Antimicrobial synthetic fabric and method of manufacturing the same

Abstract

The present disclosure relates to antimicrobial synthetic textiles and methods of making antimicrobial synthetic textiles. The disclosure further relates to the use of polycarboxylic acids as antimicrobial finishes on synthetic textiles.

Description

[Technical Field]

[0001] The present disclosure relates to antimicrobial synthetic textiles and methods of making antimicrobial synthetic textiles. The disclosure further relates to the use of polycarboxylic acids as antimicrobial finishes on synthetic textiles. [Background technology]

[0002] Antimicrobial textiles offer several benefits in professional healthcare and home environments, such as reduced microbial growth and odor control. Home textiles have always accounted for a large portion of the global textile trade. The exponential spread of COVID-19 worldwide, along with the growing demand for smart medical textiles in healthcare facilities, is also boosting the antimicrobial textile market. Synthetic polyester fabrics dominate antimicrobial fabric consumption, accounting for nearly half of the global market share, and are likely to exhibit a compound annual growth rate (CAGR) of over 9.2% by 2027.

[0003] Antimicrobial agents used in textiles range from synthetic organic compounds such as triclosan, quaternary ammonium compounds (QACs), polybiguanides, brominated phenols, and N-halamines to metals such as silver, copper, and zinc. Many of these commonly used antimicrobial agents have several undesirable properties. For example, silver ions and QACs are poorly biodegradable and, if released into the environment, are highly toxic to aquatic organisms. Additionally, some commonly used antimicrobial chemicals potentially contribute to antimicrobial resistance (AMR), i.e., the emergence of antibiotic-resistant bacteria and other types of multidrug-resistant microorganisms. Silver, copper, and zinc are known to be released in large quantities into aquatic ecosystems from antimicrobial coatings. Studies have shown that, on average, 60% of triclosan, triclocarban, and silver antimicrobials in textiles wash away after 10 washes, and up to 100% of the material washes away over time.

[0004] In addition to being effective against microorganisms, antimicrobial treatments applied to textiles must meet a variety of requirements. These include being suitable for textile processing, exhibiting durability against washing, dry cleaning, and hot pressing, exhibiting a favorable safety and environmental profile, and not impairing the quality or appearance of the textile. There is a long-standing need for synthetic textile treatment compositions that provide a durable and safe antimicrobial finish and that can be applied simply and inexpensively. Summary of the Invention

[0005] The object of the present disclosure is to provide a method for producing an antimicrobial synthetic textile, an antimicrobial synthetic textile obtainable by the method, and an antimicrobial synthetic textile to alleviate the above drawbacks. Also provided is the use of polycarboxylic acids as an antimicrobial finish on synthetic textiles, and articles of manufacture comprising the antimicrobial synthetic textile.

[0006] One aspect of the present invention is a method for producing an antimicrobial synthetic textile, comprising the steps of: a) providing a treatment solution comprising a polycarboxylic acid and a catalyst; b) applying a treatment solution onto the synthetic fabric to provide a polycarboxylic acid-treated synthetic fabric; c) curing the polycarboxylic acid treated synthetic fabric; The method includes:

[0007] A further aspect of the present invention is an antimicrobial synthetic textile obtainable by this method.

[0008] Another aspect of the invention is an antimicrobial synthetic textile, said synthetic textile comprising an antimicrobial finish comprising a polycarboxylic acid cured in the presence of a catalyst.

[0009] Yet another aspect is an article of manufacture comprising an antimicrobial synthetic fabric.

[0010] A still further aspect is the use of polycarboxylic acids as antimicrobial finishes on synthetic textiles.

[0011] Aspects of the invention are characterized by what is stated in the independent claims. Preferred embodiments of the invention are disclosed in the dependent claims. DETAILED DESCRIPTION OF THE INVENTION

[0012] As used herein, the term "polycarboxylic acid" refers to an organic compound having multiple carboxylic acid functional groups. In other words, a polycarboxylic acid is an acid having two or more carboxylic acid groups.

[0013] Cellulose fibers, such as cellulose and cotton, have many free hydroxyl (-OH) groups. When a polycarboxylic acid is applied to a fabric containing cellulose fibers to produce a finish, stable covalent bonds are formed through esterification of the hydroxide and carboxylic acid groups. Therefore, on such fabrics, antimicrobial finishes containing esterified polycarboxylic acids are automatically relatively durable.

[0014] In textile manufacturing, finishing refers to the process of transforming textiles, such as fibers, yarns, fabrics, or woven or knitted fabrics, into more usable materials to improve the appearance, performance, or "hand" (feel) of the finished textile or, for example, clothing made from the textile. Antimicrobial finishes cause textiles to inhibit microbial growth. Invasion of textiles by microorganisms can cause pathogenic infections and odors when the textile is worn or otherwise present next to the skin. Additionally, soiling of the textile substrate and degradation of fiber quality can occur. Antimicrobial finishes can be applied to textile materials to protect the wearer and the textile substrate itself.

[0015] Esterification is a traditional method used in wood modification technology. Esterifying the hydroxyl groups of cellulose with polycarboxylic acids such as citric acid (CA) is an inexpensive and environmentally friendly method for modifying cellulose. Polycarboxylic acids have been used in various applications on cotton fabrics. These traditional methods involve impregnating cotton fabrics with CA and sodium hypophosphite (SHP) solutions and heat-treating the fabric to result in esterification, where CA forms ester bonds with cellulose hydroxyls through the formation of anhydrides (Vukusic et al. Croat Med J 2011, 52:68-75).

[0016] Synthetic textiles lack free OH groups on their surfaces compared to naturally occurring textile cotton, making it impossible to esterify these synthetic materials with polycarboxylic acids. Therefore, it is difficult to produce antimicrobial synthetic textiles with durable polycarboxylic acid finishes.

[0017] The present invention relates to a method for producing an antimicrobial synthetic textile, an antimicrobial synthetic textile obtainable by said method, and an antimicrobial synthetic textile comprising an antimicrobial finish. The present invention further relates to the use of polycarboxylic acids as an antimicrobial finish on synthetic textiles, and to products comprising the antimicrobial synthetic textile.

[0018] As used herein, the term "textile" refers to a variety of fiber-based materials, including, but not limited to, fibers, yarns, filaments, threads, and different fabric types, such as woven, knit, nonwoven, and cloth. Also, as used herein, the term "fabric" is defined as any thin, flexible material made directly from yarns, fibers, polymer films, foams, or any combination of these techniques. Also, as used herein, the term "knit" refers to a fabric formed by intertwining yarns or threads into a series of interconnected loops. Also, as used herein, the term "fabric" refers to a fabric made from a fine, flexible network of yarns.

[0019] Typically, the smallest component of a fabric is fiber. As used herein, the term "natural fiber" refers to fiber obtained from plants or animals, and the term "synthetic fiber" refers to fibers produced by chemical synthesis, including semi-synthetic fibers synthesized from natural polymers. Similarly, "natural textiles" refer to textiles based on plant or animal fibers, and "synthetic textiles" refer to textiles based on chemically produced fibers, including semi-synthetic fibers synthesized from natural polymers.

[0020] In one aspect, the present invention relates to a method of making an antimicrobial synthetic textile, the method comprising the steps of: a) providing a treatment solution comprising a polycarboxylic acid and a catalyst; b) applying the treatment solution onto the synthetic textile to provide a polycarboxylic acid-treated synthetic textile; and c) curing the polycarboxylic acid-treated synthetic textile. Optionally, curing is carried out at a temperature ranging from 130°C to 180°C.

[0021] In a further aspect, the present invention relates to an antimicrobial synthetic textile obtainable by said method.

[0022] In another aspect, the present invention relates to an antimicrobial synthetic textile comprising an antimicrobial finish comprising a polycarboxylic acid cured in the presence of a catalyst, optionally wherein the curing is carried out at a temperature ranging from 130°C to 180°C.

[0023] The inventors have surprisingly found that polycarboxylic acids can be applied to synthetic textile finishes to obtain very strong antimicrobial efficacy with good wash durability. As shown by the examples, antimicrobial activity is demonstrated against both bacteria and fungi.

[0024] Without being bound by any one theory, producing a durable antimicrobial finish involves the use of a catalyst that is believed to crosslink and / or polymerize polycarboxylic acid molecules to produce a layer or network of crosslinked and / or polymerized polycarboxylic acid molecules on the surface of the textile.

[0025] The antimicrobial finishes disclosed herein represent a non-leaching technology, thus no or minimal amounts of actives are released into the environment during washing of the textile. Cross-linking and / or polymerization of polycarboxylic acid molecules is induced by curing synthetic textiles treated with one or more polycarboxylic acids at elevated temperatures in the presence of a catalyst.

[0026] As used herein, the term "curing" refers to the cross-linking and / or polymerization of polycarboxylic acid molecules on the surface of a synthetic textile by applying heat to the polycarboxylic acid. The curing reaction is believed to be enhanced by a catalyst, resulting in toughening or hardening of the polycarboxylic acid through cross-linking and / or polymerization.

[0027] As used herein, the term "or" has both the meaning of "and" and "or" (i.e., "and / or"). Furthermore, references to singular nouns include references to plural nouns, and thus, unless otherwise specified, singular terms may also have their plural references. In other words, the terms "a" or "an" can mean one or more.

[0028] As used herein, the term "comprising" includes the broader meanings of "including," "containing," and "comprehending," as well as the narrower expressions "consisting of" and "consisting only of."

[0029] As shown by the examples, antimicrobial activity from polycarboxylic acid finishes produced in accordance with the present invention is demonstrated on both synthetic textiles made from a single type of polymer and on polymer blends.

[0030] Synthetic textiles that can be used in all aspects of the present invention with an antimicrobial finish by the methods of the present disclosure include, but are not limited to, textiles made from polyester; polyamides such as nylon; polyacrylonitriles such as acrylic, modacrylic; olefins; vinylon; polyethylenes such as ultra-high molecular weight polyethylene (UHMWPE, UHMW), Dyneema, and Spectra; elastane; vinylon; aramids such as Kevlar, Nomex, and Twaron; polybenzimidazole (PBI); polyphenylene sulfide (PPS); polylactic acid (PLA); poly(p-phenylene-2,6-benzobisoxazole) (PBO); Vectran; and glass fiber, or any mixture thereof.

[0031] In other words, synthetic textiles are made from polymeric materials that do not have free hydroxyl groups in their structure, except possibly at the ends of the polymer chains. In other words, each polymer molecule can have at most one free hydroxyl group at each end or terminus of the molecule, such as the hydroxyl group of a carboxylic acid group, and there are no free hydroxyl groups in the polymer molecule between the ends. By terminus or terminus, we mean the end groups of the polymer molecules.

[0032] In some embodiments, the synthetic textile comprises or consists of a polymeric material, wherein the polymer molecules in the polymeric material contain at most one free hydroxyl group at each end of the polymer molecule and no free hydroxyl groups between the ends, and the free hydroxyl groups are independently selected from hydroxyl groups and carboxylic acid groups.

[0033] Polycarboxylic acids that may be used in the methods disclosed herein or in all aspects of the invention, including antimicrobial synthetic textiles or synthetic textiles with an antimicrobial finish, include citric acid (CA; CAS 77-92-9), isocitric acid (ICA; CAS 320-77-4), tricarballylic acid (TCA; CAS 99-14-9), 1,2,4-butanetricarboxylic acid (BTRCA; CAS 923-42-2), 1,2,3,4-butanetetracarboxylic acid (BTCA; CAS 1703-58-8), oxalic acid (CAS 144-62-7), tartaric acid (L(+)-tartaric acid CAS 87-69-4, and other isomers), succinic acid (CAS 110-15-6), malic acid (CAS 6915-15-7), malonic acid (CAS Polycarboxylic acids include, but are not limited to, glutamic acid (L-isomer CAS 56-86-0 and other isomers), aspartic acid (L-isomer CAS 56-84-8 and other isomers), glutaric acid (CAS 110-94-1), 1,3,5-pentanetricarboxylic acid (CAS 6940-58-5), gluconic acid, mannaric acid, galactaric acid, maleic acid, and adipic acid. Polycarboxylic acids may also be in any isomeric, salt, or hydrate form, including, but not limited to, sodium citrate, anhydrous (CAS 13742-35-0) and citric acid monohydrate (CAS 5949-29-1).

[0034] All aspects of the present invention, including the antimicrobial synthetic fabrics and methods of the present invention, involve a catalyst believed to enhance the rate of crosslinking and / or polymerization reactions between polycarboxylic acid molecules. In all aspects of the present invention, the catalyst may be sodium hypophosphite, anhydrous CAS 7681-53-0 (SHP; NaH2PO2), or an SHP hydrate such as CAS 123333-67-5 or monohydrate CAS 10039-56-2; or monosodium phosphate, anhydrous CAS 7558-80-7 (MSP; NaH2PO4), or an MSP hydrate such as monohydrate CAS 10049-21-5 or dihydrate CAS 10049-21-5, or any mixture thereof.

[0035] In some embodiments, the polycarboxylic acid and the catalyst are provided dissolved in a solvent. Thus, the treatment solution that is cured to form an antimicrobial finish includes the polycarboxylic acid, the catalyst, and the solvent. Suitable solvents include, but are not limited to, one or more solvents selected from aqueous solvents, water, alcohol, ether, ethyl acetate, ketone, or DMSO. That is, any one of the listed solvents or any mixture of the listed solvents that is suitable for dissolving the polycarboxylic acid in question is also suitable for use in the antimicrobial synthetic textile and method of the present invention. Preferably, the solvent is an aqueous solvent such as water or a water-alcohol mixture.

[0036] In some embodiments, the concentration of polycarboxylic acid in the processing solution ranges from 1 to 20 wt.%, preferably 2 to 18 wt.%, more preferably 5 to 15 wt.%, and even more preferably 6 to 14 wt.%, based on the total weight of the processing solution. Additionally or alternatively, polycarboxylic acid concentrations of 1 wt.%, 2 wt.%, 3 wt.%, 4 wt.%, 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, 10 wt.%, 11 wt.%, 12 wt.%, 13 wt.%, 14 wt.%, 15 wt.%, 16 wt.%, 17 wt.%, 18 wt.%, 19 wt.%, or 20 wt.%, based on the total weight of the processing solution, or a concentration range between any two of the foregoing concentrations, can be used in the processing solution.

[0037] In some embodiments, the catalyst concentration in the treatment solution ranges from 1 to 20 wt%, preferably 2 to 18 wt%, more preferably 5 to 15 wt%, and even more preferably 6 to 14 wt%, based on the total weight of the treatment solution. Additionally or alternatively, catalyst concentrations of 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, or 20 wt%, based on the total weight of the treatment solution, or a concentration range between any two of the foregoing concentrations, may be used in the treatment solution.

[0038] Polycarboxylic acids, especially citric acid and isocitric acid, can begin to degrade at temperatures above 175°C. For this reason, textiles treated with polycarboxylic acids such as CA or ICA may have a tendency to yellow, especially at high temperatures and / or during long heat treatments, due to the decomposition of the polycarboxylic acids into unsaturated acids such as aconitic acid. Therefore, it is also important to maintain short cure times to avoid degradation.

[0039] According to the results shown in Example 3, wash-durable antimicrobial activity was achieved when curing was carried out at temperatures ranging from 150°C to 180°C. However, the inventors expect that in larger scale industrial applications, heat transfer to the fabric in the industrial dryer will be more efficient than in laboratory-scale experiments such as Example 3. Therefore, lower temperatures of 130°C or 140°C will be sufficient at the industrial scale compared to laboratory-scale curing.

[0040] In some embodiments, curing is carried out on the methods disclosed herein or antimicrobial synthetic textiles or synthetic textiles comprising an antimicrobial finish at temperatures of 130° C. to 180° C., or 135° C. to 180° C., or 140° C. to 180° C., or 145° C. to 180° C., or 150° C. to 180° C., or 150° C. to 175° C., or 150° C. to 170° C. Additionally or alternatively, the curing temperature can be 130° C., 135° C., 140° C., 145° C., 150° C., 155° C., 160° C., 165° C., 170° C., 175° C., or 180° C., or any temperature range between any two of the temperatures of 130° C., 135° C., 140° C., 145° C., 150° C., 155° C., 160° C., 165° C., 170° C., 175° C., or 180° C.

[0041] In another embodiment, curing is carried out on the methods disclosed herein or on the antimicrobial synthetic textile or synthetic textile including the antimicrobial finish for a period ranging from 5 to 180 seconds, or from 10 to 150 seconds, or from 15 to 120 seconds, or from 30 to 60 seconds. Additionally or alternatively, the cure time can be 5 seconds, 10 seconds, 15 seconds, 20 seconds, 25 seconds, 30 seconds, 35 seconds, 40 seconds, 45 seconds, 50 seconds, 55 seconds, 60 seconds, 65 seconds, 70 seconds, 75 seconds, 80 seconds, 85 seconds, 90 seconds, 95 seconds, 100 seconds, 105 seconds, 110 seconds, 115 seconds, or 120 seconds, or any time range between any two of the 5, 10, 15, 20 seconds, 25 seconds, 30 seconds, 35 seconds, 40 seconds, 45 seconds, 50 seconds, 55 seconds, 60 seconds, 65 seconds, 70 seconds, 75 seconds, 80 seconds, 85 seconds, 90 seconds, 95 seconds, 100 seconds, 105 seconds, 110 seconds, 115 seconds, or 120 second periods.

[0042] The inventors have also surprisingly discovered that a single-step process of curing can also be used to simultaneously dry synthetic textiles - in other words, a two-step process with a separate drying step before the curing step is not required to achieve a durable antimicrobial finish.

[0043] As used herein, the term "drying" refers to the application of heat to a synthetic textile to achieve a reduction in moisture content. Typically, drying is carried out at a lower temperature than curing, for example, to avoid degradation of polycarboxylic acids and to avoid the onset or initiation of curing reactions. Single-stage curing provides a rapid and energy-efficient process compared to traditional two-stage drying and curing.

[0044] In some embodiments, in the methods or antimicrobial synthetic textiles disclosed herein, a drying step by applying heat to the polycarboxylic acid-treated synthetic textile is not performed prior to the curing step. In other words, drying is achieved in a single curing step performed at a temperature of 130°C to 180°C, or 135°C to 180°C, or 140°C to 180°C, or 145°C to 180°C, or 150°C to 180°C, or 150°C to 175°C, or 150°C to 170°C. Additionally or alternatively, the temperature can be 130°C, 135°C, 140°C, 145°C, 150°C, 155°C, 160°C, 165°C, 170°C, 175°C or 180°C, or any temperature range between any two of the temperatures 130°C, 135°C, 140°C, 145°C, 150°C, 155°C, 160°C, 165°C, 170°C, 175°C or 180°C.

[0045] Preferably, the single curing step is carried out for a period in the range of 5 to 180 seconds, or 10 to 150 seconds, or 15 to 120 seconds, or 30 to 60 seconds. Additionally or alternatively, the cure time can be 5 seconds, 10 seconds, 15 seconds, 20 seconds, 25 seconds, 30 seconds, 35 seconds, 40 seconds, 45 seconds, 50 seconds, 55 seconds, 60 seconds, 65 seconds, 70 seconds, 75 seconds, 80 seconds, 85 seconds, 90 seconds, 95 seconds, 100 seconds, 105 seconds, 110 seconds, 115 seconds, or 120 seconds, or any time range between any two of the 5, 10, 15, 20 seconds, 25 seconds, 30 seconds, 35 seconds, 40 seconds, 45 seconds, 50 seconds, 55 seconds, 60 seconds, 65 seconds, 70 seconds, 75 seconds, 80 seconds, 85 seconds, 90 seconds, 95 seconds, 100 seconds, 105 seconds, 110 seconds, 115 seconds, or 120 second periods.

[0046] As used herein, the term "wet pick-up" refers to the amount of fluid or solution, by weight percent, picked up by the fabric during a method step. Wet pick-up is affected by factors such as fabric properties and solution properties. As used herein, the term "dry pick-up" refers to the amount of treatment chemical, by weight percent, remaining on the fabric after the solution or solvent liquid has evaporated.

[0047] The inventors have discovered that combinations of polycarboxylic acid concentrations, such as citric acid concentrations, and catalyst concentrations, such as SHP concentrations, in the wet pick-up range of 0.5% to 20% polycarboxylic acid and catalyst dry pick-up yield durable antimicrobially effective finishes. Preferably, the polycarboxylic acid and catalyst dry pick-up ranges from 2% to 18% or 3% to 15%. Additionally or alternatively, the dry pick-up can be 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% or 20% or any wet pick-up range between any two of the wet pick-up values ​​of 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% or 20%.

[0048] As will be readily understood by those skilled in the art, adjustment of the dry pick-up of a textile can be accomplished by adjusting the wet pick-up or concentration of the treatment chemicals. As illustrated in the examples herein, treating a synthetic textile with a 10% by weight CA solution, a 10% by weight SHP solution, and 70% wet pick-up results in a dry pick-up of 7% for both CA and SHP.

[0049] In a further aspect, the present invention relates to the use of a polycarboxylic acid as an antimicrobial finish on synthetic textiles, wherein the polycarboxylic acid is one or more selected from citric acid (CA), isocitric acid (ICA), tricarballylic acid (TCA), 1,2,4-butanetricarboxylic acid (BTRCA), 1,2,3,4-butanetetracarboxylic acid (BTCA), oxalic acid, tartaric acid, succinic acid, malic acid, malonic acid, glutamic acid, aspartic acid, glutaric acid, 1,3,5-pentanetricarboxylic acid, gluconic acid, mannaric acid, galactaric acid, maleic acid, and adipic acid, or salts, hydrates, or isomers thereof.

[0050] In some embodiments, in the use of polycarboxylic acids as antimicrobial finishes on synthetic textiles, the polycarboxylic acids are cured in the presence of a catalyst selected from sodium hypophosphite (SHP), monosodium phosphate (MSP), or any mixture thereof.

[0051] All of the embodiments disclosed herein in the context of the antimicrobial synthetic textiles of the present invention and the methods of making the antimicrobial synthetic textiles of the present invention also apply to the use of polycarboxylic acids as antimicrobial finishes on synthetic textiles.

[0052] In a still further aspect, the present invention relates to any item and / or product made from the antimicrobial synthetic textile or synthetic textile comprising an antimicrobial finish obtainable by the method of the present invention, including, but not limited to, clothing, furniture, interior decoration, and products for healthcare and hospital use.

[0053] In one aspect, the present invention relates to products made from, containing, or comprising the antimicrobial synthetic textile. The antimicrobial synthetic textile can be produced by the method of the present invention. The products can be selected from clothing; footwear; personal protective equipment; accessories such as hats, scarves, gloves, belts, and ties; bags; luggage; backpacks; towels; interior textiles such as bedding, cushions, throws, curtains, drapes, upholstery, floor and wall coverings, and car interiors; sports and outdoor equipment, medical textiles such as wound dressings, bandages, masks, gloves, and surgical gowns; toys; industrial products such as filters, conveyor belts, geotextiles, industrial fabrics, shade netting, crop covers, packaging, insulation, gaskets, seals, and tire cords; and electronic devices such as headphones, microphones, and speakers.

[0054] Regarding discoloration of textiles treated with polycarboxylic acids due to the formation of colored decomposition products, the use of polyols in the treatment solution can prevent yellowing of the textile. This is because the presence of polyols is expected to prevent undesirable side reactions that produce unsaturated acids such as aconitic acid. Such polyols include, but are not limited to, xylitol, sorbitol, glycerol, and pentaerythritol. Furthermore, the use of BTCA, TBA, and / or BTRCA as the polycarboxylic acid is believed to prevent or reduce the formation of yellow by-products because these polycarboxylic acids form anhydrides upon heating without producing significant amounts of unsaturated acids.

[0055] In certain embodiments, the antimicrobial synthetic textiles and methods and uses of the present invention involve a polyol selected from xylitol, sorbitol, glycerol, pentaerythritol, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, polyethylene glycol (PEG) 200, PEG 400, PEG 600, tris(methylol)ethane, and any combination thereof. The polyol may be included in a treatment solution comprising a polycarboxylic acid and a catalyst, i.e., the polyol is applied to the synthetic textile along with the polycarboxylic acid before curing to produce the antimicrobial finish.

[0056] In some embodiments, the polyol is included in the treatment solution at a concentration ranging from 0.1 to 5 wt.%, preferably 0.2 to 3 wt.%, more preferably 0.3 to 2 wt.%, and even more preferably 0.5 to 1 wt.%, based on the total weight of the treatment solution. Additionally or alternatively, a polyol concentration of 0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%, 0.6 wt.%, 0.7 wt.%, 0.8 wt.%, 0.9 wt.%, 1.0 wt.%, 1.1 wt.%, 1.2 wt.%, 1.3 wt.%, 1.4 wt.%, 1.5 wt.%, 1.6 wt.%, 1.7 wt.%, 1.8 wt.%, 1.9 wt.%, 2.0 wt.%, 2.5 wt.%, 3.0 wt.%, 3.5 wt.%, 4.0 wt.%, 4.5 wt.%, or 5.0 wt.%, based on the total weight of the treatment solution, or a concentration range between any two of the foregoing concentrations, may be used in the treatment solution.

[0057] The treatment solution may contain additional auxiliary ingredients, including terpene-containing essential oils (e.g., peppermint oil) for antimicrobial effectiveness and odor control. Odor control may also be achieved with metal oxides. As will be readily understood by those skilled in the art, additional auxiliary ingredients may include surfactants to reduce the surface tension of water, rheology modifiers to change the rheology of the solution, antifoam additives such as polydimethylsiloxane to reduce foaming, and additional biocides approved for use in the textile industry. Surfactants can alleviate problems caused by water hardness. Preferably, the surfactant is a bio-based surfactant, such as a green nonionic surfactant. Water-soluble polymers may act as rheology modifiers.

[0058] Polycarboxylic acids each have their own pK a For example, citric acid has pK values ​​of 3.128, 4.761, and 6.396 at 25°C. aCitric acid is a tricarboxylic acid with a pK of 1. The most effective range for antimicrobial activity is below pH 3.1, where at least half of the CA molecules have all three carboxylic acid groups protonated, i.e., the CA is in the H3A form. For example, at pH 4.7, none of the CA is in the H3A form, half is in the H2A form, and half is in the HA form. The same applies to its own specific pK a The values ​​also apply to other polycarboxylic acids.

[0059] The present inventors have surprisingly discovered that the pH of the treatment solution affects the quality of the resulting antimicrobial finish. Using a pH in the range of 2 to 7 for the treatment solution applied to the synthetic textile to produce the polycarboxylic acid-treated synthetic textile results in the most durable finish. In some cases, the pH can range from 2 to 6, or 2 to 5, or 2 to 4, or 2 to 3. As will be readily understood by those skilled in the art, adjusting the pH of the treatment solution can be accomplished using an acid and / or a base.

[0060] GRAS (Generally Recognized as Safe) additives can be safely used for odor reduction and bacterial control in textile materials. GRAS substances are food substances that are generally recognized by qualified experts as safe under the intended conditions of use and are therefore not subject to premarket review and approval by the FDA. These include citric acid, malic acid, and their derivatives. Among GRAS substances, there is a group that is listed as minimal risk pesticides and therefore can claim to have antimicrobial efficacy when used in textiles. Citric acid is included in this group.

[0061] In addition, other naturally occurring GRAS substances, such as chitosan and chitosan derivatives, are considered safe green antimicrobial substances. Chitosan has broad-spectrum antimicrobial activity based on quaternary nitrogen and is particularly effective at pH values ​​below 6. Chitosan can provide a synergistic antimicrobial effect when combined with polycarboxylic acids in all aspects of the present invention, such as the method for producing an antimicrobial synthetic textile or the antimicrobial textile or use according to the present invention.

[0062] Citric acid is an active substance listed in Annex I (EU) that has been identified as a low-risk substance. Biocidal products containing such substances with low toxicity are eligible for the simplified authorization procedure in the EU. For example, silver-based technologies are not considered low-risk because their mode of action is based on leaching, which is essentially "toxic by design." The development of antimicrobial textile finishes is required to meet an appropriate level of "Safety by Design" (SbD) strategy. The SbD concept refers to identifying risks and uncertainties related to humans and the environment early in the innovation process to minimize uncertainty, potential hazards, and / or exposure. The SbD approach addresses the safety of materials / products and related processes throughout their entire lifecycle, from the research and development (R&D) stage to production, use, recycling, and disposal. Citric acid is safe for the environment and poses no risk to humans. Citric acid is naturally found in fruits and vegetables, particularly citrus fruits.

[0063] In some embodiments, the methods of the present invention may include treating the antimicrobial synthetic textile with one or more additional textile treatment agents or substances that improve the properties of the textile.

[0064] In a further aspect, the antimicrobial synthetic textiles of the present invention may be treated with additional textile treatments or substances that improve the properties of the textile. Thus, the synthetic textiles include, in addition to the antimicrobial finish, a finish with one or more additional textile treatments or substances.

[0065] In still a further aspect, the use of the present invention, i.e., the use of polycarboxylic acids as an antimicrobial finish on synthetic textiles, may include treating the antimicrobial synthetic textile with one or more additional textile treatment agents or substances that improve the properties of the textile.

[0066] Such one or more additional agents or substances may be added to a treatment solution containing a polycarboxylic acid and a catalyst that is cured to form the antimicrobial finish. Additionally or alternatively, treating the textile with the additional agent(s) may be carried out in a separate step that precedes or follows the antimicrobial finishing step.

[0067] The additional textile treatment agents or substances may be selected from one or more of anti-wrinkle agents, shrinkage control agents, optical brighteners, water repellents, oil repellents, self-cleaning agents, flame retardants, softeners, odor absorbers, odor control agents, antibacterial agents, antifungal agents, antiviral agents, insect repellents, moisture management agents, antistatic agents, anti-pilling agents, anti-slip agents, and UV protection agents. In one embodiment, the antibacterial agent is chitosan.

[0068] The following embodiments are further provided:

[0069] 1. A method for producing an antimicrobial synthetic textile, comprising: a) providing a treatment solution comprising a polycarboxylic acid and a catalyst; b) applying a treatment solution onto the synthetic fabric to produce a polycarboxylic acid-treated synthetic fabric; c) curing the polycarboxylic acid treated synthetic fabric; Including, the polycarboxylic acid is one or more selected from citric acid (CA), isocitric acid (ICA), tricarballylic acid (TCA), 1,2,4-butanetricarboxylic acid (BTRCA), 1,2,3,4-butanetetracarboxylic acid (BTCA), oxalic acid, tartaric acid, succinic acid, malic acid, malonic acid, glutamic acid, aspartic acid, glutaric acid, 1,3,5-pentanetricarboxylic acid, or a salt or hydrate or isomer thereof; The process wherein the catalyst is one or more selected from sodium hypophosphite (SHP), SHP hydrate, monosodium phosphate (MSP), MSP hydrate, or any mixture thereof.

[0070] 2. The method of embodiment 1, wherein curing is carried out at a temperature ranging from 150°C to 180°C, or from 150°C to 175°C, or from 160°C to 175°C, or from 160°C to 170°C, or from 150°C to 170°C.

[0071] 3. The method of embodiment 1 or embodiment 2, wherein curing is carried out for a period ranging from 30 to 180 seconds, or from 30 to 150 seconds, or from 30 to 120 seconds, or from 60 to 120 seconds.

[0072] 4. The method of any one of the preceding embodiments 1 to 3, wherein the treatment solution has a pH in the range of 2 to 7, or 2 to 6, or 2 to 5, or 2 to 4, or 2 to 3.

[0073] 5. The method of any one of the preceding embodiments 1 to 4, wherein the dry pick-up of polycarboxylic acid and / or catalyst is in the range of 3% to 12%, preferably in the range of 4% to 10% or 5% to 9%.

[0074] 6. The method of any one of the preceding embodiments 1 to 5, wherein the synthetic fabric is selected from polyester; polyamide such as nylon; polyacrylonitrile such as acrylic, modacrylic; olefin; Vinyon; polyethylene such as ultra-high molecular weight polyethylene (UHMWPE, UHMW), Dyneema, and Spectra; elastane; vinylon; aramid such as Kevlar, Nomex, and Twaron; polybenzimidazole (PBI); polyphenylene sulfide (PPS); polylactic acid (PLA); poly(p-phenylene-2,6-benzobisoxazole) (PBO); Vectran; glass fiber, or any mixture thereof.

[0075] 7. The method of any one of the preceding embodiments 1 to 6, wherein the polycarboxylic acid and catalyst are dissolved in a solvent selected from an aqueous solvent, water, an alcohol, an ether, ethyl acetate, a ketone, DMSO, or any mixture thereof to produce the treatment solution.

[0076] 8. An antimicrobial synthetic textile produced by the method of any one of embodiments 1 to 7.

[0077] 9. A synthetic textile comprising an antimicrobial finish comprising a polycarboxylic acid cured in the presence of a catalyst, wherein the polycarboxylic acid is one or more selected from citric acid (CA), isocitric acid (ICA), tricarballylic acid (TCA), 1,2,4-butanetricarboxylic acid (BTRCA), 1,2,3,4-butanetetracarboxylic acid (BTCA), oxalic acid, tartaric acid, succinic acid, malic acid, malonic acid, glutamic acid, aspartic acid, glutaric acid, 1,3,5-pentanetricarboxylic acid, or salts or hydrates or isomers thereof, and the catalyst is one or more selected from sodium hypophosphite (SHP), SHP hydrate, monosodium phosphate (MSP), MSP hydrate, or any mixture thereof.

[0078] 10. The synthetic textile of embodiment 9, wherein curing is carried out at a temperature ranging from 150°C to 180°C, or from 150°C to 175°C, or from 160°C to 175°C, or from 160°C to 170°C, or from 150°C to 170°C, and optionally, curing is carried out for a period ranging from 30 to 180 seconds, or from 30 to 150 seconds, or from 30 to 120 seconds, or from 60 to 120 seconds.

[0079] 11. The synthetic textile of embodiment 9 or embodiment 10, wherein the dry pick-up of the polycarboxylic acid and / or catalyst is in the range of 3% to 12%, preferably in the range of 4% to 10% or 5% to 9%.

[0080] 12. The synthetic fabric of any one of embodiments 9 to 11, wherein the synthetic fabric is selected from polyester; polyamide such as nylon; polyacrylonitrile such as acrylic, modacrylic; olefin; vinylon; polyethylene such as ultra-high molecular weight polyethylene (UHMWPE, UHMW), Dyneema, and Spectra; elastane; vinylon; aramid such as Kevlar, Nomex, and Twaron; polybenzimidazole (PBI); polyphenylene sulfide (PPS); polylactic acid (PLA); poly(p-phenylene-2,6-benzobisoxazole) (PBO); Vectran; glass fiber, or a mixture thereof.

[0081] 13. Use of a polycarboxylic acid as an antimicrobial finish on a synthetic textile, wherein the polycarboxylic acid is one or more selected from citric acid (CA), isocitric acid (ICA), tricarballylic acid (TCA), 1,2,4-butanetricarboxylic acid (BTRCA), 1,2,3,4-butanetetracarboxylic acid (BTCA), oxalic acid, tartaric acid, succinic acid, malic acid, malonic acid, glutamic acid, aspartic acid, glutaric acid, 1,3,5-pentanetricarboxylic acid, or salts, hydrates or isomers thereof.

[0082] 14. The use according to embodiment 13, wherein the polycarboxylic acid is cured in the presence of a catalyst, and the catalyst is one or more selected from sodium hypophosphite (SHP), SHP hydrate, monosodium phosphate (MSP), MSP hydrate, or any mixture thereof.

[0083] 15. The use according to embodiment 13 or 14, wherein the synthetic fabric is selected from polyester; polyamides such as nylon; polyacrylonitriles such as acrylic and modacrylic; olefins; vinylon; polyethylenes such as ultra-high molecular weight polyethylene (UHMWPE, UHMW), Dyneema and Spectra; elastane; vinylon; aramids such as Kevlar, Nomex and Twaron; polybenzimidazole (PBI); polyphenylene sulfide (PPS); polylactic acid (PLA); poly(p-phenylene-2,6-benzobisoxazole) (PBO); Vectran; glass fiber, or a mixture thereof. [Example]

[0084] Example 1 Example 1 demonstrates a method for antimicrobially finishing synthetic textiles with citric acid using sodium hypophosphite as a catalyst, which involves a two-step heat treatment that separately dries and cures the textile.

[0085] An aqueous treatment solution was prepared as follows: Citric acid (CAS No. 77-92-9) and sodium hypophosphite (SHP) monohydrate (CAS No. 10039-56-2) were in solid form when dissolved in distilled water at room temperature. The final concentrations were 10% by weight for citric acid and 10% by weight for SHP. The citric acid was dissolved first, and the SHP was added after all the citric acid was visibly dissolved.

[0086] Polyester fabric samples were immersed in a 10% by weight citric acid, 10% by weight SHP working solution, swirled for 1 minute, and then either padded to approximately 70% pickup or allowed to dry after immersion. The wet samples were placed in a stenter frame and first fully dried at 100°C for 10 minutes, then cured at 150°C for 90 seconds. After curing, the fabric samples were allowed to rehydrate overnight at room temperature and then prepared for further processing. The materials were rinsed thoroughly with tap water and then laundered. Laundering included either 0 or 10 wet-on-wet domestic wash cycles at 40°C. Laundering was performed according to the 4N program of the ISO 6330 standard in an Electrolux Professional Washer FOM71 CLS using ECE-2 standard detergent. All samples were rinsed thoroughly in deionized water before analysis.

[0087] The durability of the treated fabric and the resulting antimicrobial protection were determined by a screening test based on standard ISO 20743. Briefly, 3.6 × 10 4 Staphylococcus aureus cells were inoculated. After a 21-hour contact time, viable S. aureus cells were shaken off the specimens with 20 ml of tryptone soy broth supplemented with 0.07% lecithin and 0.5% Tween®. Serial dilutions of the shaken off fluid were plated onto tryptone soy agar plates, and the S. aureus cells were quantified by counting colonies after 24 hours of incubation.

[0088] The antibacterial activity value (A) was calculated according to formula [1]: A=(lgC t -lgC0)-(lgT t -lgT0)=FG [1] where F is the growth value on the control specimen (F = (lgC t -lgC0)); G is the growth value on the antibacterial test specimen (G = (lgT t-lgT0)) and lg C t is the common logarithm of the bacterial count obtained from the control sample after 18 to 24 hours of incubation; lg C0 is the common logarithm of the bacterial count in the inoculum; lg T t (Ig T0 is the common logarithm of the bacterial count obtained from the antimicrobial test specimen after 18-24 hours of incubation; lg T0 is the common logarithm of the bacterial count in the inoculum.) The data used to calculate the A values ​​and A are shown in Table 1.

[0089] [Table 1]

[0090] The results showed an A value of 5.8 for both the treated and unwashed polyester fabrics, indicating a greater than 5-log (99.999%) reduction in S. aureus colonies compared to the untreated control polyester fabric. The ISO 20743 (2021) standard provides the following criteria for the effectiveness of antimicrobial properties: log reduction < 2 = low antimicrobial activity; log reduction 2-3 = significant antimicrobial activity; log reduction > 3 = strong antimicrobial activity. Therefore, the treated fabrics retained strong antimicrobial activity against Staphylococcus aureus even after 10 wash cycles.

[0091] Example 2 Example 2 illustrates the preparation of an aqueous treatment solution based on a crosslinker, citric acid, and a catalyst, sodium hypophosphite monohydrate; the production of a polyester material with antimicrobial properties; and the demonstration of the antimicrobial properties of the produced polyester fabric against gram-positive and gram-negative bacteria after various wash cycles.

[0092] To prepare the aqueous treatment solution, solid forms of citric acid, anhydrous (CA; CAS No. 77-92-9) and sodium hypophosphite monohydrate (SHP; CAS No. 10039-56-2) were dissolved in tap water at room temperature. The final concentrations were 9 wt% for CA and 9 wt% for SHP. Citric acid was dissolved first, and after all the CA was visibly dissolved, SHP was added. To examine the effect of citric acid alone, a similar CA solution was prepared without SHP in the solution.

[0093] Polyester materials with antimicrobial properties were produced by immersing polyester fabric samples in two different working solutions containing a) 9 wt% citric acid and 9 wt% sodium hypophosphite monohydrate, or b) 9 wt% citric acid, swirling for 1 minute, and then padding to approximately 70% pickup. The wet samples were placed in a stenter frame and dried and cured in one step at 160°C for 90 seconds. After curing, the fabric samples were rehydrated overnight at room temperature. The treated textile materials were rinsed thoroughly with tap water and then subjected to laundering. Laundering included either 0, 10, or 25 wet-on-wet domestic wash cycles at 40°C. Laundering was performed in an Electrolux Professional Washer FOM71 CLS using the 4N program of the ISO 6330 standard (2021) using ECE-2 standard detergent. All samples were rinsed thoroughly in deionized water before analysis.

[0094] The durability of the treated fabric and the resulting antimicrobial protection were determined by a screening test based on standard ISO 20743 (2021). Briefly, treated polyester fabric pieces (0.4 g) were soaked in 4.5 × 10 4 Gram-positive Staphylococcus aureus (ATCC 6538) or 4.7 × 10 cells 4The specimens were inoculated with either Gram-negative Klebsiella pneumoniae (ATCC 4352) or 100% ethanol. After an overnight contact period, viable bacterial cells were shaken off from the specimens using 20 ml of tryptone soy broth supplemented with 0.07% lecithin (wt.) and 0.5% Tween® (vol.). Serial dilutions of the shaken off broth were plated onto tryptone soy agar plates, and bacterial cells were quantified by counting colonies after overnight incubation.

[0095] The antibacterial activity value (A) was calculated in the same manner as in Example 1. The A value and the data used to calculate A are shown in Tables 2 and 3.

[0096] [Table 2]

[0097] [Table 3]

[0098] The ISO 20743 standard (2021) provides the following criteria for antimicrobial effectiveness: log reduction <2 = low antimicrobial activity; log reduction 2–3 = significant antimicrobial activity; log reduction >3 = strong antimicrobial activity. Results with gram-positive Staphylococcus aureus (S. aureus) showed that samples treated with citric acid and sodium hypophosphite monohydrate had strong antimicrobial activity (log reduction >3) after rinsing and 10 or 25 wash cycles. CA alone showed significant antimicrobial activity (log reduction 2–3) for rinsed samples, but after 10 or 25 wash cycles, only low antimicrobial activity remained. Results with the gram-negative bacterium Klebsiella pneumoniae were essentially the same, except that after 25 wash cycles, samples treated with CA and SHP had significant, rather than strong, antimicrobial activity.

[0099] Example 3 Example 3 shows the effect of drying and curing temperature on the formation of antimicrobial properties on polyester fabric.

[0100] To prepare the aqueous treatment solution, solid forms of citric acid, anhydrous (CA; CAS No. 77-92-9) and sodium hypophosphite monohydrate (SHP; CAS No. 10039-56-2) were dissolved in tap water at room temperature. The final concentrations were 9 wt. % for CA and 9 wt. % for SHP. Xylitol (CAS 87-99-0) was added to the treatment solution to a final concentration of 0.5 wt. % to reduce yellowing of the textile samples. The pH of the treatment solution was 3.0.

[0101] Polyester materials with antimicrobial properties were produced by immersing polyester fabric samples in the treatment solution, swirling for 1 minute, and then padding to approximately 70% pickup. The wet samples were placed in a stenter frame and dried and cured in one step at either 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, or 180°C for 90 seconds. After curing, the fabric samples were rehydrated overnight at room temperature. The treated textile materials were rinsed thoroughly with tap water and then subjected to laundering. Laundering consisted of 10 wet-on-wet domestic wash cycles at 40°C. Laundering was performed in an Electrolux Professional Washer FOM71 CLS using the 4N program of the ISO 6330 standard (2021) with ECE-2 standard detergent. All samples were rinsed thoroughly in deionized water before analysis.

[0102] The durability of the treated fabric and the resulting antimicrobial protection were determined by a screening test based on standard ISO 20743 (2021). Briefly, 4.8 × 10 β-glucan was applied to a treated polyester fabric piece (0.4 g). 4The specimens were inoculated with gram-positive Staphylococcus aureus (ATCC 6538). After an overnight contact time, surviving bacterial cells were shaken off from the specimens with 20 ml of tryptone soy broth supplemented with 0.07% lecithin and 0.5% Tween®. Serial dilutions were plated onto tryptone soy agar plates, and bacterial cells were quantified by counting colonies after overnight incubation.

[0103] The antibacterial activity value (A) was calculated in the same manner as in Example 1. The A value and the data used to calculate A are shown in Table 4.

[0104] [Table 4]

[0105] The results showed that strong antimicrobial activity (log reduction >3) against Gram-positive Staphylococcus aureus (S. aureus) was achieved when the drying and curing steps were performed at either 160°C or 170°C. Furthermore, significant antimicrobial activity was achieved when the drying and curing steps were performed at 150°C, and low antimicrobial activity was achieved when the drying and curing steps were performed at 180°C. However, we expect that in larger-scale industrial applications, heat transfer to the fabric in the industrial dryer will be more efficient than in laboratory-scale experiments such as this example. Therefore, lower temperatures will be sufficient at the industrial scale compared to laboratory-scale drying and curing. Drying and curing temperatures of 130°C or 140°C are likely to be sufficient.

[0106] By visual inspection, no yellowing of the fabric was observed even at 180° C. This is believed to be influenced by the presence of the polyol xylitol in the samples.

[0107] Example 4 Example 4 illustrates the preparation of aqueous treatment solutions based on citric acid and either a) sodium hypophosphite monohydrate or b) monosodium phosphate dihydrate as reaction catalysts; the production of polyester materials with antimicrobial properties; and the demonstration of the antimicrobial properties of the produced polyester fabrics against Gram-positive bacteria after various wash cycles.

[0108] Aqueous treatment solutions were prepared as follows: citric acid, anhydrous (CA; CAS No. 77-92-9) and a) sodium hypophosphite (SHP) monohydrate (CAS No. 10039-56-2) or b) monosodium phosphate (MSP) dihydrate (NaH2PO4·2H2O; CAS No. 13472-35-0), which were in solid form when dissolved in deionized water at room temperature. The final concentrations were 9 wt% for citric acid, 9 wt% for a) SHP, or 13.5 wt% for b) NaH2PO4·2H2O. The pH of treatment solution a) was 2.88 and 2.99 for b).

[0109] Polyester materials with antimicrobial properties were produced by immersing polyester fabric samples in two different working solutions containing a) 9 wt% citric acid (CA) and either a) 9 wt% SHP or b) 13.5 wt% NaH2PO4·2H2O, swirling for 1 minute, and then padding to approximately 70% pickup. The wet samples were placed in a stenter frame and dried and cured in one step at 160°C for 90 seconds. After curing, the fabric samples were allowed to rehydrate overnight at room temperature and then prepared for further processing. As in Example 4, the materials were rinsed thoroughly with tap water and then subjected to laundering.

[0110] Determination of the durability and resulting antimicrobial protection of the treated fabric was carried out as in Example 4. The treated fabric pieces were then treated with 4.3 x 10 4The specimens were inoculated with gram-positive Staphylococcus aureus (ATCC 6538). After an overnight contact period, surviving bacterial cells were shaken off from the specimens with 20 ml of tryptone soy broth supplemented with 0.07% lecithin (wt.) and 0.5% Tween® (vol.). Serial dilutions were plated onto tryptone soy agar plates, and bacterial cells were quantified by counting colonies after overnight incubation.

[0111] The antibacterial activity value (A) was calculated in the same manner as in Example 1. The A value and the data used to calculate A are shown in Table 5.

[0112] [Table 5]

[0113] Polyester fabric samples treated with citric acid and either SHP or MSP as the reaction catalyst had strong antimicrobial properties (log reduction >3) both before washing and after 10 washing cycles. Thus, both catalysts have similar activity.

[0114] Example 5 Example 5 shows the effect of adding low molecular weight chitosan to the treatment solution on the antimicrobial properties against gram-positive bacteria.

[0115] Treatment solutions were prepared essentially as in Example 2, except that the final concentrations were 10 wt% for CA and 10 wt% for SHP, and low molecular weight chitosan (LMW-CS; CAS No. 9012-76-4) was added to a final concentration of 1 wt%. Treatment of polyester fabric samples and testing of their antimicrobial properties was carried out essentially as described in Example 2, except that in this case the wet pickup was approximately 63% and the samples were dried and cured in two stages, first at 100°C for 10 minutes and then at 160°C for 90 seconds.

[0116] The antibacterial activity value (A) was calculated in the same manner as in Example 1. The values ​​and data used in calculating A are shown in Table 6.

[0117] [Table 6]

[0118] The results showed that both the treated samples washed 0 times and 10 times had a greater than 5-log (>99.999%) reduction in Staphylococcus aureus colony counts compared to the untreated control polyester fabric. The presence of chitosan did not diminish the antimicrobial activity of CA. Chitosan is known to be an antimicrobial agent against fungi and both gram-negative and gram-positive bacteria, and may therefore have an additive effect on the antimicrobial activity of the treatment solution; chitosan derivatives, in particular, are also active against viruses.

[0119] Example 6 Example 6 illustrates the preparation of an aqueous treatment solution; the manufacture of polyester materials (100% PES; Fabrics A and B) with antifungal properties; and the demonstration of the antifungal properties of the manufactured polyester fabrics against the fungus Aspergillus brasiliensis after several washing cycles. Samples A and B were polyester fabrics from two different manufacturers.

[0120] The treatment solution was prepared essentially as in Example 2, except that sorbitol (CAS No. 50-70-4) was added to a final concentration of 0.6 wt % and the pH of the solution was adjusted to 2.9. The treatment and washing of polyester fabric samples A and B was carried out essentially as described in Example 1.

[0121] The durability of the treated fabric and the resulting antifungal protection were determined by a screening test based on standard ISO 13629-2. Briefly, 2.0 × 10 4The specimens were inoculated with Aspergillus brasiliensis spores (ATCC 16404). After a 44-hour contact time, viable A. brasiliensis spores were shaken off the specimens using 20 ml of tryptone soy broth supplemented with 0.07% lecithin and 0.5% Tween®. A. brasiliensis spores were quantified by plating serial dilutions onto Sabouraud dextrose agar plates and counting fungal colonies after 48 hours of incubation. Antifungal activity values ​​(A) were calculated essentially as specified in standard ISO 13629-2, similar to the antimicrobial activity values ​​in Example 1. The antifungal (A) values ​​and the data used to calculate A are shown in Table 7.

[0122] [Table 7]

[0123] Based on the criteria for antifungal effectiveness set out in standard ISO 13629-2, both treated 100% polyester fabrics (A and B) were fungistatic with only a small effect, both as-treated and after 10 or 6 washing cycles. No yellowing of the fabrics was observed by visual inspection, which is believed to be influenced by the presence of the polyol sorbitol in the samples.

[0124] Example 7 Example 7 illustrates the preparation of an aqueous treatment solution; the manufacture of two polyester / elastane blend fabrics (PES / EA 88 / 12 and PES / EA 92 / 8) with antimicrobial properties; and the demonstration of the antimicrobial properties of the manufactured synthetic blend fabrics against Staphylococcus aureus after several washing cycles.

[0125] Treatment solutions were prepared as in Example 6. Treatment and washing of the synthetic blend fabric samples was carried out essentially as described in Example 1.

[0126] Determination of the durability and resulting antimicrobial protection of the treated fabrics, and calculation of the antimicrobial activity value (A) were carried out as in Example 1.

[0127] The antibacterial (A) values ​​and the data used to calculate A are shown in Table 8.

[0128] [Table 8]

[0129] The treated synthetic polyester / elastane blend fabrics had strong antibacterial properties against Staphylococcus aureus as-treated and significant or strong antibacterial properties after eight wash cycles. No yellowing of the fabric was observed by visual inspection, which is believed to be influenced by the presence of the polyol sorbitol in the samples.

[0130] Example 8 Example 8 demonstrates a method for antimicrobially finishing synthetic 100% polyester fabric with 1,2,3,4-butanetetracarboxylic acid using sodium hypophosphite as a catalyst. The method involves a two-step heat treatment in which the fabric is dried and cured separately.

[0131] 1,2,3,4-Butanetetracarboxylic acid (BTCA, CAS No. 1703-58-8), sodium hypophosphite monohydrate (SHP, CAS No. 10039-56-2), and xylitol (CAS No. 87-99-0) were dissolved in deionized water at room temperature. The final concentrations were 9% for BTCA, 9% for SHP, and 0.5% for xylitol. The pH of the treatment solution was adjusted to 3.0 by adding a sufficient amount of 1 mol / L sodium hydroxide solution (NaOH, CAS No. 1310-73-2).

[0132] Polyester fabric (100% PES) samples were immersed in a treatment solution containing 9% BTCA, 9% SHP, and 0.5% xylitol, swirled for 1 minute, and then padded to approximately 70% wet pick-up. The wet samples were placed in a stenter frame and first thoroughly dried at 100°C for 5 minutes, then cured at 150°C for 90 seconds. To test the wash durability of the treatment, a subset of the prepared samples was washed 10 times essentially as described in Example 1.

[0133] Determination of the durability and resulting antimicrobial protection of the treated fabric was carried out as in Example 1. The treated fabric pieces were then treated with 2.3 x 10 4 The cells were inoculated with Gram-positive Staphylococcus aureus (ATCC 6538). The contact time for the antimicrobial test was 24 hours.

[0134] The antibacterial activity value (A) was calculated in the same manner as in Example 1. The A value and the data used to calculate A are shown in Table 9.

[0135] [Table 9]

[0136] The results showed that strong antimicrobial properties (ISO 20743 standard: log reduction >3) against Gram-positive Staphylococcus aureus (S. aureus) were achieved by treating 100% PES fabric with a solution containing 9% BTCA, 9% SHP, and 0.5% xylitol. After 10 washing cycles, there were 92% fewer bacterial cells on the treated and washed sample than on the untreated sample of the same fabric. No yellowing of the fabric was observed by visual inspection, which is likely influenced by the presence of the polyol xylitol in the sample.

[0137] Example 9 Example 9 demonstrates the antimicrobial finishing of synthetic 100% polyester fabric with tricarballylic acid using sodium hypophosphite as a catalyst. This finishing method involves a one-step heat treatment that dries and cures the fabric.

[0138] Tricarballylic acid (TCA, CAS No. 99-14-9) and sodium hypophosphite monohydrate (SHP, CAS No. 10039-56-2) were dissolved in deionized water at room temperature to a final concentration of 8.25% for TCA and 9% for SHP.

[0139] Polyester fabric (100% PES) samples were immersed in a treatment solution containing 8.25% TCA and 9% SHP, swirled for 1 minute, and then padded to approximately 70% wet pick-up. The wet samples were placed in a stenter frame and heat-treated at 160°C for 90 seconds for drying and curing. After curing, the fabric samples were rinsed thoroughly with tap water and allowed to rehydrate overnight at room temperature.

[0140] Determination of the resulting antimicrobial protection of the treated fabric was carried out as in Example 1. Treated fabric pieces were inoculated with 5.1 x 10 4 The cells were inoculated with Gram-positive Staphylococcus aureus (ATCC 6538). The contact time for the antimicrobial test was 24 hours.

[0141] The antibacterial activity value (A) was calculated in the same manner as in Example 1. The A value and the data used to calculate A are shown in Table 10.

[0142] [Table 10]

[0143] Results showed that strong antimicrobial properties (ISO 20743: log reduction >3) against Gram-positive Staphylococcus aureus (S. aureus) were achieved by treating 100% PES fabric with a solution containing 8.25% TCA and 9% SHP.

[0144] It is obvious to those skilled in the art that as technology advances, the concept of the present invention can be implemented in various ways. The present invention and its embodiments are not limited to the above examples but may vary within the scope of the claims.

Claims

1. 1. A method for producing an antimicrobial synthetic textile, comprising: a) providing a treatment solution comprising a polycarboxylic acid and a catalyst; b) applying the treatment solution onto a synthetic fabric to provide a polycarboxylic acid-treated synthetic fabric; c) curing the polycarboxylic acid treated synthetic fabric; A method comprising:

2. 2. The method of claim 1, wherein the polycarboxylic acid is one or more selected from citric acid (CA), isocitric acid (ICA), tricarballylic acid (TCA), 1,2,4-butanetricarboxylic acid (BTRCA), 1,2,3,4-butanetetracarboxylic acid (BTCA), oxalic acid, tartaric acid, succinic acid, malic acid, malonic acid, glutamic acid, aspartic acid, glutaric acid, 1,3,5-pentanetricarboxylic acid, gluconic acid, mannaric acid, galactaric acid, maleic acid, adipic acid, or salts, hydrates, or isomers thereof.

3. 3. The method of claim 1 or 2, wherein the catalyst is one or more selected from sodium hypophosphite (SHP), SHP hydrate, monosodium phosphate (MSP), MSP hydrate, or any mixture thereof.

4. 4. The method according to any one of claims 1 to 3, wherein the concentration of the polycarboxylic acid is in the range of 1 to 20 wt.%, preferably 2 to 18 wt.%, more preferably 5 to 15 wt.%, even more preferably 6 to 14 wt.%, based on the total weight of the treatment solution.

5. 5. The method according to any one of claims 1 to 4, wherein the concentration of the catalyst is in the range of 1 to 20 wt%, preferably 2 to 18 wt%, more preferably 5 to 15 wt%, even more preferably 6 to 14 wt%, based on the total weight of the treatment solution.

6. 6. The method of any one of claims 1 to 5, wherein curing is carried out at a temperature in the range of from 130°C to 180°C, or from 135°C to 180°C, or from 140°C to 180°C, or from 145°C to 180°C, or from 150°C to 180°C, or from 150°C to 175°C, or from 150°C to 170°C.

7. 7. The method of any one of claims 1 to 6, wherein curing is carried out for a period in the range of from 5 to 180 seconds, or from 10 to 150 seconds, or from 15 to 120 seconds, or from 30 to 60 seconds.

8. 8. The method of claim 1, wherein the curing step c) is not preceded by a drying step.

9. The method of any one of claims 1 to 8, wherein the treatment solution has a pH in the range of 2 to 7, or 2 to 6, or 2 to 5, or 2 to 4, or 2 to 3.

10. 10. The method according to any one of claims 1 to 9, wherein the dry pick-up of polycarboxylic acid and / or catalyst is in the range of 0.5% to 20%, preferably in the range of 2% to 18% or 3% to 15%.

11. 11. The method of any one of claims 1 to 10, wherein the synthetic textile comprises or consists of a polymeric material, wherein the polymer molecules in the polymeric material contain at most one free hydroxyl group at each end of the polymer molecule and no free hydroxyl groups between the ends, and wherein the free hydroxyl groups are independently selected from hydroxyl groups and carboxylic acid groups.

12. 12. The method of any one of claims 1 to 11, wherein the synthetic fabric is selected from polyester; polyamides such as nylon; polyacrylonitriles such as acrylic and modacrylic; olefins; vinylon; polyethylenes such as ultra-high molecular weight polyethylene (UHMWPE, UHMW), Dyneema, and Spectra; elastane; vinylon; aramids such as Kevlar, Nomex, and Twaron; polybenzimidazole (PBI); polyphenylene sulfide (PPS); polylactic acid (PLA); poly(p-phenylene-2,6-benzobisoxazole (PBO)); Vectran; glass fiber, or any mixture thereof.

13. 13. The method of any one of claims 1 to 12, wherein the polycarboxylic acid and catalyst are dissolved in a solvent selected from an aqueous solvent, water, an alcohol, an ether, ethyl acetate, a ketone, DMSO, or any mixture thereof to provide the treatment solution.

14. 14. The method of claim 13, wherein the solvent is selected from an aqueous solvent or water.

15. 15. The method of any one of claims 1 to 14, wherein the treatment solution optionally further comprises a polyol selected from xylitol, sorbitol, glycerol, pentaerythritol, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, polyethylene glycol (PEG) 200, PEG 400, PEG 600, tris(methylol)ethane, and any combination thereof, at a concentration ranging from 0.1 to 5 wt. %, preferably from 0.2 to 3 wt. %, more preferably from 0.3 to 2 wt. %, and even more preferably from 0.5 to 1 wt. %, based on the total weight of the treatment solution.

16. 16. The method of any one of claims 1 to 15, further comprising treating the antimicrobial synthetic textile with one or more additional textile treatments selected from anti-wrinkle agents, shrinkage control agents, optical brighteners, water repellents, oil repellents, self-cleaning agents, flame retardants, softeners, odor absorbers, odor control agents, antibacterial agents, antifungal agents, antiviral agents, insect repellents, moisture management agents, antistatic agents, anti-pilling agents, anti-slip agents, and UV protection agents, optionally wherein the one or more additional textile treatments are included in the treatment solution.

17. 17. The method of any one of claims 1 to 16, wherein the textile comprises fibers, yarns, filaments, threads, and fabrics such as woven, knit, nonwoven, and cloth.

18. 18. An antimicrobial synthetic textile produced according to the method of any one of claims 1 to 17.

19. 1. An antimicrobial synthetic textile comprising an antimicrobial finish, said antimicrobial finish comprising a polycarboxylic acid cured in the presence of a catalyst.

20. 20. The antimicrobial synthetic textile of claim 19, wherein the polycarboxylic acid is one or more selected from citric acid (CA), isocitric acid (ICA), tricarballylic acid (TCA), 1,2,4-butanetricarboxylic acid (BTRCA), 1,2,3,4-butanetetracarboxylic acid (BTCA), oxalic acid, tartaric acid, succinic acid, malic acid, malonic acid, glutamic acid, aspartic acid, glutaric acid, 1,3,5-pentanetricarboxylic acid, gluconic acid, mannaric acid, galactaric acid, maleic acid, adipic acid, or salts, hydrates, or isomers thereof.

21. 21. The antimicrobial synthetic textile of claim 19 or 20, wherein the catalyst is one or more selected from sodium hypophosphite (SHP), SHP hydrate, monosodium phosphate (MSP), MSP hydrate, or any mixture thereof.

22. 22. The antimicrobial synthetic textile according to any one of claims 19 to 21, wherein the treatment solution that is cured to form the antimicrobial finish comprises the polycarboxylic acid in a concentration in the range of 1 to 20 wt.%, preferably 2 to 18 wt.%, more preferably 5 to 15 wt.%, even more preferably 6 to 14 wt.%, based on the total weight of the treatment solution.

23. 23. The antimicrobial synthetic textile according to any one of claims 19 to 22, wherein the treatment solution that is cured to form the antimicrobial finish comprises the catalyst at a concentration in the range of 1 to 20 wt.%, preferably 2 to 18 wt.%, more preferably 5 to 15 wt.%, even more preferably 6 to 14 wt.%, based on the total weight of the treatment solution.

24. 24. The antimicrobial synthetic textile of any one of claims 22 to 23, wherein the treatment solution optionally further comprises a polyol selected from xylitol, sorbitol, glycerol, pentaerythritol, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, polyethylene glycol (PEG) 200, PEG 400, PEG 600, tris(methylol)ethane, and any combination thereof, at a concentration in the range of 0.1 to 5 wt. %, preferably 0.2 to 3 wt. %, more preferably 0.3 to 2 wt. %, and even more preferably 0.5 to 1 wt. %, based on the total weight of the treatment solution.

25. 25. The antimicrobial synthetic textile of any one of claims 19 to 24, treated with one or more additional textile treatments selected from anti-wrinkle agents, shrinkage control agents, optical brighteners, water repellents, oil repellents, self-cleaning agents, flame retardants, softeners, odor absorbers, odor control agents, antibacterial agents, antifungal agents, antiviral agents, insect repellents, moisture management agents, antistatic agents, anti-pilling agents, anti-slip agents, and UV protection agents.

26. 25. The antimicrobial synthetic textile of any one of claims 22 to 24, further treated with one or more additional textile treatments selected from anti-wrinkle agents, shrinkage control agents, optical brighteners, water repellents, oil repellents, self-cleaning agents, flame retardants, softeners, odor absorbers, odor control agents, antibacterial agents, antifungal agents, antiviral agents, insect repellents, moisture management agents, antistatic agents, anti-pilling agents, anti-slip agents, and UV protection agents, wherein said one or more additional textile treatments are included in the treatment solution.

27. 27. The antimicrobial synthetic textile of any one of claims 19 to 26, wherein curing is carried out at a temperature in the range of from 130°C to 180°C, or from 135°C to 180°C, or from 140°C to 180°C, or from 145°C to 180°C, or from 150°C to 180°C, or from 150°C to 175°C, or from 150°C to 170°C, optionally for a period of time in the range of from 5 to 180 seconds, or from 10 to 150 seconds, or from 15 to 120 seconds, or from 30 to 60 seconds.

28. 28. The antimicrobial synthetic textile according to any one of claims 19 to 27, wherein the dry pick-up of polycarboxylic acid and / or catalyst is in the range of 0.5% to 20%, preferably in the range of 2% to 18% or 3% to 15%.

29. 29. The antimicrobial synthetic textile of any one of claims 19 to 28, comprising or consisting of a polymeric material, wherein the polymer molecules in the polymeric material contain at most one free hydroxyl group at each end of the polymer molecule and no free hydroxyl groups between the ends, the free hydroxyl groups being independently selected from hydroxyl groups and carboxylic acid groups.

30. 30. The antimicrobial synthetic textile of any one of claims 19 to 29, wherein the antimicrobial synthetic textile is selected from polyester; polyamide such as nylon; polyacrylonitrile such as acrylic and modacrylic; olefin; vinylon; polyethylene such as ultra-high molecular weight polyethylene (UHMWPE, UHMW), Dyneema, and Spectra; elastane; vinylon; aramid such as Kevlar, Nomex, and Twaron; polybenzimidazole (PBI); polyphenylene sulfide (PPS); polylactic acid (PLA); poly(p-phenylene-2,6-benzobisoxazole (PBO)); Vectran; glass fiber, or mixtures thereof.

31. 31. The antimicrobial synthetic textile of any one of claims 19 to 30, comprising fibers, yarns, filaments, threads, and fabrics such as wovens, knits, nonwovens, and cloth.

32. Use of polycarboxylic acids as antimicrobial finishes on synthetic textiles.

33. 33. The use of claim 32, wherein the polycarboxylic acid is one or more selected from citric acid (CA), isocitric acid (ICA), tricarballylic acid (TCA), 1,2,4-butanetricarboxylic acid (BTRCA), 1,2,3,4-butanetetracarboxylic acid (BTCA), oxalic acid, tartaric acid, succinic acid, malic acid, malonic acid, glutamic acid, aspartic acid, glutaric acid, 1,3,5-pentanetricarboxylic acid, gluconic acid, mannaric acid, galactaric acid, maleic acid, adipic acid, or salts, hydrates or isomers thereof.

34. 34. The use according to claim 32 or 33, wherein the polycarboxylic acid is cured in the presence of a catalyst, the catalyst being one or more selected from sodium hypophosphite (SHP), SHP hydrate, monosodium phosphate (MSP), MSP hydrate, or any mixture thereof.

35. 35. Use according to claim 34, wherein the treatment solution which is cured to form the antimicrobial finish comprises said polycarboxylic acid in a concentration in the range of 1 to 20 wt.%, preferably 2 to 18 wt.%, more preferably 5 to 15 wt.%, even more preferably 6 to 14 wt.%, based on the total weight of the treatment solution.

36. 36. Use according to claim 34 or 35, wherein the treatment solution which is cured to form the antimicrobial finish comprises the catalyst at a concentration in the range of 1 to 20 wt.%, preferably 2 to 18 wt.%, more preferably 5 to 15 wt.%, even more preferably 6 to 14 wt.%, based on the total weight of the treatment solution.

37. 37. The use according to claim 35 or 36, wherein the treatment solution optionally further comprises a polyol selected from xylitol, sorbitol, glycerol, pentaerythritol, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, polyethylene glycol (PEG) 200, PEG 400, PEG 600, tris(methylol)ethane, and any combination thereof, at a concentration in the range of 0.1 to 5 wt. %, preferably 0.2 to 3 wt. %, more preferably 0.3 to 2 wt. %, and even more preferably 0.5 to 1 wt. %, based on the total weight of the treatment solution.

38. 38. The use of any one of claims 32 to 37, wherein the synthetic textile is treated with one or more additional textile treatments selected from anti-wrinkle agents, shrinkage control agents, optical brighteners, water repellents, oil repellents, self-cleaning agents, flame retardants, softeners, odor absorbers, odor control agents, antibacterial agents, antifungal agents, antiviral agents, insect repellents, moisture management agents, antistatic agents, anti-pilling agents, anti-slip agents, and UV protection agents.

39. 38. The use of any one of claims 35 to 37, wherein the synthetic textile is further treated with one or more additional textile treatments selected from anti-wrinkle agents, shrinkage control agents, optical brighteners, water repellents, oil repellents, self-cleaning agents, flame retardants, softeners, odor absorbers, odor control agents, antibacterial agents, antifungal agents, antiviral agents, insect repellents, moisture management agents, antistatic agents, anti-pilling agents, anti-slip agents, and UV protection agents, and wherein the one or more additional textile treatments are included in the treatment solution.

40. 40. Use according to any one of claims 34 to 39, wherein curing is carried out at a temperature in the range of from 130°C to 180°C, or from 135°C to 180°C, or from 140°C to 180°C, or from 145°C to 180°C, or from 150°C to 180°C, or from 150°C to 175°C, or from 150°C to 170°C, optionally for a period in the range of from 5 to 180 seconds, or from 10 to 150 seconds, or from 15 to 120 seconds, or from 30 to 60 seconds.

41. 41. The use of any one of claims 32 to 40, wherein the synthetic textile comprises or consists of a polymeric material, wherein the polymer molecules in the polymeric material contain at most one free hydroxyl group at each end of the polymer molecule and no free hydroxyl groups between the ends, and wherein the free hydroxyl groups are independently selected from hydroxyl groups and carboxylic acid groups.

42. 42. The use according to any one of claims 32 to 41, wherein the synthetic textile is selected from polyester; polyamides such as nylon; polyacrylonitriles such as acrylic and modacrylic; olefins; vinylon; polyethylenes such as ultra-high molecular weight polyethylene (UHMWPE, UHMW), Dyneema, and Spectra; elastane; vinylon; aramids such as Kevlar, Nomex, and Twaron; polybenzimidazole (PBI); polyphenylene sulfide (PPS); polylactic acid (PLA); poly(p-phenylene-2,6-benzobisoxazole (PBO)); Vectran; glass fiber, or mixtures thereof.

43. 43. The use of any one of claims 32 to 42, wherein the textile comprises fibers, yarns, filaments, threads, and fabrics such as woven, knit, nonwoven, and cloth.

44. 32. An article of manufacture comprising the antimicrobial synthetic textile of any one of claims 18 to 31, optionally selected from clothing; footwear; personal protective equipment; accessories such as hats, scarves, gloves, belts and ties; bags; luggage; backpacks; towels; interior textiles such as bedding, cushions, throws, curtains, drapes, upholstery, floor and wall coverings and car interiors; sports and outdoor equipment, medical textiles such as wound dressings, bandages, masks, gloves and surgical gowns; toys; industrial products such as filters, conveyor belts, geotextiles, industrial fabrics, shade netting, crop covers, packaging, insulation, gaskets, seals and tire cords; and electronic devices such as headphones, microphones and speakers.

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