at a ratio of from about 1 spun yarn to 1 multifilament yarn to about 8 spun yarns to about 1 multifilament yarn. In one particular application, the spun yarns contain PBI fibers in an amount greater than about 20% by weight, such as in an amount greater than about 30% by weight, and in an amount less than about 100% by weight, such as in an amount less than about 60% by weight.

[0015] In one aspect, the fabric material can have a basis weight of from about 5 osy to about 8.5 osy. In one aspect, for instance, the basis weight can be from about 5 osy to about 6.8 osy. In an alternative embodiment, the basis weight can be from about 6.8 osy to about 8.5 osy.

[0016] The present disclosure is also directed to a protective garment made from the fabric material as described above. For instance, the protective garment can comprise a fireman turnout coat and the fabric material can form an exterior surface of the protective garment. For instance, the fabric material can comprise the outer shell material of the garment. Alternatively, the protective garment can comprise an inner lining, a hood, footwear, or a glove. The fabric material can comprise a single layer of fabric or can comprise a multi-layer fabric.

[0017] Other features and aspects of the present disclosure are discussed in greater detail below.BRIEF DESCRIPTION OF THE DRAWINGS

[0018] 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 the present disclosure; Figure 2 is a cross-sectional view of an inner liner incorporated into the garment illustrated in Figure 1; Figures 3A-3F are diagrammatical views of illustrative examples of spray ratings 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 the present disclosure.

[0019] Repeat use of reference characters in the present specification and drawings is intended to represent the same or analogous features or elements of the present invention.Definitions and Standardized Procedures

[0020] The following definitions and procedures are offered in order to better describe and quantify the performance of protective garments and fabrics made according to the present invention in comparison to prior art constructions.Water Repellency: Spray Test AATCC TM22-2017

[0021] As used herein, a fabric spray rating refers to a rating a fabric or a material receives according to AATCC TM22-2017. In general, a spray test measures the resistance of a material to wetting by water.

[0022] According to the present invention, the following is the procedure used to determine the spray rating of a material. 1. A 7"x7" sample of the material to be tested is first conditioned at 65 ± 2% relative humidity and at 70 ± 2 °F for a minimum of four hours prior to testing. 2. The fabric sample is fastened securely on a 6" metal hoop so that the fabric is wrinkle free. The hoop is supported on a tester's stand so that the fabric is facing up. Twills, gabardines, piques or similar fabrics of ribbed construction are positioned on the stand so that the ribs are diagonal to the flow of water running off the fabric. A funnel attached to a nozzle for holding water is placed 6" above the center of the fabric. 3. 250 milliliters of water at 80 ± 2 °F are poured from a cup or other container into the funnel, allowing the water to spray onto the fabric. 4. Once the water has run through the funnel, one edge of the hoop is held and the opposite edge is firmly rapped once against a solid object with the fabric facing the object. The hoop is then rotated 180° and it is rapped once more at the point previously held. 5. The wetted or spotted fabric sample is then compared with the standards shown in FIGS. 3A-3F. The fabric is assigned a spray rating that corresponds to the nearest standard. As shown on FIGS. 3A-3F, the fabric can be rated from 0 to 100 wherein 0 indicates that the entire fabric is wetted with the water, while a rating of 100 indicates that none of the fabric was wetted by the water. Water Absorption Resistance Test

[0023] The following water absorption test is for determining the resistance to water absorption of a fabric or material. The test is based upon NFPA 1971-2018, 8-25. In particular, the water absorption test is conducted according to the above-identified test method after the fabric or material has been subjected to five laundry cycles in accordance with NFPA 1971, 8-1.2 (or AATCC TM135-2018 - 1, V, Ai).

[0024] According to the present invention, the following is the procedure used to determine the water absorption rating of a material. 1. Three 8"x8" samples of the material to be tested are subjected to five laundry cycles in accordance with NFPA 1971, 8-1.2. Test method NFPA 1972, 8-1.2 is substantially similar to the laundering test described above. In this test, however, the specimens are conditioned in an atmosphere of 70 ± 2 °F and 65 ± 2% relative humidity before and after being washed. Further, the machine settings and parameters are as follows: water levelnormalwash cyclenormal / cotton sturdywash temperature140 ± 5 °Fdrying cycletumble / cotton sturdydetergent66 ± 1 g of 1993 AATCC standard Reference Detergent 2. Each sample is securely mounted, with the coated side of the material up, to embroidery hoops with sufficient tension to ensure a uniformly smooth surface. The hoop is supported on a tester's stand. The material is positioned so that the direction of the flow of water down the sample shall coincide with the warpwise direction of the sample as placed on the stand. A funnel attached to a nozzle for holding water is placed 24" above the center of the material. The plane of the surface of the sample is placed at a 45° angle with the horizontal. 3. 500 ml of water at a temperature of 80 ± 2 °F are poured quickly into the funnel and allowed to spray onto the specimen. 4. As rapidly as possible, the sample is removed from the hoops and placed between two sheets of blotting paper on a flat horizontal surface. A metal roller approximately 41 / 2" long and weighing 21 / 4 pounds is rolled quickly forward and back one time over the paper without application of any pressure other than the weight of the roller. 5. A square having dimensions of 4"x4" is cut out of the center of the sample and weighed to the nearest 0.05 grams. Not more than 30 seconds shall elapse between the time the water has ceased flowing through the spray nozzle and the start of the weighing. 6. The same 4"x4" square sample is then left in a conditioning room until it has dried and reached moisture equilibrium with the surrounding atmosphere. The sample is then weighed again. 7. The water absorbed shall be calculated as follows:waterabsorption,percent=W−OO×100 herein W is the weight of the wet sample and O is the weight of the dried sample. The water absorption rating of the sample is the average of the results obtained from the three specimens tested.Resistance of Fabrics to Penetration by Liquid

[0025] The resistance of fabrics to penetration by hydraulic fluid, a 30% sulfuric acid solution, and O-xylene (simulation of diesel fuel) is conducted according to EN Test 469 / ISO Test 6530.Water Penetration Test / Water Absorption Resistance Test

[0026] This test method shall apply to the protective garment outer shell and collar lining materials.Sample Preparation:

[0027] Samples for conditioning shall be at least 1 m (1.1 yd) square of each material.

[0028] Specimens except CBRN garment and material specimens shall be conditioned as specified in 8.1.9 followed by conditioning as specified in 8.1.2 of NFPA 1951.Specimens:

[0029] Specimens shall be 200 mm × 200 mm (8 in. x 8 in.).

[0030] At least 3 specimens shall be tested.Apparatus:

[0031] The test apparatus is as specified in AATCC 42, Water Resistance: Impact Penetration Test, with the following modifications: (1) A metal roller 113 mm and 6 mm (4.5 in. & 1 / 4 in.) long and weighing 1 kg (2.2 lb.) shall be used. (2) Embroidery hoops, measuring 150 mm to 180 mm (6 in. to 7 in.) in diameter shall be used for mounting the specimen. Procedure.

[0032] The conditioned specimen shall be securely mounted in the embroidery hoops with sufficient tension to ensure a uniformly smooth surface.

[0033] The direction of the flow of water down the specimen shall coincide with the warpwise direction of the specimen as placed on the stand.

[0034] The mounted specimen shall be placed on the block with the center of the specimen directly beneath the center of the nozzle and the plane of the surface of the specimen at a 45-degree angle with the horizontal.

[0035] A 500 mL volume of distilled water at a temperature of 27 ± 1 °C (80.6 °F ± 1.8 °F) shall be poured quickly into the funnel and allowed to spray onto the specimen.

[0036] The following operations shall then be executed immediately: (1) The specimen shall be removed from the hoops and placed between sheets of blotting paper on a flat horizontal surface. (2) The metal roller shall be rolled quickly forward and back one time over the paper without application of any pressure other than the weight of the roller. (3) A square 100 mm x 100 mm (4 in. x 4 in.) shall be cut out of the center of the wet portion of the specimen and weighed to the nearest 0.05 g. This weight shall be designated the "wet weight." Not more than 30 seconds shall elapse between the time the water has ceased flowing through the spray nozzle and the start of the weighing. (4) The same 100 mm (4 in.) square shall be conditioned as specified in 8.1.2 until it has dried and reached moisture equilibrium with the surrounding standard atmosphere for textiles. (5) Following this conditioning it shall be reweighed. (6) This weight shall be designated the "dry weight".

[0037] The percent water absorption shall be calculated using the following equation: Percent water absorption = [(wet weight - dry weight) / (dry weight)] × 100.

[0038] The percent water absorption for each specimen shall be recorded and reported.

[0039] The average percent water absorption for all tested specimens shall be calculated and reported.Dimensional Changes of Fabrics and Home Laundering (Laundry Cycles) AATCC TM135-2018

[0040] Laundering is preferably performed in a KENMORE automatic washer, followed by drying in a KENMORE automatic dryer. The following laundering test is used to determine the fabric's ability to withstand laundering. Typically, after laundering, the fabric is then subjected to the above-described spray test, water repellency test, and oil repellency test. 1. 8"x10" test specimens are combined with load fabrics (hemmed pieces of cotton sheeting or 50:50 fabric sheets having a size of 36"x36") to give a total dry load of 4 pounds. 2. The dials on the washer are set as follows: Water LevelHighWash CycleNormal, 12 minutesTemperatureWarm Wash, 105 °F; Cold Rinse The test pieces and dummy load are placed in the washer and the machine is started. One ounce of TIDE (Proctor & Gamble) detergent is added while the washer is filling with soft water. If the water hardness is greater than 5 ppm, CALGON water softener (Nalco) in the amount specified by the manufacturer is added to soften the water. 3. After the washing is complete, the wet fabric including the dummy load is placed in the automatic dryer. The dryer temperature dial is set to the proper point under high heat to give a maximum vent temperature of from about 155 °F to about 160 °F. The time dial is set for "Normal Cycle" for 45 minutes. The machine is started and drying is allowed to continue until the cycle is complete. The above represents one laundry cycle. 4. The fabrics are then rewashed and redried until 10 cycles have been completed. Optionally, the test fabrics can be pressed with a hand iron, or the equivalent, at 280 °F to about 320 °F for 30 seconds on each side with the face side pressed last. The fabrics are then conditioned before testing for water is, repellency, oil repellency, or spray rating. As used herein, water repellency, oil repellency and spray ratings are all determined without ironing the fabric after being laundered, unless otherwise denoted.

[0041] When used in the healthcare industry, for example, the protective garment of the present disclosure can be rated according to the Association for the Advancement of Medical Instrumentation (AAMI). The current AAMI standard is described in "Liquid Barrier Performance and Classification of Protective Apparel and Drapes Intended for Use in Health Care Facilities," ANSI / AAMI PB70:2012. This AAMI standard helps to preserve the sterile field and protect health care workers during surgery and other health care procedures during which exposure to blood, body fluids and other potential infectious material might occur. This AAMI standard establishes a system of classification and associated minimum requirements for protective apparel such as gowns and drapes used in health care facilities based on their liquid barrier performance.

[0042] The present AAMI standard for liquid barrier performance is provided in the following table: Table 1AAMI Barrier Protection LevelsAAMI LevelTestResult1AATCC 42:2017e≤ 4.5 grams2AATCC 42:2017e≤ 1.0 gramAATCC 127:2017≥ 20 cm3AATCC 42:2017e≤ 1.0 gramAATCC 127:2017 (ISO 811)≥ 50 cm4Gowns: ASTM F1671 / F1671 M-13PassDrapes: ASTM F1670 / F1670 M-17aPass DETAILED DESCRIPTION

[0043] It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only and is not intended as limiting the broader aspects of the present disclosure.

[0044] In general, the present disclosure is directed to a fabric material treated with a durable water resistant treatment. The durable water resistant treatment is primarily formulated so as not to contain fluorinated compounds. For instance, the primary component of the durable water resistant treatment is a non-fluorinated binder. In accordance with the present disclosure, a minor amount of a fluorocarbon compound is added to the durable water resistant treatment in order to dramatically improve oil and fuel resistance. In this manner, fabric materials can be produced that contain very low levels of fluorine but have resistance not only to water, but also to other chemicals, including fuels.

[0045] Recently, for instance, those skilled in the art have attempted to formulate durable water resistant treatments that do not contain any fluorocarbon polymers. Although many of these durable water resistant treatments provide water resistance, many of the treated fabrics are still susceptible to absorbing various different non-aqueous chemicals, such as fuels, hydrocarbons, oils, and the like. Consequently, many durable water resistant treatments being proposed that do not contain fluorocarbon chemicals are not well suited for use with protective fabrics, especially fabrics that may be exposed to fires, open flames, or arc flashes. The present inventors discovered, however, that adding very minor amounts of a fluorocarbon compound to a durable water resistant treatment primarily made from non-fluorinated components can dramatically and unexpectedly improve resistance to oils, fuels, and other chemicals.

[0046] The resulting fabric material treated in accordance with the present disclosure, for instance, can contain very low levels of fluorine and still provide protection to a wearer from not only water, but also from many different chemicals, including fuels. Fabric materials treated in accordance with the present disclosure, for instance, can contain fluorine in an amount less than about 3,500 ppm, such as in an amount less than about 3,200 ppm, such as in an amount less than about 3,000 ppm, such as in an amount less than about 2,800 ppm, such as in an amount less than about 2,500 ppm, such as in an amount less than about 2,300 ppm, such as in an amount less than about 1000 ppm, such as in an amount less than about 800 ppm, such as in an amount less than about 700 ppm, such as in an amount less than about 600 ppm, such as in an amount less than about 500 ppm. The fabric material may contain fluorine in an amount greater than about 50 ppm, such as in an amount greater than about 75 ppm, such as in an amount greater than about 100 ppm, such as in an amount greater than about 150 ppm, such as in an amount greater than about 200 ppm.

[0047] In general, any suitable fabric material can be treated in accordance with the present disclosure. The fabric material, for instance, can comprise a woven fabric, a knitted fabric, or a nonwoven fabric. The fabric material can comprise a single layer fabric or can comprise a multi-layer fabric. In one aspect, the fabric material can include a fabric substrate laminated to a membrane layer.

[0048] The fabric material treated in accordance with the present disclosure can be used in numerous and diverse fields. For instance, the fabric material can comprise a treated multifilament polyester fabric or polyester blend that can be used in the medical and healthcare fields. For instance, the fabric material can be used to construct medical garments and gowns.

[0049] In one embodiment, the fabric material of the present disclosure is designed to be fire resistant. The fabric material, for instance, can be used to produce protective garments. The protective garments can include fireman turnout coats, protective garments for fighting wildfires, and / or industrial garments designed to provide protection against electric arc flashes and open flames.

[0050] When producing fabric materials and garments that are designed to be flame resistant, the fabric material can contain various different types of flame resistant fibers. The flame resistant fibers can be fibers treated with a flame resistant compound or composition or can comprise inherently flame resistant fibers.

[0051] Flame resistant fabrics are particularly well suited for producing protective garments. As used herein, a protective garment refers to any article of clothing or article that is worn on the body and it can include any part of a protective ensemble. The protective garments include, for instance, footwear, trousers, jackets, coats, shirts, headwear, gloves, and the like. The fabric can also be used to construct one-piece jumpsuits, which may be well suited for use in industrial settings. Protective garments made in accordance with the present disclosure include, for instance, military garments, tactical garments, firefighter garments, industrial garments, and the like whether the garments are made from multiple layers or from a single layer of fabric.

[0052] The garments can be constructed so as to be worn in all types of environments and can be worn by people with different occupations. In one embodiment, the garment may comprise a military garment, such as a battledress uniform. The garment may also comprise various other military apparel, such as flight suits, military jackets, military parkas, and the like.

[0053] In one embodiment, the fabric may be used to construct a garment worn by firefighters. For instance, referring to FIG. 1, one embodiment of a fireman turnout coat 10 constructed in accordance with the present disclosure is illustrated. Garment 10 includes a relatively tough outer shell 12 having a liner assembly 14 located therein. Outer shell 12 and liner assembly 14 together function to protect a wearer from heat and flame such as may be encountered during firefighting activities.

[0054] In the illustrated embodiment, liner assembly 14 is constructed as a separate unit that may be removed from outer shell 12. A zipper 16 is provided for removably securing liner assembly 14 to outer shell 12. It should be appreciated, however, that other suitable means of attachment, including a more permanent type of attachment such as stitches, may also be used between liner assembly 14 and outer shell 12.

[0055] The construction of protective garment 10 is more particularly illustrated in FIG. 2. As shown, liner assembly 14 includes a plurality of material layers quilted together. The outermost layers, i.e. lining layers 20 and 22, are connected together about their respective peripheries 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 adjacent the wearers body during use, whereas lining layer 22 will be adjacent outer shell 12.

[0056] Thermal barrier layer 24 can be made from various materials. For instance, an aramid felt, such as a felt produced from NOMEX meta-aramid fibers obtained from DuPont can be used. The felt functions as an insulator to inhibit transfer of heat from the ambient-environment to the wearer.

[0057] Moisture barrier 26 is preferably a suitable polymeric membrane that is impermeable to liquid water but is permeable to water vapor. Moisture barrier layer 26 is designed to prevent water contacting the exterior surface of garment 10 from reaching the wearer while at the same time permitting the escape of perspiration from the wearer.

[0058] In the embodiment described above, the fireman turnout coat 10 includes multiple layers. In other embodiments, however, it should be understood that a coat or jacket made in accordance with the present disclosure may include a single layer or may include an outer shell attached to a liner. For example, wildland firefighter garments are typically one or two layers.

[0059] Referring to FIG. 3, a pair of trousers made in accordance with the present disclosure is shown. The trousers 40 as shown in FIG. 3 can be used in conjunction with the turnout coat 10 illustrated in FIG. 1. The trousers 40 also include an outer shell 12 made from the fabric of the present disclosure.

[0060] Any of the fabric layers illustrated in the figures can be treated in accordance with the present disclosure. For instance, the outer shell 12, the lining layer 20, the lining layer 22, and / or the thermal barrier layer 24 as shown in FIGS. 1 and 3 can be treated in accordance with the present disclosure with a durable water resistant treatment.

[0061] As described above, when producing protective garments, the fabric material of the present disclosure can contain flame resistant fibers, such as inherently flame resistant fibers. For example, the fabric material can contain inherently flame resistant fibers in an amount greater than about 50% by weight, such as in an amount greater than about 60% by weight, such as in an amount greater than about 70% by weight, such as in an amount greater than about 80% by weight, such as in an amount greater than about 90% by weight, such as in an amount greater than about 95% by weight. In one embodiment, for instance, the fabric material is made exclusively from inherently flame resistant fibers or contains inherently flame resistant fibers in an amount up to about 97% by weight, such as about 98% by weight. For instance, the fabric material can contain only inherently flame resistant fibers in combination with anti-static fibers. The anti-static fibers, for instance, may comprise fibers containing carbon, such as bicomponent fibers containing a carbon core. The carbon core can be surrounded by any suitable polymer, such as a polyester polymer or polyamide polymer.

[0062] The inherently flame resistant fibers can include, for instance, aramid fibers such as para-aramid fibers and / or meta-aramid fibers. Other inherently flame resistant fibers include polybenzimidazole (PBI) fibers or poly(p-phenylene-2,6-bezobisoxazole) (PBO fibers) and the like. Wool fibers are also inherently flame resistant fibers.

[0063] In one embodiment, for instance, the fabric material only contains aramid fibers such as para-aramid fibers alone or in combination with meta-aramid fibers. In still another embodiment, the fabric material contains only meta-aramid fibers. In still another embodiment, the fabric material contains aramid fibers in combination with PBI fibers. The PBI fibers can be present in the fabric material, for instance, in an amount greater than about 20% by weight, such as in an amount greater than about 25% by weight, such as in an amount greater than about 30% by weight, such as in an amount greater than about 35% by weight, such as in an amount greater than about 40% by weight, such as in an amount greater than about 45% by weight, such as in an amount greater than about 50% by weight, and generally in an amount less than about 70% by weight, such as in an amount less than about 60% by weight.

[0064] In addition to any of the inherently flame resistant fibers described above, the fabric material may contain other fibers. For instance, the fabric material may also include fibers treated with a flame retardant such as FR cellulose fibers including FR viscose fibers and FR rayon fibers. In addition, the fabric material may include antistatic fibers, nylon fibers, and the like. For example, a fabric material treated in accordance with the present disclosure can contain nylon fibers in an amount up to about 20% by weight. For instance, nylon fibers can be present in an amount of from about 18% to about 2% by weight, such as from about 15% to about 8% by weight.

[0065] The yarns used to produce the fabric material can vary depending upon the particular application and the desired result. In one embodiment, for instance, the fabric material may contain only spun yarns, may contain only filament yarns, or may contain both spun yarns and filament yarns. The number ratio between spun yarns and filament yarns, for instance, can be from about 1:1 to about 10:1. For example, in one embodiment, the fabric material may contain spun yarns to filament yarns in a number ratio of from about 1:1 to about 8:1, such as from about 2:1 to about 5:1, such as from about 2:1 to about 4:1, such as from about 2:1 to about 3:1. The spun yarns and filament yarns can extend in both the warp direction and the weft direction. The yarns can be spaced such that a single filament yarn is separated by spun yarns. Alternatively, two filament yarns can be separated by spun yarns. When the fabric material is a woven fabric, the fabric can have any suitable weave such as a plain weave, a twill weave, a rip stop weave, or the like.

[0066] In one embodiment, the filament yarns may be made from an inherently flame resistant material. For example, the filament yarns may be made from an aramid filament, such as a para-aramid or a meta-aramid filament.

[0067] In other embodiments, the filament yarns may be made from other flame resistant materials. For instance, the filament yarns may be made from poly-p-phenylenebenzobisoxazole fibers (PBO fibers), and / or FR cellulose fibers, such as FR viscose filament fibers.

[0068] The filament yarns can be combined with spun yarns. Alternatively, the fabric material can be made using only filament yarns or only spun yarns. In accordance with the present 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.

[0069] Instead of or in addition to containing polybenzimidazole fibers, the spun yarns may contain aramid fibers as described above, modacrylic fibers, preoxidized carbon fibers, melamine fibers, polyamide imide fibers, wool fibers, polyimide fibers, and mixtures thereof.

[0070] In one particular embodiment, the spun yarns contain polybenzimidazole fibers in an amount greater than about 20% by weight, such as in an amount greater than about 30% by weight, such as in an amount greater than about 40% by weight. The polybenzimidazole fibers may be present in the spun yarns in an amount less than about 60% by weight, such as in an amount less than about 55% by weight. The remainder of the fibers, on the other hand, may comprise para-aramid fibers.

[0071] In one embodiment, various other fibers may be present in the spun yarns. When the fabric is used to produce turnout coats for firemen, the spun yarns can be made exclusively from inherently flame resistant fibers. When the fabric is being used in other applications, however, various other fibers may be present in the spun yarns. For instance, the spun yarns may contain fibers treated with a fire retardant, such as FR cellulose fibers. Such fibers can include FR cotton, FR rayon, FR acetate, FR triacetate, and FR lyocell, and the like. The spun yarns may also contain nylon fibers if desired, such as antistatic fibers.

[0072] In one aspect, the fabric treated with the water resistant treatment may comprise an outer shell material. The weight of the outer shell material can vary depending upon the particular type of protective garment being produced. The weight of the outer shell material, for instance, is generally greater than about 4 ounces per square yard, such as greater than about 5 ounces per square yard, such as greater than about 5.5 ounces per square yard, such as greater than about 6 ounces per square yard and generally less than about 8.5 ounces per square yard, such as less than about 8 ounces per square yard, such as less than about 7.5 ounces per square yard.

[0073] In another aspect, the fabric material treated in accordance with the present disclosure is a liner fabric. The liner fabric, for instance, can be positioned adjacent to the wearer's body during use. The lining fabric can be made from a combination of spun yarns and filament yarns as described above. The filament yarns can have a size of greater than about 100 denier, such as greater than about 200 denier, and less than about 500 denier, such as less than about 400 denier. In order to increase the lubricity of the liner fabric, the spun yarns and filament yarns can be woven together such that the filament yarns comprise more than about 50% of the surface area of one side of the fabric. For instance, the filament yarns may comprise greater than about 60%, such as greater than about 70%, such as greater than about 80% of one side of the fabric. The side of the fabric with more exposed filament yarns is then used as the interior face of the garment. The filament yarns provide a fabric with high lubricity characteristics that facilitates donning of the garment. For example, the lining fabric can be woven together using a twill weave, such as a 2x1 or 3x1 weave. The lining fabric can have a basis weight of less than about 5 ounces per square yard, such as less than about 4 ounces per square yard, and generally greater than about 2.5 ounces per square yard, such as greater than about 3 ounces per square yard.

[0074] In another aspect, the fabric material treated in accordance with the present disclosure is the barrier layer 24 as shown in FIG. 2. Barrier layer 24, for instance, can comprise a batting material, such as a felt. Once treated, the layer 24 can have the same characteristics as described above with respect to spray rating and water absorption.

[0075] In accordance with the present disclosure, the fabric material is treated with a durable water resistant treatment. In accordance with the present disclosure, the durable water resistant treatment primarily contains non-fluorinated compounds. The non-fluorinated compounds can comprise one or more binders, one or more repelling agents, one or more crosslinking agents, one or more waxes, one or more softeners, and the like. In accordance with the present disclosure, the non-fluorinated components are combined with a minor amount of a fluorocarbon compound in order to dramatically boost chemical resistance in addition to water resistance.

[0076] In one embodiment, the fluorocarbon compound can comprise a short chain fluorinated polymer or oligomer. For instance, the fluorocarbon compound can have a carbon chain length of about 6 carbon atoms or less. Short-chain fluorocarbon compounds help reduce the presence of unintentionally added regulated PFASs, including perfluorooctanoic acid (PFOA) and its salts, perfluorooctane sulfonate (PFOS) and related substances, C9-C14 perfluorocarboxylic acids and their salts, and other long-chain perfluoroalkyl carboxylic acids. For instance, the fluorocarbon compound contained in the durable water resistant treatment can be made exclusively from a C6 fluorocarbon polymer or can contain the C6 fluorocarbon polymer in an amount greater than about 50% by weight, such as in an amount greater than about 70% by weight, such as in an amount greater than about 80% by weight and can be present in combination with C3, C4, and / or C5 fluorocarbon compounds.

[0077] In one embodiment, the durable water resistant treatment and the resulting fabric material can be completely free of C8 or longer perfluorocarboxylic acids. For instance, the durable water resistant treatment or fabric material can be free of perfluorooctanoic acid. The durable water resistant treatment and the fabric material can also be free of alkylphenolethoxylates. In other embodiments, however, longer chain perfluorocarbon compounds can be present, including C8 fluorocarbon compounds.

[0078] In the past, durable water resistant treatments containing fluorocarbon polymers, typically contained the fluorocarbon polymers in an amount greater than 15% by weight, such as in an amount greater than about 16% by weight, such as in an amount greater than about 18% by weight. Fluorocarbon compounds are present in the durable water resistant treatment of the present disclosure, however, in much smaller amounts. For instance, one or more fluorocarbon compounds can be present in the durable water resistant treatment in an amount less than about 10% by weight, such as in an amount less than about 8% by weight, such as in an amount less than about 6% by weight, such as in an amount less than about 5% by weight, such as in an amount less than about 4% by weight, such as in an amount less than about 3% by weight. One or more fluorocarbon compounds can be present in the dried treatment (once applied to the fabric and dried) in an amount less than about 23% by weight, such as in an amount less than about 20% by weight, such as in an amount less than about 15% by weight, such as in an amount less than about 12% by weight, such as in an amount less than about 10% by weight. In one aspect, as described above, the resulting fabric material contains fluorine in an amount less than about 2,500 ppm, such as in an amount less than about 1,500 ppm, such as in an amount less than about 900 ppm, such as in an amount less than about 700 ppm.

[0079] In one embodiment, the fluorocarbon compound is added to the durable water resistant treatment as a blend of the fluorocarbon compound, an emulsifier, and a glycol, such as dipropylene glycol. The blend can be free of alkylphenol ethoxylates. In one aspect, the fluorinated compound can comprise a fluoroalkyl acrylate.

[0080] As described above, the non-fluorinated components contained within the durable water resistant treatment include a binder. The binder contained in the durable water resistant treatment, in one embodiment, can comprise a polyurethane polymer. Of particular advantage, the polyurethane polymer can be water-based and thus can be applied to the fabric in an aqueous dispersion. In one embodiment, the polyurethane polymer is an anionic polyurethane. The polyurethane polymer can also be an aliphatic polyurethane. In one particular embodiment, the polyurethane polymer that makes up the binder is a polyester / ether polyurethane polymer, such as an aliphatic polyester / ether polyurethane polymer.

[0081] In an alternative embodiment, the binder can comprise an acrylic polymer. The acrylic polymer, for instance, can comprise an acrylate, such as a polyacrylate polymer.

[0082] In still another embodiment, the binder can comprise a silicone polymer. The silicone polymer can comprise a polysiloxane, such as a polydimethylsiloxane. Alternatively, the silicone polymer can comprise a silane.

[0083] The durable water resistant treatment of the present disclosure can contain a single binder or can contain a blend of binders. For instance, the durable water resistant treatment can contain a polyurethane polymer in combination with a silicone polymer. Alternatively, the treatment can contain a silicone polymer in combination with an acrylic polymer. In still another embodiment, the treatment can contain a polyurethane polymer in combination with a silicone polymer. In yet another embodiment, the treatment can contain a polyurethane polymer, an acrylic polymer and a silicone polymer. In other embodiments, the binder can comprise two different types of polyurethane polymers or two different types of acrylic polymers. The polymers can differ by molecular weight, functional groups, or the like.

[0084] Optionally, the above binder can be combined with an extender, such as a crosslinking agent. The extender may also comprise a polyurethane polymer. Thus, in one embodiment, the durable water resistant treatment includes a first polyurethane polymer combined with a second polyurethane polymer. The extender, for instance, can comprise a modified polyurethane polymer. For instance, the extender may be a blocked isocyanate. The extender can be cationic or nonionic. The extender is for further increasing water and oil resistance.

[0085] When the extender is a blocked isocyanate, the extender can comprise a latent crosslinking agent. For instance, at elevated temperatures, the blocked isocyanate can cause crosslinking to occur between other polymers contained in the treatment. For instance, the crosslinking agent can cause the binder to crosslink. In one embodiment, the blocked isocyanate is free from butanoane oxime. Although in an alternative embodiment, the blocked isocyanate can comprise an oxime-blocked isocyanate.

[0086] In addition to a binder and / or an extender, in one embodiment, the durable water resistant treatment can further include a softener. The softener, for instance, 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 lower molecular weight polyethylene polymer.

[0087] The durable water resistant treatment can also contain other waxes in addition to or as an alternative to a polyethylene wax. For instance, in one embodiment, the wax can comprise the paraffin wax. In one embodiment, for instance, an acrylic polymer and a paraffin wax can be preblended and added to the durable water resistant treatment.

[0088] In one aspect, the durable water resistant treatment can also contain a repelling agent. The repelling agent can comprise, for instance, an acrylic polymer, such as a polyacrylate. The repelling agent can be different than the binder. The repelling agent, for instance, can be added not only to provide water and / or chemical resistance, but can also make the fabric more durable.

[0089] 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 can vary depending on the particular formulation. In one embodiment, for instance, the binder can be present in relation to the extender in a weight ratio of from about 20:1 to about 2:1, such as in a weight ratio of from about 10:1 to 3:1. In one embodiment, the binder and extender are present in a weight ratio of from about 8:1 to about 3:1 based on the dried weight of the finish.

[0090] When included in the formulation, the softener can generally be present in amounts less than the binder, the repelling agent or the extender. For example, in one embodiment, the softener can be present in relation to the binder in a weight ratio of from about 1:1 to about 1:4, such as from about 1:1.5 to about 1:3.

[0091] In order to produce a liquid resistant fabric in accordance with the present invention, first, a woven or knitted fabric is constructed or obtained that is suitable for use as a fabric material in a protective garment. As described above, the fabric should be made from flame resistant fibers.

[0092] Prior to applying the durable water resistant treatment, the fabric can be first scoured, although scouring may not be necessary for all applications. When scoured, the material can be scoured with an alkaline solution.

[0093] After being scoured, the fabric is then put on a tenter frame, dried and heat set. For instance, after scouring, the fabric should be dried so that the moisture level is substantially equivalent to the natural moisture level of the fibers used to make the fabric. For instance, for most fibers, the moisture level should be less than about 10%, and particularly less than about 7%.

[0094] After the fabric has been dried and heat set, a durable water resistant composition according to the present disclosure is applied to at least one side of the fabric. Although the composition can be sprayed on the fabric or printed on the fabric, preferably the fabric is dipped into a bath containing the durable water resistant treatment in dispersion form.

[0095] The amount of the water-resistant composition applied to the fabric will depend upon the particular formulation and the particular application.

[0096] After the durable water resistant treatment is applied to the fabric, the fabric is then heated to a temperature sufficient for the coating to dry and / or cure. Once the durable water resistant treatment is cured and affixed to the fabric, the fabric can then be used in constructing protective garments in accordance with the present disclosure.

[0097] In one aspect, the dried finish can contain the binder in an amount greater than about 10% by weight, such as in an amount greater than about 15% by weight, such as in an amount greater than about 20% by weight, such as in an amount greater than about 25% by weight, such as in an amount greater than about 30% by weight, such as in an amount greater than about 35% by weight, such as in an amount greater than about 40% by weight, such as in an amount greater than about 45% by weight, such as in an amount greater than about 50% by weight, such as in an amount greater than about 55% by weight, such as in an amount greater than about 60% by weight, and generally less than about 80% by weight, such as less than about 70% by weight, such as less than about 65% by weight, such as less than about 60% by weight, such as less than about 55% by weight, such as less than about 50% by weight, such as less than about 45% by weight, such as less than about 30% by weight.

[0098] The extender can be present in the dried finish in an amount greater than about 3% by weight, such as in an amount greater than about 8% by weight, such as in an amount greater than about 10% by weight, and generally in an amount less than about 30% by weight, such as in an amount less than about 25% by weight, such as in an amount less than about 20% by weight. The repelling agent can be present in the dried durable water resistant treatment in an amount greater than about 10% by weight, such as in an amount greater than about 20% by weight, such as in an amount greater than about 25% by weight, such as in an amount greater than about 35% by weight and generally in an amount less than about 70% by weight, such as in an amount less than about 65% by weight, such as in an amount less than about 55% by weight. When a softener is present, the softener can be present in the dried treatment in an amount greater than about 3% by weight, such as in an amount greater than about 10% by weight, and generally in an amount less than about 25% by weight, such as in an amount less than about 20% by weight, such as in an amount less than about 15% by weight based upon the weight of the dried water resistant treatment.

[0099] As described above, the fabric materials treated in accordance with the present disclosure have excellent water resistance. In addition, the fabric materials display excellent chemical resistance against all different types of chemicals, including fuels, oils, acids, and the like.

[0100] For example, fabric materials treated in accordance with the present disclosure can have a spray rating of at least 70 or higher, such as at least 80 or higher, such as at least 90 or higher even after ten laundry cycles. In one embodiment, for instance, the fabric can maintain a 100 spray rating after ten laundry cycles.

[0101] Similarly, the fabric material can also display excellent resistance to water absorption. For example, when tested according to the water absorption test (NFPA 1971 8.25), the fabric can have a water absorption of about 15% or less, such as about 10% or less, such as about 5% or less, such as about 4% or less, such as about 3% or less, such as about 2% or less, such as about 1 % or less. The above water absorption properties can be retained by the fabric after 5 laundry cycles or even after ten laundry cycles.

[0102] In addition to water, fabric material treated in accordance with the present disclosure also provide protection against various chemical agents such as fuels, oils and / or acids when tested according to ISO Test 6530. For example, when tested against O-xylene (which simulates diesel fuel) fabric materials treated in accordance with the present disclosure, especially fabric materials containing inherently flame resistant fibers, display an initial index of repellency of greater than about 80%, such as greater than about 83%, such as greater than about 85%, such as greater than about 87%. The fabric material can display an index of repellency after 10 laundry cycles of still greater than 80%, such as greater than about 82%. The fabric material can display an index of penetration initially and after 10 laundry cycles of less than about 10%, such as less than about 8%, such as less than about 6%, such as less than about 5%. The fabric material can display an index of absorption initially of less than about 10%, such as less than about 9%, such as less than about 8%. After 10 laundry cycles, the fabric material can display an index of absorption of less than about 20%, such as less than about 15%.

[0103] When tested against hydraulic fluid, the fabric material can display an index of repellency initially and after 10 laundry cycles of greater than about 80%, such as greater than about 85%, such as greater than about 87%. The fabric material can display an index of penetration initially and after 10 laundry cycles of less than about 3%, such as less than about 2%. The fabric material can display an index of absorption initially and after 10 laundry cycles of less than about 10%, such as less than about 8%.

[0104] When tested against a 30% sulfuric acid solution, fabric materials made according to the present disclosure can have an index of repellency of greater than about 85%, such as greater than about 95%, such as greater than about 96%, such as greater than about 97%. The fabric material can have an index of penetration when tested against a 30% sulfuric acid solution of less than about 5%, such as less than about 2%, such as less than about 1 %, such as less than about 0.5%. The fabric material can display an index of absorption of less than about 2%, such as less than about 1%, such as less than about 0.8%. The above properties can be displayed by the fabric material either initially or even after 10 laundry cycles.

[0105] Fabric materials made in accordance with the present disclosure can also display excellent abrasion resistance. For example, a fabric having a basis weight of from about 5 osy to about 9 osy, such as from about 5.5 osy to about 8.5 osy, such as from about 6 osy to about 7.5 osy can have an abrasion resistance of greater than about 90,000 cycles, such as greater than about 95,000 cycles, such as greater than about 98,000 cycles, such as greater than about 100,000 cycles when tested according to ASTM D4966 Test Method. The abrasion resistance is generally less than about 200,000 cycles.

[0106] When testing lighter fabrics, such as linear materials, fabric materials made according to the present disclosure can have an abrasion resistance of greater than about 40,000 cycles, such as greater than about 42,000 cycles, such as greater than about 44,000 cycles, such as greater than about 46,000 cycles, such as greater than about 48,000 cycles, and generally less than about 80,000 cycles. The lighter fabric materials, for instance, can have a basis weight of from about 2 osy to about 5 osy, such as from about 2 osy to about 4 osy, such as from about 2.5 osy to about 3.8 osy.

[0107] As described above, the durable water resistant treatment of the present disclosure can be formulated to be water-based. The durable water resistant treatment, for instance, can comprise an aqueous dispersion of the different ingredients or components. Thus, the durable water resistant treatment of the present disclosure is exceptionally safe for handling and use. In this regard, the durable water resistant treatment of the present disclosure can be applied to the protective garments during their useful life to further reinforce the water resistant properties of the garment. For example, in one embodiment, the durable water resistant treatment can be added to a wash cycle for absorption by the garment. The garment can then be placed in a dryer which causes the durable water resistant treatment to cure and further improve the water resistant properties of the garment.

[0108] The present disclosure may be better understood with reference to the following example.ExampleExample No. 1

[0109] The following tests were performed in order to demonstrate some of the advantages and benefits of fabrics treated in accordance with the present disclosure.

[0110] A flame resistant woven fabric suitable for use as an outer shell material was impregnated with durable water resistant treatments in accordance with the present disclosure and compared with the same fabric treated with a water resistant treatment containing conventional amounts of fluorocarbon chemicals.

[0111] The fabric that was tested is as follows: 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 spun yarn to filament yarn ratio was 2:1 and the fabric had a basis weight of 7 osy.

[0112] Durable water resistant treatments were formulated and applied to the fabric above. The durable water resistant treatments are listed in the table below. A, B, and C were in accordance with the present disclosure and compared with a conventional fluorinated DWR. Table No. 1CHEM NAME% WTFormulaCioppino ACioppino BCioppino CConventional Fluorinated DWRIPA (Isopropyl Alcohol)0.50.50.52Blocked Isocyanate3.13.33.36Blend of Acrylic Polymer and Paraffin18.218.218.2Weathering and UV resistance aid6Softener4C6 Fluoropolymer, Emulsifier, and Dipropylene Glycol (30% solids)1.52.2518-23

[0113] Fabric No. 1 above was dipped into a bath containing each of the durable water resistant treatments. The fabric was patted and dried.

[0114] Fabric No. 1 treated with treatments A, B, and C were tested according to EN Test 469 / ISO Test 6530 against O-xylene and compared to a similar commercially treated fabric that is treated with a durable water resistant treatment not containing any fluorinated compounds. The following results were obtained: Table No. 2ISO 6530 XyleneIndex of PenetrationIndex of RepellencyIndex of AbsorptionCioppino A0.4691.096.170.4690.516.512.9787.547.77Cioppino B1.7190.635.710.4692.005.031.6094.973.54Cioppino C1.7190.865.830.0095.092.863.5487.897.31Fabric treated with no fluorinated compounds38.0625.4940.5737.941.2658.29

[0115] As shown above, fabrics treated according to the present disclosure exhibited dramatically better chemical resistance.

[0116] Durable water resistant A as shown in Table 1 was then applied to Fabric No. 2. Fabric No. 2 was identical to Fabric No. 1 only had a basis weight of 6 osy. Durable water resistant treatment A was applied using a pad application. The treated fabric underwent laundering up to 10X at 40°C and tumble dried. Table 3 shows the liquid repellency of the treated fabric against hydraulic fluid and O-Xylene both before and after undergoing 10X laundering. Table No. 3LiquidWashIndex of PenetrationIndex of RepellencyIndex of AbsorptionOriginal (0X)0.1192.466.970.1190.45.371.1494.746.42.0690.971.831.7190.516.51Hydraulic fluid0.5792.574.810X0.596.344.910.990.637.310.593.493.891.1975.60.591.895.490.696.114.11Index of PenetrationIndex of RepellencyIndex of Absorption4.3487.895.940.892.576.069.0386.174.34Original (0X)0.6994.44.234.6990.975.6O-Xylene9.7184.343.895.9490.43.5410.5180.238.1110X4.2384.2310.634.4684.6913.030.9187.6610.17

[0117] Next, durable water resistant treatment B was applied to Fabric No. 1 and tested against O-xylene both before and after 10 laundry cycles. The following results were obtained: Table No. 4LiquidWashIndex of PenetrationIndex of RepellencyIndex of AbsorptionFabric No. 1 with Cioppino B0X0.696.131.894.43.11.494.62.50.697.12.71.195.13.80.195.73Fabric No. 1 with Cioppino B10X washed with CitroSqueeze096.74.30.897.93.3

[0118] Durable water resistant treatment C was then applied to Fabric No. 1 and tested against O-xylene and 30% sulfuric acid both initially and after 5 laundry cycles. The following results were obtained: Table No. 5LiquidWashIndex of PenetrationIndex of RepellencyIndex of AbsorptionOriginal (0X)0.199.30.6099.80.20.199.70.3099.70.30.898.90.3Sulfuric Acid 30%0.399.20.65X0.299.40.4099.80.20.399.30.40.399.30.30.799.10.3099.90.1Original (0X)Index of PenetrationIndex of RepellencyIndex of Absorption196.52.52.6952.52.795.320.797.51.83.794.32O-Xylene3.294.42.55X2.593.34.21.6953.3197.61.42.2952.83.191.35.62.4961.6

[0119] Fabric No. 1 treated with durable water resistant A and with durable water resistant C were then tested for fluorine content. Fluorine content was determined according to EN Test 14582 by combustion bomb with oxygen and determined using ion chromatography. Other commercially available fabrics (Style No. 1 and Style No. 2) were also tested. Both of these fabrics are made from inherently flame resistant fibers and are both treated with a conventional durable water resistant treatment containing high amounts of fluorocarbon polymers. The following results were obtained: Table No. 6Fluorine (F) Content according to EN 14582:2016 by combustion bomb with oxygen and determined by Ion Chromatography.Tested SampleResult (ppm)Limit of detection # (ppm)Fabric No. 1 treated with Cioppino A49420Fabric No. 1 treated with Cioppino C209020Style No. 1371020Style No. 2680020

[0120] As shown above, fabrics treated in accordance with the present disclosure contained extremely minor amounts of fluorine, especially in comparison to conventional fabrics. The fluorine concentration on the fabric treated in accordance with the present disclosure, for instance, is more than 13X lower than the conventional fabrics. The fabric material of the present disclosure, however, displays the same or better chemical resistant properties than the conventional fabrics even after multiple laundry cycles.Example No. 2

[0121] Treatment Cioppino C was applied to Fabric No. 1 according to the method described in Example No. 1 and tested for various properties.

[0122] The following results were obtained.

[0123] Three samples were subjected to the Spray Test: Spray Test (AATCC TM 22-2022) L C R Initial100100100After 5 Laundry Cycles100100100After 10 Laundry Cycles100100100

[0124] For the above samples, after the indicated number of laundry cycles, a single final rinse cycle with no detergent was conducted followed by a permanent press tumble dry.

[0125] Two samples were subjected to a Water Alcohol Test: Water alcohol (AATCC TM 193-2023) 1 (2% Alcohol) 2 (5% Alcohol) 3 (10% Alcohol) Initial (sample 1)AAAInitial (sample 2)AAAAfter Five Laundry Cycles (sample 1)AAAAfter Five Laundry Cycles (sample 2)AAAAfter Ten Laundry Cycles (sample 1)AAAAfter Ten Laundry Cycles (sample 2)AAA Water alcohol (AATCC TM 193-2023) 4 (20% Alcohol) 5 (30% Alcohol) 6 (40% Alcohol) Initial (sample 1)AAAInitial (sample 2)AAAAfter Five Laundry Cycles (sample 1)AAAAfter Five Laundry Cycles (sample 2)AAAAfter Ten Laundry Cycles (sample 1)AAAAfter Ten Laundry Cycles (sample 2)AAA A = PASS excellent, B=borderline PASS, C=FAIL with some beading, D=FAIL, completely wet out - AATCC TM 193

[0126] Two samples were subjected to an Oil Repellency Test: Oil repellency (AATCCTM 118-2020) 1 (Kaydol) 2 (65:35 Kaydol:n-hexadecane) 3 (n-hexadecane) Initial (sample 1)AAAInitial (sample 2)AAAAfter Five Laudry Cycles (sample 1)AAAAfter Five Laundry Cycles (sample 2)AAAAfter Ten Laundry Cycles (sample 1)AAAAfter Ten Laundry Cycles (sample 2)AAAOil repellency (AATCC TM 118-2020) 4 (n-tetradecane) 5 (n-dodecane) 6 (n-decane) Initial (sample 1)ABBInitial (sample 2)ABBAfter Five Laudry Cycles (sample 1)ABDAfter Five Laundry Cycles (sample 2)ABDAfter Ten Laundry Cycles (sample 1)ABDAfter Ten Laundry Cycles (sample 2)ABDA = PASS excellent, B=borderline PASS, C=FAIL with some beading, D=FAIL, completely wet out - AATCC TM 193

[0127] Results of Water Penetration Test (Water Absorption Resistance) and Chemical Runoff Test: Water penetration 24 hrs % water absorbed Sample 1, 0x0.3%Sample 1, 5x0.0%Sample 1, 10x0.0% Chemical Runoff, ISO 6530, 2005 edition

[0128] Xylene Ir % Avgs Sample 1, 0x100.0%Sample 1, 5x98.7%Sample 1, 10x95.4%

[0129] These and other modifications and variations to the present invention may be practiced by those of ordinary skill in the art, without departing from the spirit and scope of the present invention, which is more particularly set forth in the appended claims. In addition, it should be understood that aspects of the various embodiments may be interchanged both in whole or in part. Furthermore, those of ordinary skill in the art will appreciate that the foregoing description is by way of example only and is not intended to limit the invention so further described in such appended claims.

Examples

example

Example

Example No. 1

[0109]The following tests were performed in order to demonstrate some of the advantages and benefits of fabrics treated in accordance with the present disclosure.

[0110]A flame resistant woven fabric suitable for use as an outer shell material was impregnated with durable water resistant treatments in accordance with the present disclosure and compared with the same fabric treated with a water resistant treatment containing conventional amounts of fluorocarbon chemicals.

[0111]The fabric that was tested is as follows: 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 spun yarn to filament yarn ratio was 2:1 and the fabric had a basis weight of 7 osy.

[0112]Durable water resistant treatments were formulated and applied to the fabric above. The durable water resistant treatments are listed in the table below. A, B, and C were in accordance with the presen...

example no.2

Example No. 2

[0121]Treatment Cioppino C was applied to Fabric No. 1 according to the method described in Example No. 1 and tested for various properties.

[0122]The following results were obtained.

[0123]Three samples were subjected to the Spray Test:

Spray Test (AATCC TM 22-2022) L C R

Initial100100100

After 5 Laundry Cycles100100100

After 10 Laundry Cycles100100100

[0124]For the above samples, after the indicated number of laundry cycles, a single final rinse cycle with no detergent was conducted followed by a permanent press tumble dry.

[0125]Two samples were subjected to a Water Alcohol Test:

Water alcohol (AATCC TM 193-2023) 1 (2% Alcohol) 2 (5% Alcohol) 3 (10% Alcohol)

Initial (sample 1)AAA

Initial (sample 2)AAA

After Five Laundry Cycles (sample 1)AAA

After Five Laundry Cycles (sample 2)AAA

After Ten Laundry Cycles (sample 1)AAA

After Ten Laundry Cycles (sample 2)AAA

Water alcohol (AATCC TM 193-2023) 4 (20% Alcohol) 5 (30% Alcohol) 6 (40% Alcohol) Initial (sample 1)A...

BACKGROUND

[0001] Various different types of protective garments exist that are intended to provide protection to the wearer. In certain embodiments, for instance, the protective garments are designed to provide protection from liquids, such as water and / or oil. Such protective garments, for instance, are typically worn by first responders, medical personnel, public service providers, and military personnel.

[0002] Notably, the absorbing and retaining of moisture and / or oil may result in detrimental effects to both the garment and the wearer. For instance, if the garment retains moisture, the protective garment can become significantly heavier and / or affect the thermal properties of the garment making the garment less effective in shielding its wearer from thermal heat. Additionally, for instance, if the garment absorbs and / or retains oil, the protective garment may have reduced breathability, reduced chemical resistance, and / or may be subject to staining. Thus, water repellency and oil repellency are important considerations in garment and fabric material treatments.

[0003] In the past, treatments utilized to provide water repellency and / or oil repellency have contained fluorocarbon chemicals. In general, fluorocarbon chemicals are durable and provide for adequate water resistance and oil resistance. Recently, however, various manufacturers, including fabric makers, have been placed under increased pressure to reduce the amount of fluorocarbons incorporated into products. For instance, the manufacture and handling of fluorocarbons has been subject to greater scrutiny and governmental regulation.

[0004] Thus, a need currently exists for a treatment for fabrics that not only provides water resistance but is also resistant to oils, fuels, and the like. In particular, a need exists for a treatment for fabrics that provides resistance to all different types of liquids and contains a reduced level of fluorocarbon chemistries. Further, a need exists for fire resistant fabrics that are capable of accepting a fabric treatment as described above.SUMMARY

[0005] In general, the present disclosure is directed to a fabric material that is not only water resistant but is also resistant to oils, fuels, and the like. In one aspect, the fabric material can also be fire resistant. In this regard, the present disclosure is also directed to protective garments made from the fabric. The present disclosure is further directed to a fabric treatment containing reduced fluorine levels that, once applied to a fabric, makes the fabric water and chemical resistant.

[0006] In one aspect, for instance, the present disclosure is directed to a fabric for producing protective garments. The fabric comprises a fabric material containing inherently flame resistant fibers. The inherently flame resistant fibers can comprise para-aramid fibers, meta-aramid fibers, modacrylic fibers, polybenzimidazole fibers, polybenzoxazole fibers, metacrylic fibers, wool fibers, or mixtures thereof. The inherently flame resistant fibers can comprise greater than about 50% by weight, such as greater than about 60% by weight, such as greater than about 70% by weight, such as greater than about 80% by weight, such as greater than about 90% by weight, such as greater than about 95% by weight of the fabric material. The fabric material further comprises a durable water resistant treatment. The durable water resistant treatment comprises a non-fluorinated binder in combination with a fluorocarbon compound.

[0007] In accordance with the present disclosure, the treated fabric material of the present disclosure contains fluorine in reduced amounts while still displaying excellent water and fuel resistance. For instance, the treated fabric material can contain fluorine in an amount less than about 3,500 ppm, such as in an amount less than about 3,300 ppm, such as in an amount less than about 3,000 ppm, such as in an amount less than about 2,800 ppm, such as in an amount less than about 2,500 ppm, such as in an amount less than about 2,300 ppm, such as in an amount less than about 2,200 ppm, such as in an amount less than about 2,000 ppm, such as in an amount less than about 900 ppm, such as in an amount less than about 700 ppm. The resulting fabric material, for instance, can contain fluorine in an amount greater than about 100 ppm, such as in an amount greater than about 150 ppm, such as in an amount greater than about 200 ppm, such as in an amount greater than about 250 ppm, such as in an amount greater than about 300 ppm.

[0008] In one aspect, the fluorocarbon compound incorporated into the durable water resistant treatment comprises a fluoropolymer or oligomer containing relatively short carbon chains. For instance, in one aspect, the durable water resistant treatment and the fabric material can be free of any C8 or longer chain perfluoroalkyl and polyfluoroalkyl substances such as perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorooctane sulfonate (PFOS), and long chain fluorotelomer alcohols within the chemistry (8:2 FTOH) and / or does not contain an alkylphenol ethoxylate.

[0009] The fabric material of the present disclosure can display excellent water resistance in combination with oil and fuel resistance. For instance, the fabric material can maintain a water absorption of less than about 10%, such as less than about 8%, such as less than about 6%, such as less than about 4% after 10 laundry cycles. The fabric material can also maintain a spray rating of at least 70, such as at least 80, such as at least 90 after 10 laundry cycles. In addition, when tested according to ISO Test 6530 against O-xylene, the fabric material can display an index of repellency of greater than about 80%, such as greater than about 85%, such as greater than about 87%, and can display an index of repellency after 10 laundry cycles of greater than about 80%, such as greater than about 82%. The fabric material can display an index of penetration against O-xylene of less than about 10%, such as less than about 5%, and after 10 laundry cycles, of less than about 10%, such as less than about 6%. The fabric material can display an index of absorption against O-xylene of less than about 10%, such as less than about 9%, such as less than about 8%. After 10 laundry cycles, the fabric material can display an index of absorption of less than about 20%, such as less than about 15%.

[0010] When tested against hydraulic fluid according to ISO Test 6530, the fabric material can display an index of repellency initially and after 10 laundry cycles of greater than about 80%, such as greater than about 85%, such as greater than about 87%, can display an index of penetration initially and after 10 laundry cycles of less than about 3%, such as less than about 2%, and can display an index of absorption initially and after 10 laundry cycles of less than about 10%, such as less than about 8%.

[0011] When tested against 30% sulfuric acid according to ISO Test 6530, the fabric material can display an index of repellency initially and after 10 laundry cycles of greater than about 95%, such as greater than about 96%, such as greater than about 97%, can display an index of penetration initially and after 10 laundry cycles of less than about 2%, such as less than about 1%, and can display an index of absorption initially and after 10 laundry cycles of less than about 1%, such as less than about 0.8%.

[0012] In one aspect, the fluorocarbon compound contained in the durable water resistant treatment comprises a smaller chain fluorocarbon polymer or oligomer. For instance, the carbon chain length of the fluorocarbon compound can be a C2 to a C6 chain length, such as a C6 chain length. In one aspect, the fluorocarbon compound comprises a fluoroalkyl acrylate.

[0013] The non-fluorinated binder contained in the durable water resistant treatment can comprise an acrylic polymer, a polyurethane polymer, a silicone polymer, or mixtures thereof. The durable water resistant treatment can also contain various other components. For instance, the durable water resistant treatment can contain a wax, such as a paraffin and / or a polyethylene wax. The durable water resistant treatment can also contain a repelling agent which may comprise an acrylic polymer. In one embodiment, for instance, the durable water resistant treatment contains a non-fluorinated binder comprising an acrylic polymer, a polyurethane polymer, a silicone polymer, or mixtures thereof in combination with an acrylic polymer repelling agent and a wax, such as a paraffin. The durable water resistant treatment can also contain a latent crosslinking agent, such as a blocked isocyanate.

[0014] As described above, the fabric material can contain inherently flame resistant fibers. The fabric material can comprise a woven fabric that contains only spun yarns or spun yarns in combination with multifilament yarns. In one aspect, the fabric material contains spun yarns comprised of aramid fibers blended with PBI fibers and filament yarns comprised of aramid fibers, such as para-aramid or meta-aramid filaments or stretched broken filaments. The spun yarns and the multifilament yarns can both extend in the warp direction and the weft direction and can be present in the fabric material, for instance, at a ratio of from about 1 spun yarn to 1 multifilament yarn to about 8 spun yarns to about 1 multifilament yarn. In one particular application, the spun yarns contain PBI fibers in an amount greater than about 20% by weight, such as in an amount greater than about 30% by weight, and in an amount less than about 100% by weight, such as in an amount less than about 60% by weight.

[0015] In one aspect, the fabric material can have a basis weight of from about 5 osy to about 8.5 osy. In one aspect, for instance, the basis weight can be from about 5 osy to about 6.8 osy. In an alternative embodiment, the basis weight can be from about 6.8 osy to about 8.5 osy.

[0016] The present disclosure is also directed to a protective garment made from the fabric material as described above. For instance, the protective garment can comprise a fireman turnout coat and the fabric material can form an exterior surface of the protective garment. For instance, the fabric material can comprise the outer shell material of the garment. Alternatively, the protective garment can comprise an inner lining, a hood, footwear, or a glove. The fabric material can comprise a single layer of fabric or can comprise a multi-layer fabric.

[0017] Other features and aspects of the present disclosure are discussed in greater detail below.BRIEF DESCRIPTION OF THE DRAWINGS

[0018] 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 the present disclosure; Figure 2 is a cross-sectional view of an inner liner incorporated into the garment illustrated in Figure 1; Figures 3A-3F are diagrammatical views of illustrative examples of spray ratings 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 the present disclosure.

[0019] Repeat use of reference characters in the present specification and drawings is intended to represent the same or analogous features or elements of the present invention.Definitions and Standardized Procedures

[0020] The following definitions and procedures are offered in order to better describe and quantify the performance of protective garments and fabrics made according to the present invention in comparison to prior art constructions.Water Repellency: Spray Test AATCC TM22-2017

[0021] As used herein, a fabric spray rating refers to a rating a fabric or a material receives according to AATCC TM22-2017. In general, a spray test measures the resistance of a material to wetting by water.

[0022] According to the present invention, the following is the procedure used to determine the spray rating of a material. 1. A 7"x7" sample of the material to be tested is first conditioned at 65 ± 2% relative humidity and at 70 ± 2 °F for a minimum of four hours prior to testing. 2. The fabric sample is fastened securely on a 6" metal hoop so that the fabric is wrinkle free. The hoop is supported on a tester's stand so that the fabric is facing up. Twills, gabardines, piques or similar fabrics of ribbed construction are positioned on the stand so that the ribs are diagonal to the flow of water running off the fabric. A funnel attached to a nozzle for holding water is placed 6" above the center of the fabric. 3. 250 milliliters of water at 80 ± 2 °F are poured from a cup or other container into the funnel, allowing the water to spray onto the fabric. 4. Once the water has run through the funnel, one edge of the hoop is held and the opposite edge is firmly rapped once against a solid object with the fabric facing the object. The hoop is then rotated 180° and it is rapped once more at the point previously held. 5. The wetted or spotted fabric sample is then compared with the standards shown in FIGS. 3A-3F. The fabric is assigned a spray rating that corresponds to the nearest standard. As shown on FIGS. 3A-3F, the fabric can be rated from 0 to 100 wherein 0 indicates that the entire fabric is wetted with the water, while a rating of 100 indicates that none of the fabric was wetted by the water. Water Absorption Resistance Test

[0023] The following water absorption test is for determining the resistance to water absorption of a fabric or material. The test is based upon NFPA 1971-2018, 8-25. In particular, the water absorption test is conducted according to the above-identified test method after the fabric or material has been subjected to five laundry cycles in accordance with NFPA 1971, 8-1.2 (or AATCC TM135-2018 - 1, V, Ai).

[0024] According to the present invention, the following is the procedure used to determine the water absorption rating of a material. 1. Three 8"x8" samples of the material to be tested are subjected to five laundry cycles in accordance with NFPA 1971, 8-1.2. Test method NFPA 1972, 8-1.2 is substantially similar to the laundering test described above. In this test, however, the specimens are conditioned in an atmosphere of 70 ± 2 °F and 65 ± 2% relative humidity before and after being washed. Further, the machine settings and parameters are as follows: water levelnormalwash cyclenormal / cotton sturdywash temperature140 ± 5 °Fdrying cycletumble / cotton sturdydetergent66 ± 1 g of 1993 AATCC standard Reference Detergent 2. Each sample is securely mounted, with the coated side of the material up, to embroidery hoops with sufficient tension to ensure a uniformly smooth surface. The hoop is supported on a tester's stand. The material is positioned so that the direction of the flow of water down the sample shall coincide with the warpwise direction of the sample as placed on the stand. A funnel attached to a nozzle for holding water is placed 24" above the center of the material. The plane of the surface of the sample is placed at a 45° angle with the horizontal. 3. 500 ml of water at a temperature of 80 ± 2 °F are poured quickly into the funnel and allowed to spray onto the specimen. 4. As rapidly as possible, the sample is removed from the hoops and placed between two sheets of blotting paper on a flat horizontal surface. A metal roller approximately 41 / 2" long and weighing 21 / 4 pounds is rolled quickly forward and back one time over the paper without application of any pressure other than the weight of the roller. 5. A square having dimensions of 4"x4" is cut out of the center of the sample and weighed to the nearest 0.05 grams. Not more than 30 seconds shall elapse between the time the water has ceased flowing through the spray nozzle and the start of the weighing. 6. The same 4"x4" square sample is then left in a conditioning room until it has dried and reached moisture equilibrium with the surrounding atmosphere. The sample is then weighed again. 7. The water absorbed shall be calculated as follows:waterabsorption,percent=W−OO×100 herein W is the weight of the wet sample and O is the weight of the dried sample. The water absorption rating of the sample is the average of the results obtained from the three specimens tested.Resistance of Fabrics to Penetration by Liquid

[0025] The resistance of fabrics to penetration by hydraulic fluid, a 30% sulfuric acid solution, and O-xylene (simulation of diesel fuel) is conducted according to EN Test 469 / ISO Test 6530.Water Penetration Test / Water Absorption Resistance Test

[0026] This test method shall apply to the protective garment outer shell and collar lining materials.Sample Preparation:

[0027] Samples for conditioning shall be at least 1 m (1.1 yd) square of each material.

[0028] Specimens except CBRN garment and material specimens shall be conditioned as specified in 8.1.9 followed by conditioning as specified in 8.1.2 of NFPA 1951.Specimens:

[0029] Specimens shall be 200 mm × 200 mm (8 in. x 8 in.).

[0030] At least 3 specimens shall be tested.Apparatus:

[0031] The test apparatus is as specified in AATCC 42, Water Resistance: Impact Penetration Test, with the following modifications: (1) A metal roller 113 mm and 6 mm (4.5 in. & 1 / 4 in.) long and weighing 1 kg (2.2 lb.) shall be used. (2) Embroidery hoops, measuring 150 mm to 180 mm (6 in. to 7 in.) in diameter shall be used for mounting the specimen. Procedure.

[0032] The conditioned specimen shall be securely mounted in the embroidery hoops with sufficient tension to ensure a uniformly smooth surface.

[0033] The direction of the flow of water down the specimen shall coincide with the warpwise direction of the specimen as placed on the stand.

[0034] The mounted specimen shall be placed on the block with the center of the specimen directly beneath the center of the nozzle and the plane of the surface of the specimen at a 45-degree angle with the horizontal.

[0035] A 500 mL volume of distilled water at a temperature of 27 ± 1 °C (80.6 °F ± 1.8 °F) shall be poured quickly into the funnel and allowed to spray onto the specimen.

[0036] The following operations shall then be executed immediately: (1) The specimen shall be removed from the hoops and placed between sheets of blotting paper on a flat horizontal surface. (2) The metal roller shall be rolled quickly forward and back one time over the paper without application of any pressure other than the weight of the roller. (3) A square 100 mm x 100 mm (4 in. x 4 in.) shall be cut out of the center of the wet portion of the specimen and weighed to the nearest 0.05 g. This weight shall be designated the "wet weight." Not more than 30 seconds shall elapse between the time the water has ceased flowing through the spray nozzle and the start of the weighing. (4) The same 100 mm (4 in.) square shall be conditioned as specified in 8.1.2 until it has dried and reached moisture equilibrium with the surrounding standard atmosphere for textiles. (5) Following this conditioning it shall be reweighed. (6) This weight shall be designated the "dry weight".

[0037] The percent water absorption shall be calculated using the following equation: Percent water absorption = [(wet weight - dry weight) / (dry weight)] × 100.

[0038] The percent water absorption for each specimen shall be recorded and reported.

[0039] The average percent water absorption for all tested specimens shall be calculated and reported.Dimensional Changes of Fabrics and Home Laundering (Laundry Cycles) AATCC TM135-2018

[0040] Laundering is preferably performed in a KENMORE automatic washer, followed by drying in a KENMORE automatic dryer. The following laundering test is used to determine the fabric's ability to withstand laundering. Typically, after laundering, the fabric is then subjected to the above-described spray test, water repellency test, and oil repellency test. 1. 8"x10" test specimens are combined with load fabrics (hemmed pieces of cotton sheeting or 50:50 fabric sheets having a size of 36"x36") to give a total dry load of 4 pounds. 2. The dials on the washer are set as follows: Water LevelHighWash CycleNormal, 12 minutesTemperatureWarm Wash, 105 °F; Cold Rinse The test pieces and dummy load are placed in the washer and the machine is started. One ounce of TIDE (Proctor & Gamble) detergent is added while the washer is filling with soft water. If the water hardness is greater than 5 ppm, CALGON water softener (Nalco) in the amount specified by the manufacturer is added to soften the water. 3. After the washing is complete, the wet fabric including the dummy load is placed in the automatic dryer. The dryer temperature dial is set to the proper point under high heat to give a maximum vent temperature of from about 155 °F to about 160 °F. The time dial is set for "Normal Cycle" for 45 minutes. The machine is started and drying is allowed to continue until the cycle is complete. The above represents one laundry cycle. 4. The fabrics are then rewashed and redried until 10 cycles have been completed. Optionally, the test fabrics can be pressed with a hand iron, or the equivalent, at 280 °F to about 320 °F for 30 seconds on each side with the face side pressed last. The fabrics are then conditioned before testing for water is, repellency, oil repellency, or spray rating. As used herein, water repellency, oil repellency and spray ratings are all determined without ironing the fabric after being laundered, unless otherwise denoted.

[0041] When used in the healthcare industry, for example, the protective garment of the present disclosure can be rated according to the Association for the Advancement of Medical Instrumentation (AAMI). The current AAMI standard is described in "Liquid Barrier Performance and Classification of Protective Apparel and Drapes Intended for Use in Health Care Facilities," ANSI / AAMI PB70:2012. This AAMI standard helps to preserve the sterile field and protect health care workers during surgery and other health care procedures during which exposure to blood, body fluids and other potential infectious material might occur. This AAMI standard establishes a system of classification and associated minimum requirements for protective apparel such as gowns and drapes used in health care facilities based on their liquid barrier performance.

[0042] The present AAMI standard for liquid barrier performance is provided in the following table: Table 1AAMI Barrier Protection LevelsAAMI LevelTestResult1AATCC 42:2017e≤ 4.5 grams2AATCC 42:2017e≤ 1.0 gramAATCC 127:2017≥ 20 cm3AATCC 42:2017e≤ 1.0 gramAATCC 127:2017 (ISO 811)≥ 50 cm4Gowns: ASTM F1671 / F1671 M-13PassDrapes: ASTM F1670 / F1670 M-17aPass DETAILED DESCRIPTION

[0043] It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only and is not intended as limiting the broader aspects of the present disclosure.

[0044] In general, the present disclosure is directed to a fabric material treated with a durable water resistant treatment. The durable water resistant treatment is primarily formulated so as not to contain fluorinated compounds. For instance, the primary component of the durable water resistant treatment is a non-fluorinated binder. In accordance with the present disclosure, a minor amount of a fluorocarbon compound is added to the durable water resistant treatment in order to dramatically improve oil and fuel resistance. In this manner, fabric materials can be produced that contain very low levels of fluorine but have resistance not only to water, but also to other chemicals, including fuels.

[0045] Recently, for instance, those skilled in the art have attempted to formulate durable water resistant treatments that do not contain any fluorocarbon polymers. Although many of these durable water resistant treatments provide water resistance, many of the treated fabrics are still susceptible to absorbing various different non-aqueous chemicals, such as fuels, hydrocarbons, oils, and the like. Consequently, many durable water resistant treatments being proposed that do not contain fluorocarbon chemicals are not well suited for use with protective fabrics, especially fabrics that may be exposed to fires, open flames, or arc flashes. The present inventors discovered, however, that adding very minor amounts of a fluorocarbon compound to a durable water resistant treatment primarily made from non-fluorinated components can dramatically and unexpectedly improve resistance to oils, fuels, and other chemicals.

[0046] The resulting fabric material treated in accordance with the present disclosure, for instance, can contain very low levels of fluorine and still provide protection to a wearer from not only water, but also from many different chemicals, including fuels. Fabric materials treated in accordance with the present disclosure, for instance, can contain fluorine in an amount less than about 3,500 ppm, such as in an amount less than about 3,200 ppm, such as in an amount less than about 3,000 ppm, such as in an amount less than about 2,800 ppm, such as in an amount less than about 2,500 ppm, such as in an amount less than about 2,300 ppm, such as in an amount less than about 1000 ppm, such as in an amount less than about 800 ppm, such as in an amount less than about 700 ppm, such as in an amount less than about 600 ppm, such as in an amount less than about 500 ppm. The fabric material may contain fluorine in an amount greater than about 50 ppm, such as in an amount greater than about 75 ppm, such as in an amount greater than about 100 ppm, such as in an amount greater than about 150 ppm, such as in an amount greater than about 200 ppm.

[0047] In general, any suitable fabric material can be treated in accordance with the present disclosure. The fabric material, for instance, can comprise a woven fabric, a knitted fabric, or a nonwoven fabric. The fabric material can comprise a single layer fabric or can comprise a multi-layer fabric. In one aspect, the fabric material can include a fabric substrate laminated to a membrane layer.

[0048] The fabric material treated in accordance with the present disclosure can be used in numerous and diverse fields. For instance, the fabric material can comprise a treated multifilament polyester fabric or polyester blend that can be used in the medical and healthcare fields. For instance, the fabric material can be used to construct medical garments and gowns.

[0049] In one embodiment, the fabric material of the present disclosure is designed to be fire resistant. The fabric material, for instance, can be used to produce protective garments. The protective garments can include fireman turnout coats, protective garments for fighting wildfires, and / or industrial garments designed to provide protection against electric arc flashes and open flames.

[0050] When producing fabric materials and garments that are designed to be flame resistant, the fabric material can contain various different types of flame resistant fibers. The flame resistant fibers can be fibers treated with a flame resistant compound or composition or can comprise inherently flame resistant fibers.

[0051] Flame resistant fabrics are particularly well suited for producing protective garments. As used herein, a protective garment refers to any article of clothing or article that is worn on the body and it can include any part of a protective ensemble. The protective garments include, for instance, footwear, trousers, jackets, coats, shirts, headwear, gloves, and the like. The fabric can also be used to construct one-piece jumpsuits, which may be well suited for use in industrial settings. Protective garments made in accordance with the present disclosure include, for instance, military garments, tactical garments, firefighter garments, industrial garments, and the like whether the garments are made from multiple layers or from a single layer of fabric.

[0052] The garments can be constructed so as to be worn in all types of environments and can be worn by people with different occupations. In one embodiment, the garment may comprise a military garment, such as a battledress uniform. The garment may also comprise various other military apparel, such as flight suits, military jackets, military parkas, and the like.

[0053] In one embodiment, the fabric may be used to construct a garment worn by firefighters. For instance, referring to FIG. 1, one embodiment of a fireman turnout coat 10 constructed in accordance with the present disclosure is illustrated. Garment 10 includes a relatively tough outer shell 12 having a liner assembly 14 located therein. Outer shell 12 and liner assembly 14 together function to protect a wearer from heat and flame such as may be encountered during firefighting activities.

[0054] In the illustrated embodiment, liner assembly 14 is constructed as a separate unit that may be removed from outer shell 12. A zipper 16 is provided for removably securing liner assembly 14 to outer shell 12. It should be appreciated, however, that other suitable means of attachment, including a more permanent type of attachment such as stitches, may also be used between liner assembly 14 and outer shell 12.

[0055] The construction of protective garment 10 is more particularly illustrated in FIG. 2. As shown, liner assembly 14 includes a plurality of material layers quilted together. The outermost layers, i.e. lining layers 20 and 22, are connected together about their respective peripheries 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 adjacent the wearers body during use, whereas lining layer 22 will be adjacent outer shell 12.

[0056] Thermal barrier layer 24 can be made from various materials. For instance, an aramid felt, such as a felt produced from NOMEX meta-aramid fibers obtained from DuPont can be used. The felt functions as an insulator to inhibit transfer of heat from the ambient-environment to the wearer.

[0057] Moisture barrier 26 is preferably a suitable polymeric membrane that is impermeable to liquid water but is permeable to water vapor. Moisture barrier layer 26 is designed to prevent water contacting the exterior surface of garment 10 from reaching the wearer while at the same time permitting the escape of perspiration from the wearer.

[0058] In the embodiment described above, the fireman turnout coat 10 includes multiple layers. In other embodiments, however, it should be understood that a coat or jacket made in accordance with the present disclosure may include a single layer or may include an outer shell attached to a liner. For example, wildland firefighter garments are typically one or two layers.

[0059] Referring to FIG. 3, a pair of trousers made in accordance with the present disclosure is shown. The trousers 40 as shown in FIG. 3 can be used in conjunction with the turnout coat 10 illustrated in FIG. 1. The trousers 40 also include an outer shell 12 made from the fabric of the present disclosure.

[0060] Any of the fabric layers illustrated in the figures can be treated in accordance with the present disclosure. For instance, the outer shell 12, the lining layer 20, the lining layer 22, and / or the thermal barrier layer 24 as shown in FIGS. 1 and 3 can be treated in accordance with the present disclosure with a durable water resistant treatment.

[0061] As described above, when producing protective garments, the fabric material of the present disclosure can contain flame resistant fibers, such as inherently flame resistant fibers. For example, the fabric material can contain inherently flame resistant fibers in an amount greater than about 50% by weight, such as in an amount greater than about 60% by weight, such as in an amount greater than about 70% by weight, such as in an amount greater than about 80% by weight, such as in an amount greater than about 90% by weight, such as in an amount greater than about 95% by weight. In one embodiment, for instance, the fabric material is made exclusively from inherently flame resistant fibers or contains inherently flame resistant fibers in an amount up to about 97% by weight, such as about 98% by weight. For instance, the fabric material can contain only inherently flame resistant fibers in combination with anti-static fibers. The anti-static fibers, for instance, may comprise fibers containing carbon, such as bicomponent fibers containing a carbon core. The carbon core can be surrounded by any suitable polymer, such as a polyester polymer or polyamide polymer.

[0062] The inherently flame resistant fibers can include, for instance, aramid fibers such as para-aramid fibers and / or meta-aramid fibers. Other inherently flame resistant fibers include polybenzimidazole (PBI) fibers or poly(p-phenylene-2,6-bezobisoxazole) (PBO fibers) and the like. Wool fibers are also inherently flame resistant fibers.

[0063] In one embodiment, for instance, the fabric material only contains aramid fibers such as para-aramid fibers alone or in combination with meta-aramid fibers. In still another embodiment, the fabric material contains only meta-aramid fibers. In still another embodiment, the fabric material contains aramid fibers in combination with PBI fibers. The PBI fibers can be present in the fabric material, for instance, in an amount greater than about 20% by weight, such as in an amount greater than about 25% by weight, such as in an amount greater than about 30% by weight, such as in an amount greater than about 35% by weight, such as in an amount greater than about 40% by weight, such as in an amount greater than about 45% by weight, such as in an amount greater than about 50% by weight, and generally in an amount less than about 70% by weight, such as in an amount less than about 60% by weight.

[0064] In addition to any of the inherently flame resistant fibers described above, the fabric material may contain other fibers. For instance, the fabric material may also include fibers treated with a flame retardant such as FR cellulose fibers including FR viscose fibers and FR rayon fibers. In addition, the fabric material may include antistatic fibers, nylon fibers, and the like. For example, a fabric material treated in accordance with the present disclosure can contain nylon fibers in an amount up to about 20% by weight. For instance, nylon fibers can be present in an amount of from about 18% to about 2% by weight, such as from about 15% to about 8% by weight.

[0065] The yarns used to produce the fabric material can vary depending upon the particular application and the desired result. In one embodiment, for instance, the fabric material may contain only spun yarns, may contain only filament yarns, or may contain both spun yarns and filament yarns. The number ratio between spun yarns and filament yarns, for instance, can be from about 1:1 to about 10:1. For example, in one embodiment, the fabric material may contain spun yarns to filament yarns in a number ratio of from about 1:1 to about 8:1, such as from about 2:1 to about 5:1, such as from about 2:1 to about 4:1, such as from about 2:1 to about 3:1. The spun yarns and filament yarns can extend in both the warp direction and the weft direction. The yarns can be spaced such that a single filament yarn is separated by spun yarns. Alternatively, two filament yarns can be separated by spun yarns. When the fabric material is a woven fabric, the fabric can have any suitable weave such as a plain weave, a twill weave, a rip stop weave, or the like.

[0066] In one embodiment, the filament yarns may be made from an inherently flame resistant material. For example, the filament yarns may be made from an aramid filament, such as a para-aramid or a meta-aramid filament.

[0067] In other embodiments, the filament yarns may be made from other flame resistant materials. For instance, the filament yarns may be made from poly-p-phenylenebenzobisoxazole fibers (PBO fibers), and / or FR cellulose fibers, such as FR viscose filament fibers.

[0068] The filament yarns can be combined with spun yarns. Alternatively, the fabric material can be made using only filament yarns or only spun yarns. In accordance with the present 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.

[0069] Instead of or in addition to containing polybenzimidazole fibers, the spun yarns may contain aramid fibers as described above, modacrylic fibers, preoxidized carbon fibers, melamine fibers, polyamide imide fibers, wool fibers, polyimide fibers, and mixtures thereof.

[0070] In one particular embodiment, the spun yarns contain polybenzimidazole fibers in an amount greater than about 20% by weight, such as in an amount greater than about 30% by weight, such as in an amount greater than about 40% by weight. The polybenzimidazole fibers may be present in the spun yarns in an amount less than about 60% by weight, such as in an amount less than about 55% by weight. The remainder of the fibers, on the other hand, may comprise para-aramid fibers.

[0071] In one embodiment, various other fibers may be present in the spun yarns. When the fabric is used to produce turnout coats for firemen, the spun yarns can be made exclusively from inherently flame resistant fibers. When the fabric is being used in other applications, however, various other fibers may be present in the spun yarns. For instance, the spun yarns may contain fibers treated with a fire retardant, such as FR cellulose fibers. Such fibers can include FR cotton, FR rayon, FR acetate, FR triacetate, and FR lyocell, and the like. The spun yarns may also contain nylon fibers if desired, such as antistatic fibers.

[0072] In one aspect, the fabric treated with the water resistant treatment may comprise an outer shell material. The weight of the outer shell material can vary depending upon the particular type of protective garment being produced. The weight of the outer shell material, for instance, is generally greater than about 4 ounces per square yard, such as greater than about 5 ounces per square yard, such as greater than about 5.5 ounces per square yard, such as greater than about 6 ounces per square yard and generally less than about 8.5 ounces per square yard, such as less than about 8 ounces per square yard, such as less than about 7.5 ounces per square yard.

[0073] In another aspect, the fabric material treated in accordance with the present disclosure is a liner fabric. The liner fabric, for instance, can be positioned adjacent to the wearer's body during use. The lining fabric can be made from a combination of spun yarns and filament yarns as described above. The filament yarns can have a size of greater than about 100 denier, such as greater than about 200 denier, and less than about 500 denier, such as less than about 400 denier. In order to increase the lubricity of the liner fabric, the spun yarns and filament yarns can be woven together such that the filament yarns comprise more than about 50% of the surface area of one side of the fabric. For instance, the filament yarns may comprise greater than about 60%, such as greater than about 70%, such as greater than about 80% of one side of the fabric. The side of the fabric with more exposed filament yarns is then used as the interior face of the garment. The filament yarns provide a fabric with high lubricity characteristics that facilitates donning of the garment. For example, the lining fabric can be woven together using a twill weave, such as a 2x1 or 3x1 weave. The lining fabric can have a basis weight of less than about 5 ounces per square yard, such as less than about 4 ounces per square yard, and generally greater than about 2.5 ounces per square yard, such as greater than about 3 ounces per square yard.

[0074] In another aspect, the fabric material treated in accordance with the present disclosure is the barrier layer 24 as shown in FIG. 2. Barrier layer 24, for instance, can comprise a batting material, such as a felt. Once treated, the layer 24 can have the same characteristics as described above with respect to spray rating and water absorption.

[0075] In accordance with the present disclosure, the fabric material is treated with a durable water resistant treatment. In accordance with the present disclosure, the durable water resistant treatment primarily contains non-fluorinated compounds. The non-fluorinated compounds can comprise one or more binders, one or more repelling agents, one or more crosslinking agents, one or more waxes, one or more softeners, and the like. In accordance with the present disclosure, the non-fluorinated components are combined with a minor amount of a fluorocarbon compound in order to dramatically boost chemical resistance in addition to water resistance.

[0076] In one embodiment, the fluorocarbon compound can comprise a short chain fluorinated polymer or oligomer. For instance, the fluorocarbon compound can have a carbon chain length of about 6 carbon atoms or less. Short-chain fluorocarbon compounds help reduce the presence of unintentionally added regulated PFASs, including perfluorooctanoic acid (PFOA) and its salts, perfluorooctane sulfonate (PFOS) and related substances, C9-C14 perfluorocarboxylic acids and their salts, and other long-chain perfluoroalkyl carboxylic acids. For instance, the fluorocarbon compound contained in the durable water resistant treatment can be made exclusively from a C6 fluorocarbon polymer or can contain the C6 fluorocarbon polymer in an amount greater than about 50% by weight, such as in an amount greater than about 70% by weight, such as in an amount greater than about 80% by weight and can be present in combination with C3, C4, and / or C5 fluorocarbon compounds.

[0077] In one embodiment, the durable water resistant treatment and the resulting fabric material can be completely free of C8 or longer perfluorocarboxylic acids. For instance, the durable water resistant treatment or fabric material can be free of perfluorooctanoic acid. The durable water resistant treatment and the fabric material can also be free of alkylphenolethoxylates. In other embodiments, however, longer chain perfluorocarbon compounds can be present, including C8 fluorocarbon compounds.

[0078] In the past, durable water resistant treatments containing fluorocarbon polymers, typically contained the fluorocarbon polymers in an amount greater than 15% by weight, such as in an amount greater than about 16% by weight, such as in an amount greater than about 18% by weight. Fluorocarbon compounds are present in the durable water resistant treatment of the present disclosure, however, in much smaller amounts. For instance, one or more fluorocarbon compounds can be present in the durable water resistant treatment in an amount less than about 10% by weight, such as in an amount less than about 8% by weight, such as in an amount less than about 6% by weight, such as in an amount less than about 5% by weight, such as in an amount less than about 4% by weight, such as in an amount less than about 3% by weight. One or more fluorocarbon compounds can be present in the dried treatment (once applied to the fabric and dried) in an amount less than about 23% by weight, such as in an amount less than about 20% by weight, such as in an amount less than about 15% by weight, such as in an amount less than about 12% by weight, such as in an amount less than about 10% by weight. In one aspect, as described above, the resulting fabric material contains fluorine in an amount less than about 2,500 ppm, such as in an amount less than about 1,500 ppm, such as in an amount less than about 900 ppm, such as in an amount less than about 700 ppm.

[0079] In one embodiment, the fluorocarbon compound is added to the durable water resistant treatment as a blend of the fluorocarbon compound, an emulsifier, and a glycol, such as dipropylene glycol. The blend can be free of alkylphenol ethoxylates. In one aspect, the fluorinated compound can comprise a fluoroalkyl acrylate.

[0080] As described above, the non-fluorinated components contained within the durable water resistant treatment include a binder. The binder contained in the durable water resistant treatment, in one embodiment, can comprise a polyurethane polymer. Of particular advantage, the polyurethane polymer can be water-based and thus can be applied to the fabric in an aqueous dispersion. In one embodiment, the polyurethane polymer is an anionic polyurethane. The polyurethane polymer can also be an aliphatic polyurethane. In one particular embodiment, the polyurethane polymer that makes up the binder is a polyester / ether polyurethane polymer, such as an aliphatic polyester / ether polyurethane polymer.

[0081] In an alternative embodiment, the binder can comprise an acrylic polymer. The acrylic polymer, for instance, can comprise an acrylate, such as a polyacrylate polymer.

[0082] In still another embodiment, the binder can comprise a silicone polymer. The silicone polymer can comprise a polysiloxane, such as a polydimethylsiloxane. Alternatively, the silicone polymer can comprise a silane.

[0083] The durable water resistant treatment of the present disclosure can contain a single binder or can contain a blend of binders. For instance, the durable water resistant treatment can contain a polyurethane polymer in combination with a silicone polymer. Alternatively, the treatment can contain a silicone polymer in combination with an acrylic polymer. In still another embodiment, the treatment can contain a polyurethane polymer in combination with a silicone polymer. In yet another embodiment, the treatment can contain a polyurethane polymer, an acrylic polymer and a silicone polymer. In other embodiments, the binder can comprise two different types of polyurethane polymers or two different types of acrylic polymers. The polymers can differ by molecular weight, functional groups, or the like.

[0084] Optionally, the above binder can be combined with an extender, such as a crosslinking agent. The extender may also comprise a polyurethane polymer. Thus, in one embodiment, the durable water resistant treatment includes a first polyurethane polymer combined with a second polyurethane polymer. The extender, for instance, can comprise a modified polyurethane polymer. For instance, the extender may be a blocked isocyanate. The extender can be cationic or nonionic. The extender is for further increasing water and oil resistance.

[0085] When the extender is a blocked isocyanate, the extender can comprise a latent crosslinking agent. For instance, at elevated temperatures, the blocked isocyanate can cause crosslinking to occur between other polymers contained in the treatment. For instance, the crosslinking agent can cause the binder to crosslink. In one embodiment, the blocked isocyanate is free from butanoane oxime. Although in an alternative embodiment, the blocked isocyanate can comprise an oxime-blocked isocyanate.

[0086] In addition to a binder and / or an extender, in one embodiment, the durable water resistant treatment can further include a softener. The softener, for instance, 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 lower molecular weight polyethylene polymer.

[0087] The durable water resistant treatment can also contain other waxes in addition to or as an alternative to a polyethylene wax. For instance, in one embodiment, the wax can comprise the paraffin wax. In one embodiment, for instance, an acrylic polymer and a paraffin wax can be preblended and added to the durable water resistant treatment.

[0088] In one aspect, the durable water resistant treatment can also contain a repelling agent. The repelling agent can comprise, for instance, an acrylic polymer, such as a polyacrylate. The repelling agent can be different than the binder. The repelling agent, for instance, can be added not only to provide water and / or chemical resistance, but can also make the fabric more durable.

[0089] 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 can vary depending on the particular formulation. In one embodiment, for instance, the binder can be present in relation to the extender in a weight ratio of from about 20:1 to about 2:1, such as in a weight ratio of from about 10:1 to 3:1. In one embodiment, the binder and extender are present in a weight ratio of from about 8:1 to about 3:1 based on the dried weight of the finish.

[0090] When included in the formulation, the softener can generally be present in amounts less than the binder, the repelling agent or the extender. For example, in one embodiment, the softener can be present in relation to the binder in a weight ratio of from about 1:1 to about 1:4, such as from about 1:1.5 to about 1:3.

[0091] In order to produce a liquid resistant fabric in accordance with the present invention, first, a woven or knitted fabric is constructed or obtained that is suitable for use as a fabric material in a protective garment. As described above, the fabric should be made from flame resistant fibers.

[0092] Prior to applying the durable water resistant treatment, the fabric can be first scoured, although scouring may not be necessary for all applications. When scoured, the material can be scoured with an alkaline solution.

[0093] After being scoured, the fabric is then put on a tenter frame, dried and heat set. For instance, after scouring, the fabric should be dried so that the moisture level is substantially equivalent to the natural moisture level of the fibers used to make the fabric. For instance, for most fibers, the moisture level should be less than about 10%, and particularly less than about 7%.

[0094] After the fabric has been dried and heat set, a durable water resistant composition according to the present disclosure is applied to at least one side of the fabric. Although the composition can be sprayed on the fabric or printed on the fabric, preferably the fabric is dipped into a bath containing the durable water resistant treatment in dispersion form.

[0095] The amount of the water-resistant composition applied to the fabric will depend upon the particular formulation and the particular application.

[0096] After the durable water resistant treatment is applied to the fabric, the fabric is then heated to a temperature sufficient for the coating to dry and / or cure. Once the durable water resistant treatment is cured and affixed to the fabric, the fabric can then be used in constructing protective garments in accordance with the present disclosure.

[0097] In one aspect, the dried finish can contain the binder in an amount greater than about 10% by weight, such as in an amount greater than about 15% by weight, such as in an amount greater than about 20% by weight, such as in an amount greater than about 25% by weight, such as in an amount greater than about 30% by weight, such as in an amount greater than about 35% by weight, such as in an amount greater than about 40% by weight, such as in an amount greater than about 45% by weight, such as in an amount greater than about 50% by weight, such as in an amount greater than about 55% by weight, such as in an amount greater than about 60% by weight, and generally less than about 80% by weight, such as less than about 70% by weight, such as less than about 65% by weight, such as less than about 60% by weight, such as less than about 55% by weight, such as less than about 50% by weight, such as less than about 45% by weight, such as less than about 30% by weight.

[0098] The extender can be present in the dried finish in an amount greater than about 3% by weight, such as in an amount greater than about 8% by weight, such as in an amount greater than about 10% by weight, and generally in an amount less than about 30% by weight, such as in an amount less than about 25% by weight, such as in an amount less than about 20% by weight. The repelling agent can be present in the dried durable water resistant treatment in an amount greater than about 10% by weight, such as in an amount greater than about 20% by weight, such as in an amount greater than about 25% by weight, such as in an amount greater than about 35% by weight and generally in an amount less than about 70% by weight, such as in an amount less than about 65% by weight, such as in an amount less than about 55% by weight. When a softener is present, the softener can be present in the dried treatment in an amount greater than about 3% by weight, such as in an amount greater than about 10% by weight, and generally in an amount less than about 25% by weight, such as in an amount less than about 20% by weight, such as in an amount less than about 15% by weight based upon the weight of the dried water resistant treatment.

[0099] As described above, the fabric materials treated in accordance with the present disclosure have excellent water resistance. In addition, the fabric materials display excellent chemical resistance against all different types of chemicals, including fuels, oils, acids, and the like.

[0100] For example, fabric materials treated in accordance with the present disclosure can have a spray rating of at least 70 or higher, such as at least 80 or higher, such as at least 90 or higher even after ten laundry cycles. In one embodiment, for instance, the fabric can maintain a 100 spray rating after ten laundry cycles.

[0101] Similarly, the fabric material can also display excellent resistance to water absorption. For example, when tested according to the water absorption test (NFPA 1971 8.25), the fabric can have a water absorption of about 15% or less, such as about 10% or less, such as about 5% or less, such as about 4% or less, such as about 3% or less, such as about 2% or less, such as about 1 % or less. The above water absorption properties can be retained by the fabric after 5 laundry cycles or even after ten laundry cycles.

[0102] In addition to water, fabric material treated in accordance with the present disclosure also provide protection against various chemical agents such as fuels, oils and / or acids when tested according to ISO Test 6530. For example, when tested against O-xylene (which simulates diesel fuel) fabric materials treated in accordance with the present disclosure, especially fabric materials containing inherently flame resistant fibers, display an initial index of repellency of greater than about 80%, such as greater than about 83%, such as greater than about 85%, such as greater than about 87%. The fabric material can display an index of repellency after 10 laundry cycles of still greater than 80%, such as greater than about 82%. The fabric material can display an index of penetration initially and after 10 laundry cycles of less than about 10%, such as less than about 8%, such as less than about 6%, such as less than about 5%. The fabric material can display an index of absorption initially of less than about 10%, such as less than about 9%, such as less than about 8%. After 10 laundry cycles, the fabric material can display an index of absorption of less than about 20%, such as less than about 15%.

[0103] When tested against hydraulic fluid, the fabric material can display an index of repellency initially and after 10 laundry cycles of greater than about 80%, such as greater than about 85%, such as greater than about 87%. The fabric material can display an index of penetration initially and after 10 laundry cycles of less than about 3%, such as less than about 2%. The fabric material can display an index of absorption initially and after 10 laundry cycles of less than about 10%, such as less than about 8%.

[0104] When tested against a 30% sulfuric acid solution, fabric materials made according to the present disclosure can have an index of repellency of greater than about 85%, such as greater than about 95%, such as greater than about 96%, such as greater than about 97%. The fabric material can have an index of penetration when tested against a 30% sulfuric acid solution of less than about 5%, such as less than about 2%, such as less than about 1 %, such as less than about 0.5%. The fabric material can display an index of absorption of less than about 2%, such as less than about 1%, such as less than about 0.8%. The above properties can be displayed by the fabric material either initially or even after 10 laundry cycles.

[0105] Fabric materials made in accordance with the present disclosure can also display excellent abrasion resistance. For example, a fabric having a basis weight of from about 5 osy to about 9 osy, such as from about 5.5 osy to about 8.5 osy, such as from about 6 osy to about 7.5 osy can have an abrasion resistance of greater than about 90,000 cycles, such as greater than about 95,000 cycles, such as greater than about 98,000 cycles, such as greater than about 100,000 cycles when tested according to ASTM D4966 Test Method. The abrasion resistance is generally less than about 200,000 cycles.

[0106] When testing lighter fabrics, such as linear materials, fabric materials made according to the present disclosure can have an abrasion resistance of greater than about 40,000 cycles, such as greater than about 42,000 cycles, such as greater than about 44,000 cycles, such as greater than about 46,000 cycles, such as greater than about 48,000 cycles, and generally less than about 80,000 cycles. The lighter fabric materials, for instance, can have a basis weight of from about 2 osy to about 5 osy, such as from about 2 osy to about 4 osy, such as from about 2.5 osy to about 3.8 osy.

[0107] As described above, the durable water resistant treatment of the present disclosure can be formulated to be water-based. The durable water resistant treatment, for instance, can comprise an aqueous dispersion of the different ingredients or components. Thus, the durable water resistant treatment of the present disclosure is exceptionally safe for handling and use. In this regard, the durable water resistant treatment of the present disclosure can be applied to the protective garments during their useful life to further reinforce the water resistant properties of the garment. For example, in one embodiment, the durable water resistant treatment can be added to a wash cycle for absorption by the garment. The garment can then be placed in a dryer which causes the durable water resistant treatment to cure and further improve the water resistant properties of the garment.

[0108] The present disclosure may be better understood with reference to the following example.ExampleExample No. 1

[0109] The following tests were performed in order to demonstrate some of the advantages and benefits of fabrics treated in accordance with the present disclosure.

[0110] A flame resistant woven fabric suitable for use as an outer shell material was impregnated with durable water resistant treatments in accordance with the present disclosure and compared with the same fabric treated with a water resistant treatment containing conventional amounts of fluorocarbon chemicals.

[0111] The fabric that was tested is as follows: 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 spun yarn to filament yarn ratio was 2:1 and the fabric had a basis weight of 7 osy.

[0112] Durable water resistant treatments were formulated and applied to the fabric above. The durable water resistant treatments are listed in the table below. A, B, and C were in accordance with the present disclosure and compared with a conventional fluorinated DWR. Table No. 1CHEM NAME% WTFormulaCioppino ACioppino BCioppino CConventional Fluorinated DWRIPA (Isopropyl Alcohol)0.50.50.52Blocked Isocyanate3.13.33.36Blend of Acrylic Polymer and Paraffin18.218.218.2Weathering and UV resistance aid6Softener4C6 Fluoropolymer, Emulsifier, and Dipropylene Glycol (30% solids)1.52.2518-23

[0113] Fabric No. 1 above was dipped into a bath containing each of the durable water resistant treatments. The fabric was patted and dried.

[0114] Fabric No. 1 treated with treatments A, B, and C were tested according to EN Test 469 / ISO Test 6530 against O-xylene and compared to a similar commercially treated fabric that is treated with a durable water resistant treatment not containing any fluorinated compounds. The following results were obtained: Table No. 2ISO 6530 XyleneIndex of PenetrationIndex of RepellencyIndex of AbsorptionCioppino A0.4691.096.170.4690.516.512.9787.547.77Cioppino B1.7190.635.710.4692.005.031.6094.973.54Cioppino C1.7190.865.830.0095.092.863.5487.897.31Fabric treated with no fluorinated compounds38.0625.4940.5737.941.2658.29

[0115] As shown above, fabrics treated according to the present disclosure exhibited dramatically better chemical resistance.

[0116] Durable water resistant A as shown in Table 1 was then applied to Fabric No. 2. Fabric No. 2 was identical to Fabric No. 1 only had a basis weight of 6 osy. Durable water resistant treatment A was applied using a pad application. The treated fabric underwent laundering up to 10X at 40°C and tumble dried. Table 3 shows the liquid repellency of the treated fabric against hydraulic fluid and O-Xylene both before and after undergoing 10X laundering. Table No. 3LiquidWashIndex of PenetrationIndex of RepellencyIndex of AbsorptionOriginal (0X)0.1192.466.970.1190.45.371.1494.746.42.0690.971.831.7190.516.51Hydraulic fluid0.5792.574.810X0.596.344.910.990.637.310.593.493.891.1975.60.591.895.490.696.114.11Index of PenetrationIndex of RepellencyIndex of Absorption4.3487.895.940.892.576.069.0386.174.34Original (0X)0.6994.44.234.6990.975.6O-Xylene9.7184.343.895.9490.43.5410.5180.238.1110X4.2384.2310.634.4684.6913.030.9187.6610.17

[0117] Next, durable water resistant treatment B was applied to Fabric No. 1 and tested against O-xylene both before and after 10 laundry cycles. The following results were obtained: Table No. 4LiquidWashIndex of PenetrationIndex of RepellencyIndex of AbsorptionFabric No. 1 with Cioppino B0X0.696.131.894.43.11.494.62.50.697.12.71.195.13.80.195.73Fabric No. 1 with Cioppino B10X washed with CitroSqueeze096.74.30.897.93.3

[0118] Durable water resistant treatment C was then applied to Fabric No. 1 and tested against O-xylene and 30% sulfuric acid both initially and after 5 laundry cycles. The following results were obtained: Table No. 5LiquidWashIndex of PenetrationIndex of RepellencyIndex of AbsorptionOriginal (0X)0.199.30.6099.80.20.199.70.3099.70.30.898.90.3Sulfuric Acid 30%0.399.20.65X0.299.40.4099.80.20.399.30.40.399.30.30.799.10.3099.90.1Original (0X)Index of PenetrationIndex of RepellencyIndex of Absorption196.52.52.6952.52.795.320.797.51.83.794.32O-Xylene3.294.42.55X2.593.34.21.6953.3197.61.42.2952.83.191.35.62.4961.6

[0119] Fabric No. 1 treated with durable water resistant A and with durable water resistant C were then tested for fluorine content. Fluorine content was determined according to EN Test 14582 by combustion bomb with oxygen and determined using ion chromatography. Other commercially available fabrics (Style No. 1 and Style No. 2) were also tested. Both of these fabrics are made from inherently flame resistant fibers and are both treated with a conventional durable water resistant treatment containing high amounts of fluorocarbon polymers. The following results were obtained: Table No. 6Fluorine (F) Content according to EN 14582:2016 by combustion bomb with oxygen and determined by Ion Chromatography.Tested SampleResult (ppm)Limit of detection # (ppm)Fabric No. 1 treated with Cioppino A49420Fabric No. 1 treated with Cioppino C209020Style No. 1371020Style No. 2680020

[0120] As shown above, fabrics treated in accordance with the present disclosure contained extremely minor amounts of fluorine, especially in comparison to conventional fabrics. The fluorine concentration on the fabric treated in accordance with the present disclosure, for instance, is more than 13X lower than the conventional fabrics. The fabric material of the present disclosure, however, displays the same or better chemical resistant properties than the conventional fabrics even after multiple laundry cycles.Example No. 2

[0121] Treatment Cioppino C was applied to Fabric No. 1 according to the method described in Example No. 1 and tested for various properties.

[0122] The following results were obtained.

[0123] Three samples were subjected to the Spray Test: Spray Test (AATCC TM 22-2022) L C R Initial100100100After 5 Laundry Cycles100100100After 10 Laundry Cycles100100100

[0124] For the above samples, after the indicated number of laundry cycles, a single final rinse cycle with no detergent was conducted followed by a permanent press tumble dry.

[0125] Two samples were subjected to a Water Alcohol Test: Water alcohol (AATCC TM 193-2023) 1 (2% Alcohol) 2 (5% Alcohol) 3 (10% Alcohol) Initial (sample 1)AAAInitial (sample 2)AAAAfter Five Laundry Cycles (sample 1)AAAAfter Five Laundry Cycles (sample 2)AAAAfter Ten Laundry Cycles (sample 1)AAAAfter Ten Laundry Cycles (sample 2)AAA Water alcohol (AATCC TM 193-2023) 4 (20% Alcohol) 5 (30% Alcohol) 6 (40% Alcohol) Initial (sample 1)AAAInitial (sample 2)AAAAfter Five Laundry Cycles (sample 1)AAAAfter Five Laundry Cycles (sample 2)AAAAfter Ten Laundry Cycles (sample 1)AAAAfter Ten Laundry Cycles (sample 2)AAA A = PASS excellent, B=borderline PASS, C=FAIL with some beading, D=FAIL, completely wet out - AATCC TM 193

[0126] Two samples were subjected to an Oil Repellency Test: Oil repellency (AATCCTM 118-2020) 1 (Kaydol) 2 (65:35 Kaydol:n-hexadecane) 3 (n-hexadecane) Initial (sample 1)AAAInitial (sample 2)AAAAfter Five Laudry Cycles (sample 1)AAAAfter Five Laundry Cycles (sample 2)AAAAfter Ten Laundry Cycles (sample 1)AAAAfter Ten Laundry Cycles (sample 2)AAAOil repellency (AATCC TM 118-2020) 4 (n-tetradecane) 5 (n-dodecane) 6 (n-decane) Initial (sample 1)ABBInitial (sample 2)ABBAfter Five Laudry Cycles (sample 1)ABDAfter Five Laundry Cycles (sample 2)ABDAfter Ten Laundry Cycles (sample 1)ABDAfter Ten Laundry Cycles (sample 2)ABDA = PASS excellent, B=borderline PASS, C=FAIL with some beading, D=FAIL, completely wet out - AATCC TM 193

[0127] Results of Water Penetration Test (Water Absorption Resistance) and Chemical Runoff Test: Water penetration 24 hrs % water absorbed Sample 1, 0x0.3%Sample 1, 5x0.0%Sample 1, 10x0.0% Chemical Runoff, ISO 6530, 2005 edition

[0128] Xylene Ir % Avgs Sample 1, 0x100.0%Sample 1, 5x98.7%Sample 1, 10x95.4%

[0129] These and other modifications and variations to the present invention may be practiced by those of ordinary skill in the art, without departing from the spirit and scope of the present invention, which is more particularly set forth in the appended claims. In addition, it should be understood that aspects of the various embodiments may be interchanged both in whole or in part. Furthermore, those of ordinary skill in the art will appreciate that the foregoing description is by way of example only and is not intended to limit the invention so further described in such appended claims.

Examples

example

Example

Example No. 1

[0109]The following tests were performed in order to demonstrate some of the advantages and benefits of fabrics treated in accordance with the present disclosure.

[0110]A flame resistant woven fabric suitable for use as an outer shell material was impregnated with durable water resistant treatments in accordance with the present disclosure and compared with the same fabric treated with a water resistant treatment containing conventional amounts of fluorocarbon chemicals.

[0111]The fabric that was tested is as follows: 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 spun yarn to filament yarn ratio was 2:1 and the fabric had a basis weight of 7 osy.

[0112]Durable water resistant treatments were formulated and applied to the fabric above. The durable water resistant treatments are listed in the table below. A, B, and C were in accordance with the presen...

example no.2

Example No. 2

[0121]Treatment Cioppino C was applied to Fabric No. 1 according to the method described in Example No. 1 and tested for various properties.

[0122]The following results were obtained.

[0123]Three samples were subjected to the Spray Test:

Spray Test (AATCC TM 22-2022) L C R

Initial100100100

After 5 Laundry Cycles100100100

After 10 Laundry Cycles100100100

[0124]For the above samples, after the indicated number of laundry cycles, a single final rinse cycle with no detergent was conducted followed by a permanent press tumble dry.

[0125]Two samples were subjected to a Water Alcohol Test:

Water alcohol (AATCC TM 193-2023) 1 (2% Alcohol) 2 (5% Alcohol) 3 (10% Alcohol)

Initial (sample 1)AAA

Initial (sample 2)AAA

After Five Laundry Cycles (sample 1)AAA

After Five Laundry Cycles (sample 2)AAA

After Ten Laundry Cycles (sample 1)AAA

After Ten Laundry Cycles (sample 2)AAA

Water alcohol (AATCC TM 193-2023) 4 (20% Alcohol) 5 (30% Alcohol) 6 (40% Alcohol) Initial (sample 1)A...

Claims

1. A fabric for constructing protective garments comprising: a fabric material comprising inherently flame resistant fibers, the inherently flame resistant fibers comprising para-aramid fibers, meta-aramid fibers, modacrylic fibers, polybenzimidazole fibers, polybenzoxazole fibers, wool fibers, or mixtures thereof, the inherently flame resistant fibers being present in the fabric material in an amount greater than about 50% by weight, the fabric material further comprising a durable water resistant treatment, the durable water resistant treatment comprising a non-fluoride binder in combination with a fluorocarbon compound, the treated fabric containing fluorine in an amount of less than about 3,500 ppm.

2. A fabric as defined in claim 1, wherein the fabric material contains fluorine in an amount less than about 2,800 ppm, such as in an amount less than about 2,500 ppm, such as in an amount less than about 2,300 ppm.

3. A fabric as defined in any of the preceding claims, wherein the fabric material does not contain any C8 or longer chain perfluoroalkyl and polyfluoroalkyl substances such as perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorooctane sulfonate (PFOS), and long chain fluorotelomer alcohols within the chemistry (8:2 FTOH) and / or does not contain an alkylphenol ethoxylate.

4. A fabric as defined in any of the preceding claims, wherein the fabric material, when tested according to ISO Test 6530 against O-xylene, displays an index of repellency of greater than about 80%, such as greater than about 82% after 10 laundry cycles, displays an index of penetration of less than about 10%, such as less than about 6% after 10 laundry cycles, and displays an index of absorption of less than about 20%, such as less than about 15% after 10 laundry cycles, and / or wherein the fabric material, when tested according to ISO Test 6530 against hydraulic fluid, displays an index of repellency of greater than about 80%, such as greater than about 85% after 10 laundry cycles, displays an index of penetration of less than about 3%, such as less than about 2% after 10 laundry cycles, and displays an index of absorption of less than about 10%, such as less than about 8% after 10 laundry cycles, and / or wherein the fabric material, when tested according to ISO Test 6530 against 30% sulfuric acid, displays an index of repellency of greater than about 95%, such as greater than about 96% after 5 laundry cycles, displays an index of penetration of less than about 2%, such as less than about 1% after 5 laundry cycles, and displays an index of absorption of less than about 1%, such as less than about 0.8% after 5 laundry cycles.

5. A fabric as defined in any of the preceding claims, wherein the fluorocarbon compound comprises a fluoroalkyl acrylate.

6. A fabric as defined in any of the preceding claims, wherein the non-fluorinated binder comprises an acrylic polymer.

7. A fabric as defined in any of the preceding claims, wherein the non-fluorinated binder comprises a polyurethane, a silicone, or a mixture thereof.

8. A fabric as defined in any of the preceding claims, wherein the durable water resistant treatment further comprises a wax, wherein the wax preferably comprises a paraffin.

9. A fabric as defined in any of the preceding claims, wherein the durable water resistant treatment further contains a repelling agent, the repelling agent comprising an acrylic polymer.

10. A fabric as defined in any of claims 1-8, wherein the non-fluorinated binder comprises an acrylic polymer, a polyurethane polymer, a silicone polymer, or mixtures thereof, the durable water resistant treatment further comprising an acrylic repelling agent and a wax.

11. A fabric as defined in any of the preceding claims, wherein the durable water resistant treatment further comprises a blocked isocyanate.

12. A fabric as defined in any of the preceding claims, wherein the fabric material is comprised of spun yarns and multifilament yarns.

13. A fabric as defined in claim 12, wherein the filament yarns comprise aramid yarns and the spun yarns comprise a mixture of aramid fibers and polybenzimidazole fibers, the polybenzimidazole fibers being present in the spun yarns in an amount greater than about 20% by weight.

14. A fabric as defined in any of the preceding claims, wherein the fabric material has a basis weight of from about 5 osy to about 8.5 osy.

15. A protective garment made from the fabric material as defined in any of the preceding claims, wherein the fabric material preferably forms an exterior surface of the protective garment and comprises an outer shell material, and / or wherein the protective garment preferably comprises a hood.

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