Fiber structure and manufacturing method thereof

Abstract

The present invention provides a fiber structure having excellent antibacterial properties and washing durability, and a method for producing the same. [Solution] A textile structure having polyamide fibers and containing a dye, a quinoline-based compound, and a phenol derivative, wherein the textile structure contains 0.04% by mass or more of the quinoline-based compound relative to the mass of the textile structure, and even after 10 standard washes in accordance with the "SEK Mark Textile Product Washing Method," the textile structure contains 0.04% by mass or more of the quinoline-based compound relative to the mass of the textile structure, and 0.20% by mass or more and 4.00% by mass or less of the phenol derivative relative to the mass of the textile structure.

Description

[Technical Field]

[0001] The present invention relates to a textile structure having excellent antibacterial properties and washing durability, and a method for producing the same. [Background technology]

[0002] In recent years, due to increased awareness of hygiene and health, many everyday textile products have been imparted with antibacterial properties, including hospital textile products such as white coats worn by medical professionals in medical facilities such as hospitals and clinics, as well as general clothing textile products such as casual clothing and innerwear worn by ordinary consumers. These antibacterial textile products are washed on a daily basis for repeated use. Therefore, there is a demand for textile products that have been imparted with antibacterial properties that can withstand washing.

[0003] From the viewpoint of productivity, the mainstream antibacterial processing technology for synthetic fiber products involves adding an antibacterial agent after the product has been made into a fabric or other product. However, this processing method generally has the problem of low antibacterial properties after washing, as the antibacterial agent is generally removed by washing.

[0004] To address this issue, studies have been conducted to improve antibacterial properties after washing. For example, Patent Document 1 proposes a single-bath processing method in which polyamide fibers are immersed in a treatment solution containing a mixture of 2-pyridylthiol-1-oxide zinc (hereinafter referred to as zinc pyrithione), a type of pyridine antibacterial agent, and tannins, which are compounds having a phenolic hydroxyl group, and then heat-treated in that state. It is proposed that this method allows the tannins to fix the zinc pyrithione to the polyamide fibers, resulting in a polyamide fiber structure that exhibits good antibacterial and antifungal properties even after 10 home washes at 40°C.

[0005] Patent Document 2 also proposes that zinc 2-pyridylthiol-1-oxide be applied to a fiber structure by heat treatment at a specific temperature under normal or increased pressure, thereby providing a fiber structure with antibacterial properties and excellent durability to industrial washing at a temperature of 85±2°C.

[0006] Furthermore, Patent Document 3 proposes immersing textiles in an antibacterial treatment solution containing oxolinic acid or a salt thereof and then heat treating the textiles in a treatment bath at a specific temperature under pressure, thereby providing an antibacterial agent for high-pressure treatment with excellent antibacterial properties and a treatment method therefor. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-125697 [Patent Document 2] Japanese Patent Application Laid-Open No. 2000-8275 [Patent Document 3] JP 2021-42498 A Summary of the Invention [Problem to be solved by the invention]

[0008] The methods disclosed in Patent Documents 1 and 2 achieve antibacterial properties and washing durability, but have the problem that the antibacterial agent containing zinc ions is used, making it difficult to treat the wastewater generated after the antibacterial agent is applied. Another problem is that the dyeability may be affected.

[0009] The method disclosed in Patent Document 3 uses oxolinic acid, an organic carboxylic acid compound, and therefore does not have the wastewater treatment problem that is an issue in Patent Documents 1 and 2. However, according to the studies of the present inventors, when the fiber substrate used contains polyamide fiber, it has been found that, depending on the amount of agent used and the processing step, it may not be possible to obtain the desired antibacterial properties after washing.

[0010] The present invention has been made to solve the above-mentioned problems, and aims to provide a fiber structure and a method for producing the same that have excellent antibacterial properties even after 10 standard washings when a fiber substrate having polyamide fibers is used without using an antibacterial agent containing zinc ions or the like. [Means for solving the problem]

[0011] As a result of extensive research, the inventors have found that by attaching a specific amount of a quinoline-based compound and a specific amount of a phenol derivative to a fiber substrate having polyamide fibers, a fiber structure having excellent antibacterial properties after 10 standard washes can be obtained.

[0012] Furthermore, it was also found that in order to achieve the above-mentioned effects, it is important to subject a textile substrate having polyamide fibers to a chemical treatment process using a dye and a quinoline-based compound in the same bath, and then to a phenol derivative treatment process in which a phenol derivative is added in a separate bath.

[0013] That is, the present invention has the following configuration to solve the above problems. (1) A fiber structure containing a dye, a quinoline-based compound, and a phenol derivative and having polyamide fibers, The quinoline-based compound is contained in an amount of 0.04% by mass or more relative to the mass of the fiber structure, And even after 10 standard washes in accordance with the "SEK Mark Textile Product Washing Method," the textile structure contains 0.04% by mass or more of the quinoline-based compound, The fiber structure contains the phenol derivative in an amount of 0.20 mass % or more and 4.00 mass % or less relative to the mass of the fiber structure. (2) The fiber structure according to (1), wherein the quinoline compound is at least one compound selected from the group consisting of oxolinic acid, ciprofloxacin, levofloxacin, moxifloxacin, garenoxacin, and sitafloxacin. (3) The fiber structure according to (1) or (2), wherein the quinoline-based compound is oxolinic acid. (4) The fiber structure according to any one of (1) to (3), wherein the mass ratio of the quinoline compound to the phenol derivative contained in the fiber structure is 1:1 to 1:30. (5) a processing solution preparation step of preparing a processing solution containing a dye and a quinoline-based compound; a chemical solution treatment step in which a fiber substrate having polyamide fibers is immersed in the treatment solution and heat-treated in a bath at a temperature of 80°C or higher and 110°C or lower under normal pressure or pressure; a phenol derivative treatment step of immersing a fiber substrate having polyamide fibers treated with the chemical solution in a treatment solution containing a phenol derivative and heat-treating the fiber substrate in a bath at 60°C or higher and 90°C or lower under normal pressure; a post-heat treatment process in which dry heat treatment is performed at an atmospheric temperature of 130°C or higher and 190°C or lower; A method for producing a fiber structure comprising the steps of: (6) The method for producing a fiber structure according to (5), wherein the phenol derivative treatment step uses a treatment liquid containing the phenol derivative in an amount of 0.020 mass % or more and 0.400 mass % or less relative to the mass of the treatment liquid containing the phenol derivative. [Effects of the Invention]

[0014] According to the present invention, it is possible to provide a fiber structure that contains a dye and a quinoline-based compound and that exhibits excellent antibacterial properties after 10 standard washes, and a method for producing the same. DETAILED DESCRIPTION OF THE INVENTION

[0015] [Fiber structure] The present invention is described in detail below with reference to preferred embodiments, but is not limited to these. The textile structure of the present invention contains a dye, a quinoline compound, and a phenol derivative, and the quinoline compound is present in an amount of 0.04% by mass or more relative to the mass of the textile structure, and even after 10 standard washings in accordance with the "SEK Mark Textile Product Washing Method," the quinoline compound remains at 0.04% by mass or more relative to the mass of the textile structure, and the phenol derivative remains at 0.20% by mass to 4.00% by mass relative to the mass of the textile structure.

[0016] The fiber structure of the present invention has an antibacterial activity value of A after 10 standard washes in the antibacterial evaluation method described in the SEK Mark textile product certification standards. 10 The antibacterial activity value A after 50 high-temperature accelerated washing cycles is larger than the standard fabric growth value F. 50 It also has the characteristic that the growth value of the fabric is greater than the standard fabric growth value F.

[0017] In this invention, the "SEK Mark Textile Product Certification Standards" refers to the "SEK Mark Textile Product Certification Standards" (Document Control Number: JEC301) of the Japan Textile Evaluation Technology Council, a general incorporated association, revised on April 1, 2024.

[0018] <Fiber substrate containing polyamide fibers> As the fiber substrate containing polyamide fibers that constitutes the fiber structure of the present invention, fabrics such as woven fabrics, knitted fabrics, and nonwoven fabrics can be preferably used. The form of the polyamide fibers may be either filament yarn or spun yarn, but is not limited to these. If necessary, polyamide fibers may be combined with synthetic fibers other than polyamide fibers, such as polyester and acrylic, natural fibers such as cotton, wool, and silk, and semi-synthetic fibers such as rayon and acetate, and used in the form of interwoven, interknitted, mixed woven, mixed spun, or mixed fibers.

[0019] Although the proportion of polyamide fibers contained in the fiber substrate containing polyamide fibers is not limited, a higher proportion can improve the antibacterial properties of the present invention after 10 standard washes and 50 high-temperature accelerated washes. Therefore, the polyamide fibers preferably account for 50 mass% or more, more preferably 60 mass% or more, and even more preferably 80 mass% or more of the total mass of the fiber substrate.

[0020] The polyamide fibers are melt-spun fibers made from a resin containing a polymer having an amide bond. Examples of polyamide fibers that can be used include nylon 6, which is synthesized by the ring-opening polymerization of caprolactam, and nylon 66, which is synthesized by the polycondensation of adipic acid and hexamethylenediamine. Other known polyamide fibers, such as nylon 8, nylon 6.10, and nylon 11, can also be used.

[0021] There is no particular limitation on the fineness of the polyamide fiber, but it is preferable that the single fiber fineness is 0.04 dtex or more and 5.00 dtex or less, since the effects of the present invention can be significantly exhibited.

[0022] The fiber structure of the present invention may contain any amount of other chemicals such as a water absorbing agent and a fluorescent whitening agent in addition to the dye, quinoline compound, and phenol derivative described below.

[0023] <dye> The fiber structure of the present invention contains a dye. The dye here refers to a water-soluble organic compound that is used to color synthetic fibers such as polyamide fibers and polyester fibers, natural fibers such as cotton, wool, and silk, and semi-synthetic fibers such as rayon and acetate.

[0024] The type of dye used in the present invention is not particularly limited. Considering the need to color polyamide fibers, suitable dyes include acid dyes having a sulfo group or a carboxyl group in the dye molecule, metal complex dyes bonded to metal atoms such as chromium, cobalt, or copper, and fluorescent brighteners used to enhance whiteness. Furthermore, the amount of dye attached to the fiber substrate containing polyamide fibers is not limited, as long as the amount of dye required to achieve the desired hue is attached.

[0025] <Quinoline compounds> Examples of the quinoline compounds include oxolinic acid (5-ethyl-8-oxo-[1,3]dioxolo[4,5-g]quinoline-7-carboxylic acid), ciprofloxacin (1-cyclopropyl-1,4-dihydro-6-fluoro-4-oxo-7-(1-piperazinyl)-3-quinolinecarboxylic acid), levofloxacin ((3S)-9-fluoro-3-methyl-10-(4-methyl-1-piperazinyl)-7-oxo-2,3-dihydro-7H-pyrido[1,2,3-de][1,4]benzoxazine-6-carboxylic acid), moxifloxacin ((1S,6S)-1-cyclopropyl-7-(2,8-diazabicyclo[4.3.0]non-8-isopropyl) Preferably, the quinoline compound is at least one compound selected from the group consisting of 1-cyclopropyl-8-(difluoromethoxy)-7-[(1R)-1-methyl-2,3-dihydro-1H-isoindol-5-yl]-6-fluoro-8-methoxy-4-oxo-1,4-dihydroquinoline-3-carboxylic acid), garenoxacin (1-cyclopropyl-8-(difluoromethoxy)-7-[(1R)-1-methyl-2,3-dihydro-1H-isoindol-5-yl]-4-oxo-1,4-dihydroquinoline-3-carboxylic acid), and sitafloxacin (7-[(7S)-7-amino-5-azaspiro[2.4]heptan-5-yl]-8-chloro-6-fluoro-1-[(1R,2S)-2-fluorocyclopropyl]-4-oxo-1,4-dihydroquinoline-3-carboxylic acid). Among these, oxolinic acid is more preferred as the quinoline compound.

[0026] The quinoline compounds listed above may be in the form of metal salts such as alkali metal salts, such as sodium salts or potassium salts, alkaline earth metal salts, such as calcium salts or magnesium salts, aluminum salts, or iron salts.

[0027] The content of the quinoline compound in the fiber structure is 0.04% by mass or more, preferably 0.10% by mass or more, and more preferably 0.15% by mass or more, relative to the mass of the fiber structure. By containing 0.04% by mass or more relative to the mass of the fiber structure, it becomes possible to exhibit good antibacterial properties. On the other hand, if the mass of the quinoline compound is too large, a large amount of white quinoline compound adheres to the surface of the fiber structure, which causes the fiber structure to turn white (i.e., the brightness L * The quinoline-based compound content is preferably 0.50% by mass or less, more preferably 0.30% by mass or less, relative to the mass of the fiber structure. The mass ratio of the quinoline-based compound to the mass of the fiber structure of the present invention is measured by the method described in the Examples.

[0028] Furthermore, even after 10 standard washings in accordance with the "SEK Mark Textile Product Washing Method," the content of quinoline compounds in the textile structure is 0.04 mass% or more, preferably 0.10 mass% or more, and more preferably 0.15 mass% or more, relative to the mass of the textile structure. When the content of quinoline compounds in the textile structure is 0.04 mass% or more relative to the mass of the textile structure after 10 standard washings, the antibacterial effect achieved by the present invention can be obtained.

[0029] <Phenol derivatives> The fiber structure of the present invention contains a phenol derivative, which not only inhibits the removal of dyes present in a fiber substrate containing polyamide fibers by binding to the dyes or by coating the fiber surface, but also inhibits the removal of quinoline compounds present in the fiber substrate containing polyamide fibers.

[0030] Examples of phenol derivatives used in the present invention include phenolsulfonic acid formaldehyde resins synthesized using compounds such as bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, and bisphenol Z as raw materials, novolac-type resin sulfonates, resole-type resin methanesulfonic acid, and other phenol-type synthetic tannins, thiophenol-type synthetic tannins, and dihydroxydiphenyl sulfone-type synthetic tannins.

[0031] It is important that the fiber structure of the present invention contains 0.20% by mass or more of the phenol derivative relative to the mass of the fiber structure, preferably 1.00% by mass or more. If the phenol derivative is less than 0.20% by mass, the effect of immobilizing the quinoline-based compound on the fiber structure is weakened, resulting in a decrease in antibacterial properties after washing and making it impossible to achieve the antibacterial properties of the present invention. On the other hand, if the mass of the phenol derivative is too high, a large amount of the phenol derivative adheres to the fiber structure, which reduces contact between the quinoline-based compound and fungi, potentially preventing the antibacterial performance achieved by the present invention from being achieved. Therefore, it is important that the phenol derivative is contained in an amount of 4.00% by mass or less, preferably 2.00% by mass or less. Here, the mass ratio of the phenol derivative relative to the mass of the fiber structure of the present invention is measured using the method described in the Examples.

[0032] In order to achieve antibacterial properties, the mass ratio of the quinoline compound to the phenol derivative contained in the fiber structure is preferably 1:1 to 1:30, and more preferably 1:5 to 1:20.

[0033] <Antibacterial properties of textile structures> The fiber structure of the present invention has an antibacterial activity value of A after 10 standard washes in the antibacterial evaluation method described in the SEK Mark textile product certification standard established by the Japan Textile Evaluation Technology Council. 10is greater than the standard fabric growth value F. In addition, the antibacterial activity value A after 50 high-temperature accelerated washing cycles 50 is greater than the standard fabric growth value F. Standard washing, high-temperature accelerated washing, and antibacterial testing are evaluated using the methods described below.

[0034] [Application] The textile structure provided by the present invention can be used in various applications requiring high antibacterial properties, for example, as fabric for clothing, bedding, towels, rugs, curtains, sheets, etc.

[0035] It can be used for general clothing, uniforms, formal and business clothing, work clothes, sportswear, etc.

[0036] [Method for producing fiber structure] The method for manufacturing a fiber structure of the present invention is characterized by comprising: a treatment solution preparation step of preparing a treatment solution containing a dye and a quinoline-based compound; a chemical solution treatment step of immersing a fiber substrate having polyamide fibers in the treatment solution and heat-treating it in a bath at a temperature of 80°C or higher and 110°C or lower under normal pressure or pressure; a phenol derivative treatment step of immersing the fiber substrate having polyamide fibers that has been subjected to the chemical solution treatment in a treatment solution containing a phenol derivative and heat-treating it in a bath at a temperature of 60°C or higher and 90°C or lower under normal pressure; and a post-heat treatment step of performing dry heat treatment at an ambient temperature of 130°C or higher and 190°C or lower.

[0037] <Processing solution preparation process> In the treatment solution preparation step, a treatment solution containing a dye and a quinoline-based compound is prepared. For example, the treatment solution can be prepared by adding the dye and the quinoline-based compound in any order at room temperature. The dye can be used in any amount depending on the hue of the textile product to be manufactured.

[0038] The quinoline compound is added to the treatment liquid so that the content of the quinoline compound is 0.004% by mass or more and 0.050% by mass or less, more preferably 0.010% by mass or more and 0.030% by mass or less, and even more preferably 0.015% by mass or more and 0.030% by mass or less, relative to the mass of the treatment liquid.

[0039] <Chemical treatment process> The chemical treatment step employs a bath treatment method, which refers to a method in which a fibrous substrate having polyamide fibers is immersed in a bath containing a treatment solution and then heat-treated, thereby adhering the treatment solution to the fibrous substrate having polyamide fibers.

[0040] In this process, first, a fiber substrate having polyamide fibers is placed in the treatment liquid prepared in the treatment liquid preparation process at a bath ratio (mass of fiber substrate having polyamide fibers: mass of treatment liquid) of 1:5 to 1:30, and then heat treatment is carried out in a sealed container under normal pressure or pressure in a bath at a temperature of 80°C to 110°C.

[0041] However, when a quinoline compound is treated with a chemical solution in the phenol derivative treatment step described below or in the padding step, the antibacterial performance after washing in the present invention is not exhibited. The padding step here refers to a step in which a fibrous substrate having polyamide fibers is immersed in a treatment solution, squeezed with a mangle roller or the like so that a certain amount of the treatment solution adheres to the substrate, and then subjected to a dry heat treatment in a dryer or a wet heat treatment in saturated steam at 100°C, thereby adhering the treatment solution to the fibrous substrate having polyamide fibers.

[0042] <Phenol derivative treatment process> In the phenol derivative treatment step, a treatment solution containing a phenol derivative is prepared. The phenol derivative is added to the treatment solution preferably at a concentration of 0.020% by mass to 0.400% by mass, more preferably 0.100% by mass to 0.200% by mass. The fibrous substrate containing polyamide fibers is then placed in the treatment solution containing the phenol derivative at a bath ratio (mass of fibrous substrate containing polyamide fibers:mass of treatment solution) of 1:5 to 1:30, followed by heat treatment in a sealed container at a temperature of 60°C to 90°C under normal pressure. After heat treatment, the fibrous substrate containing polyamide fibers is removed from the container and sequentially washed with water and air-dried.

[0043] <Post-heat treatment process> In the post-heat treatment step, the fiber substrate having the polyamide fibers that have been subjected to the phenol derivative treatment step is set in a pin tenter and subjected to dry heat treatment at an atmospheric temperature of 130° C. or higher and 190° C. or lower for 15 seconds to 5 minutes.

[0044] <Post-processing process> The fiber structure of the present invention is obtained through the post-heat treatment step, but in the method for producing a fiber structure of the present invention, as with general fiber structures, various further finishing steps can be carried out, such as calendaring, which improves the light reflection of the fiber structure surface and gives it a glossy feel by compressing and smoothing the fiber structure using a roller or the like, and raising, which fluffs the fiber structure surface by scratching or abrading it with a needle or abrasive cloth, to impart heat retention and flexibility. Of course, in the present invention, fiber structures obtained by carrying out these finishing steps are also considered to be fiber structures of the present invention. [Example]

[0045] Next, the method for producing a fiber structure of the present invention will be explained in more detail with reference to examples, but the method is not limited to these examples. The washing method and various test methods in the examples were as follows.

[0046] (Washing method) Standard washing and high-temperature accelerated washing were carried out in accordance with the "Washing Method for SEK Mark Textile Products," the certification standard of the Japan Textile Evaluation Technology Council.

[0047] For the standard wash, a fully automatic washing machine conforming to the C-type standard washing machine - vertical axis, top loading (pulsator type) specified in JIS L 1930:2014 "Test Methods for Home Laundry of Textile Products" (apparatus and materials) was used. The detergent used was "JAFET Standard Formula Detergent," and the wash solution was prepared by adding 40 mL of "JAFET Standard Formula Detergent" to 30 L of water. The washing conditions were then adjusted to washing method C4G specified in Appendix F of JIS L 1930:2014 "Test Methods for Home Laundry of Textile Products." Specifically, the washing conditions were: water temperature: 40 ± 3°C, water volume: 40 L, wash time: 3 minutes, spin time: 3 minutes. The rinsing conditions were: water volume: 40 L, rinse time: 2 minutes, spin time: 3 minutes, and this counted as one cycle. After repeated washing, the garments were dried at a temperature of 80°C or less. The garments were hung or laid flat to dry, away from direct sunlight.

[0048] Next, a high-temperature accelerated wash was carried out using a washing machine, with 120 mL of "JAFET standard blend detergent" added to 90 L of water to create the wash liquid. Next, the textile structure and, if necessary, a load cloth were added so that the bath ratio of this wash liquid (mass of textile structure: mass of wash liquid) was 1:30, and the total mass of the textile structure and the load cloth was adjusted to 3 kg. 1) Wash at 80°C for 120 minutes 2) Drainage The washing machine was then rinsed using a standard washing machine with a standard washing capacity and standard water volume equipped with a centrifugal wringer that conforms to the standard JIS C 9606:2007 (electric washing machine) specified in "Appendix 1 Test Methods by Symbol - Washing Method (Water Washing), Number 103" in JIS L 0217:1995 "Display Symbols and Their Display Methods for Handling Textile Products." That is, 3) Thoroughly dehydrate the fiber structure and the loaded fabric for 3 to 5 minutes. 4) 15-minute overflow rinse (aim for 3 to 5 times the amount of water replaced) 5) Dehydrate in the same way as 4). After that, steps 3) to 5) were repeated a total of four times, and then steps 1) to 5) were repeated a total of five times using a washing machine and a standard washing machine. Finally, only the fiber structure was taken out, 6) Rinse with overflow for 5 minutes using a standard washing machine (aim for 3 to 5 times the amount of water replaced). 7) Dehydrate in the same way as in 3). 8) Dry at a temperature of 80°C or less In step 8), the product was hung to dry or laid flat to dry, away from direct sunlight.

[0049] (Antibacterial test) 1) Test method: The test was performed using the bacterial liquid absorption method based on JIS L 1902:2015 "Test methods for antibacterial properties and antibacterial effects of textile products." The test was performed under the condition that the nonionic surfactant "Tween" (registered trademark) 80 was added to the test bacterial suspension in an amount of 0.050% by mass relative to the mass of the fiber structure. 2) Test strain: Staphylococcus aureus 3) Evaluation method: The evaluation criteria for antibacterial processing (specific use: red) in "18.3 Evaluation criteria for bacterial liquid absorption method" of the "SEK Mark Textile Product Certification Standards" mentioned above were followed. That is, the antibacterial activity value of the antibacterial processed textile structure after 10 standard washes was evaluated as A. 10、 Antibacterial activity after 50 high-temperature accelerated washing cycles: A 50 , the growth value of the unwashed standard cloth is F, A 10 > F, that is, A 10 If -F>0.0, the antibacterial properties are good after 10 standard washes. 10 If -F≦0.0, the antibacterial properties were judged to be poor. 50 > F, that is, A 50 - If F>0.0, the antibacterial properties are good after 50 high-temperature accelerated washings. 50 If -F≦0.0, the antibacterial property was judged to be poor. The standard cloth refers to a white cloth (cotton No. 3-1) attached to JIS L 0803, which is sold by the Japan Textile Evaluation Technology Council as a standard cloth (cotton) for antibacterial testing and is listed in the proviso of "3.1 Control specimen" in JIS L 1902:2015 "Antibacterial test method and antibacterial effect of textile products," and which has been washed with water.

[0050] Here, the antibacterial activity value A after n washings n The growth value F of the standard cloth was calculated using the following formulas (1) and (2). A n =(log C t -log C o )-(log T t -log T o ) …(1) F=log C t -log C o …(2) log C o : Common logarithm of the arithmetic mean of the viable bacterial counts of three samples immediately after inoculation of the test bacteria on the standard cloth log C t : Common logarithm of the arithmetic mean of the viable bacterial counts of three samples after 18 hours of incubation of the standard cloth log T o : Common logarithm of the arithmetic mean of the number of viable bacteria in three samples immediately after inoculation of the test bacteria on the obtained fiber structure log T t : Common logarithm of the arithmetic mean of the number of viable bacteria in three samples after 18 hours of incubation on the obtained fiber structure The antibacterial activity value A0 of the fiber structure before washing was also evaluated using the above method.

[0051] (Colorimetry) Using a spectrophotometer model CM-3700d (Konica Minolta, Inc.), the diffuse reflectance of the fiber structure was measured under a D65 light source and a 10-degree field of view, and the lightness L was calculated. * Here, the lightness L * JIS Z8781-4:2013 (Colorimetry - Part 4: CIE 1976 L * a * b * L defined in "3.3 CIE1976 Lightness Index" of the * It refers to the value.

[0052] (Ratio of the mass of quinoline-based compounds to the mass of the fiber structure) 1.00 g of the fiber structure was weighed out and immersed in a solution of methanol and aqueous sodium hydroxide solution. The resulting solution was then filtered through a filter. The mass of the quinoline-based compounds adhering to the fiber structure was then measured using high-performance liquid chromatography. The mass ratio (mass%) of the quinoline-based compounds to the mass of the accurately weighed fiber structure was then calculated.

[0053] In the column for fiber structure in Table 2, the "ratio of the mass of quinoline-based compound to the mass of fiber structure" is expressed as "amount of quinoline-based compound present."

[0054] (Ratio of mass of phenol derivative to mass of fiber structure) As described above, the same method was used to calculate the mass ratio of the quinoline-based compound to the mass of the fiber structure. Specifically, 1.00 g of the fiber structure was weighed out and immersed in a solution of methanol and aqueous sodium hydroxide solution. This was then filtered. The mass of the phenol derivative adhering to the fiber structure was then measured using high-performance liquid chromatography. The mass ratio (mass %) of the phenol derivative to the mass of the accurately weighed fiber structure was then calculated.

[0055] In the column for fiber structure in Table 2, the "ratio of the mass of the phenol derivative to the mass of the fiber structure" is expressed as the "abundance of phenol derivative present."

[0056] [Example 1] (1) Preparation of a fiber substrate containing polyamide fibers A woven fabric was used as the warp and weft yarns, consisting of polyamide fibers consisting of a 78 dtex-26 filament (single fiber fineness 3.00 dtex) multifilament composed of nylon 66 synthesized by the polycondensation reaction of adipic acid and hexamethylenediamine.The fabric was heat-set by dry heat at 180°C for 0.5 minutes to produce a fiber substrate containing polyamide fibers.

[0057] (2) Processing solution preparation process A processing solution containing an acid dye, a quinoline compound, and a dyeing acid was prepared using the following chemicals, with the mass ratio of each chemical to the mass of the processing solution being as follows: Acid dye: Kayacryl Miling Blue BW (manufactured by Nippon Kayaku Co., Ltd.), 0.200% by mass Quinoline compounds: oxolinic acid, 0.004% by mass Dyeing acid: 70% acetic acid / 30% sodium acetate mixed aqueous solution, 0.005% by mass In the production method column of Table 1, the "ratio of the mass of the quinoline-based compound to the mass of the treatment liquid" is expressed as "quinoline-based compound."

[0058] (3) Chemical treatment process A fibrous substrate having polyamide fibers was immersed in the treatment solution prepared above and subjected to chemical treatment in a bath processing machine under pressure at 100°C for 30 minutes. Thereafter, the fibrous substrate having polyamide fibers was removed from the bath processing machine and subjected to water washing and dehydration. Here, the following equipment was used for the bath processing machine, and the bath ratio was as follows. Bath processing machine: 12-color rotary pot dyeing tester (MINI-COLOUR 12EL type: manufactured by Texam Giken Co., Ltd.) Liquor ratio (mass of fiber substrate containing polyamide fiber: mass of treatment liquid): 1:10 (4) Phenol derivative treatment process A treatment liquid containing a phenol derivative was prepared using the following chemicals, and the mass ratio of the phenol derivative to the treatment liquid was adjusted as follows: Phenol derivatives: Thiophenol-type synthetic tannins containing bisphenol S, 0.100% by mass In the production method column of Table 1, the "ratio of the mass of the phenol derivative to the mass of the treatment liquid" is expressed as "phenol derivative."

[0059] The fibrous substrate having the chemically treated polyamide fibers was immersed in the treatment solution containing the phenol derivative prepared above, and the phenol derivative treatment was carried out in a bath processing machine at normal pressure and 80°C for 20 minutes. Thereafter, the fibrous substrate having the polyamide fibers was removed from the bath processing machine and washed with water and dehydrated. Here, the bath processing machine used the following equipment, and the bath ratio was as follows. In-bath processing machine: 12-color rotary pot dyeing tester (MINI-COLOUR 12EL type: manufactured by Texam Giken Co., Ltd.) Bath ratio (mass of fiber substrate containing polyamide fiber: mass of treatment liquid): 1:10 (5) Post-heat treatment process The fiber substrate containing the phenol derivative-treated polyamide fiber was set in a pin tenter and heat-set with dry heat at 170°C for 1 minute to obtain a fiber structure. The results are shown in Tables 1 and 2. In the fiber structure column of Table 2, "Antibacterial activity value after 10 standard washes" is listed as "A 10 "," "Antibacterial activity value after 50 high-temperature accelerated washings" 50 " was written.

[0060] The fiber structure obtained through the above process had an antibacterial activity index (A0-F) of 0.8 before washing and an antibacterial activity index (A 10 -F) was 0.7, and the antibacterial properties were good both before and after washing.

[0061] [Example 2] The same procedure as in Example 1 was carried out, except that the thiophenol-type synthetic tannin containing bisphenol S was used at 0.150% by mass. The fiber structure obtained through the above steps had an antibacterial activity index (A0-F) of 0.5 before washing and an antibacterial activity index (A0-F) of 0.5 after 10 standard washes. 10 -F) was 0.5, and the antibacterial properties were good both before and after washing.

[0062] [Example 3] The same procedure as in Example 1 was carried out, except that 0.008% by mass of oxolinic acid and 0.200% by mass of thiophenol-type synthetic tannin containing bisphenol S were used. The fiber structure obtained through the above steps had an antibacterial activity index (A0-F) of 1.0 before washing and an antibacterial activity index (A0-F) of 1.0 after 10 standard washes. 10 -F) was 0.9, and the antibacterial properties were good both before and after washing.

[0063] [Example 4] The same procedure as in Example 3 was carried out, except that the thiophenol-type synthetic tannin containing bisphenol S was used at 0.250 mass%. The fiber structure obtained through the above steps had an antibacterial activity index (A0-F) of 0.7 before washing and an antibacterial activity index (A0-F) of 0.8 after 10 standard washes. 10 -F) was 0.6, and the antibacterial properties were good both before and after washing.

[0064] [Example 5] The same procedure as in Example 3 was carried out except that oxolinic acid was used at 0.012% by mass. The fiber structure obtained through the above steps had an antibacterial activity index (A0-F) of 3.5 before washing and an antibacterial activity index (A0-F) of 3.5 after 10 standard washes. 10 -F) was 3.3, and the antibacterial properties were good both before and after washing.

[0065] [Example 6] The same procedure as in Example 3 was carried out except that oxolinic acid was used at 0.016% by mass. The fiber structure obtained through the above steps had an antibacterial activity index (A0-F) of 3.6 before washing and an antibacterial activity index (A0-F) of 3.6 after 10 standard washes. 10 -F) was 3.2, and the antibacterial properties were good both before and after washing.

[0066] [Example 7] The same procedure as in Example 6 was carried out, except that the thiophenol-type synthetic tannin containing bisphenol S was used at 0.300 mass%. The fiber structure obtained through the above steps had an antibacterial activity index (A0-F) of 2.2 before washing and an antibacterial activity index (A0-F) of 2.4 after 10 standard washes.10 -F) was 1.7, and the antibacterial properties were good both before and after washing.

[0067] [Example 8] The same procedure as in Example 6 was carried out, except that the thiophenol-type synthetic tannin containing bisphenol S was used at 0.400 mass%. The fiber structure obtained through the above steps had an antibacterial activity index (A0-F) of 1.0 before washing and an antibacterial activity index (A0-F) of 1.0 after 10 standard washes. 10 -F) was 0.9, and the antibacterial properties were good both before and after washing.

[0068] [Example 9] The same procedure as in Example 6 was carried out, except that the thiophenol-type synthetic tannin containing bisphenol S was used at 0.100% by mass. The fiber structure obtained through the above steps had an antibacterial activity index (A0-F) of 2.2 before washing and an antibacterial activity index (A0-F) of 2.4 after 10 standard washes. 10 -F) was 1.0, and the antibacterial properties were good both before and after washing.

[0069] [Example 10] The same procedure as in Example 6 was carried out, except that the thiophenol-type synthetic tannin containing bisphenol S was used at 0.050% by mass. The fiber structure obtained through the above steps had an antibacterial activity index (A0-F) of 2.1 before washing and an antibacterial activity index (A0-F) of 2.1 after 10 standard washes. 10 -F) was 1.0, and the antibacterial properties were good both before and after washing.

[0070] [Example 11] The same procedure as in Example 6 was carried out, except that the thiophenol-type synthetic tannin containing bisphenol S was used at 0.020% by mass. The fiber structure obtained through the above steps had an antibacterial activity index (A0-F) of 2.2 before washing and an antibacterial activity index (A0-F) of 2.4 after 10 standard washes. 10 -F) was 0.8, and the antibacterial properties were good both before and after washing. [Example 12] The same procedure as in Example 11 was carried out, except that oxolinic acid was used at 0.030% by mass. The fiber structure obtained through the above steps had an antibacterial activity index (A0-F) of 3.7 before washing and an antibacterial activity index (A0-F) of 3.7 after 10 standard washes. 10 -F) was 2.6, and the antibacterial properties were good both before and after washing.

[0071] [Example 13] The same procedure as in Example 6 was carried out, except that oxolinic acid was used at 0.030% by mass. The fiber structure obtained through the above steps had an antibacterial activity index (A0-F) of 3.7 before washing and an antibacterial activity index (A0-F) of 3.7 after 10 standard washes. 10 -F) was 3.4, and the antibacterial properties were good both before and after washing.

[0072] [Example 14] The same procedure as in Example 6 was carried out, except that oxolinic acid was used at 0.050% by mass. The fiber structure obtained through the above steps had an antibacterial activity index (A0-F) of 3.7 before washing and an antibacterial activity index (A0-F) of 3.7 after 10 standard washes. 10 -F) was 3.3, and the antibacterial properties were good both before and after washing.

[0073] [Example 15] The same procedure as in Example 6 was carried out, except that oxolinic acid was used at 0.080% by mass. The fiber structure obtained through the above steps had an antibacterial activity index (A0-F) of 3.6 before washing and an antibacterial activity index (A0-F) of 3.6 after 10 standard washes. 10 -F) was 3.5, and the antibacterial properties were good both before and after washing. * rose significantly.

[0074] [Comparative Example 1] The same procedure as in Example 6 was carried out, except that the phenol derivative treatment step was not carried out. The results are shown in Tables 1 and 2. The fiber structure obtained through the above steps had an antibacterial activity index (A0-F) of 3.6 before washing, indicating good antibacterial properties, but the antibacterial activity index (A0-F) after 10 standard washes was 3.6.10 -F) was -0.6, and the antibacterial properties after washing were poor.

[0075] Comparative Example 2 The same procedure as in Example 1 was carried out except that oxolinic acid was not added. The fiber structure obtained through the above steps had an antibacterial activity index (A0-F) of -1.7 before washing and an antibacterial activity index (A0-F) of -1.7 after 10 standard washes. 10 -F) was -1.8, and the antibacterial properties were poor both before and after washing.

[0076] Comparative Example 3 The same procedure as in Example 6 was carried out except that oxolinic acid was added in the phenol derivative treatment step rather than in the chemical solution treatment step. The fiber structure obtained through the above steps had an antibacterial activity index (A0-F) of 3.5 before washing and an antibacterial activity index (A0-F) of 3.5 after 10 standard washes. 10 -F) was -0.2, and the antibacterial properties after washing were poor.

[0077] Comparative Example 4 The same procedure as in Example 6 was carried out, except that oxolinic acid was added in the padding step after the phenol derivative treatment step, rather than in the chemical solution treatment step. In the padding treatment, a fibrous substrate having polyamide fibers was immersed in a treatment solution containing a quinoline compound, and squeezed with a mangle roller so that the treatment solution adhered to the substrate. The fibrous substrate having polyamide fibers was then set in a pin tenter and subjected to a wet heat treatment at 130°C for 2 minutes.

[0078] The fiber structure obtained through the above process had an antibacterial activity index (A0-F) of 3.4 before washing, which indicated good antibacterial properties. However, the antibacterial activity index (A 10 -F) was -0.5, and the antibacterial properties after washing were poor.

[0079] Comparative Example 5 The same procedure as in Example 6 was carried out, except that the thiophenol-type synthetic tannin containing bisphenol S was used at 0.010% by mass. The fiber structure obtained through the above steps had an antibacterial activity index (A0-F) of 3.0 before washing, indicating good antibacterial properties, but the antibacterial activity index (A0-F) after 10 standard washes was 0.010% by mass. 10 -F) was -0.9, and the antibacterial properties after washing were poor.

[0080] Comparative Example 6 The same procedure as in Example 6 was carried out, except that the thiophenol-type synthetic tannin containing bisphenol S was used at 0.500 mass%. The fiber structure obtained through the above steps had an antibacterial activity index (A0-F) of -0.2 before washing and an antibacterial activity index (A0-F) of -0.2 after 10 standard washes. 10 -F) was -0.4, and the antibacterial properties were poor both before and after washing.

[0081] Comparative Example 7 The same procedure as in Example 6 was carried out, except that the thiophenol-type synthetic tannin containing bisphenol S was used at 1.000 mass%. The fiber structure obtained through the above steps had an antibacterial activity index (A0-F) of -0.2 before washing and an antibacterial activity index (A0-F) of -0.2 after 10 standard washes. 10 -F) was -0.5, and the antibacterial properties were poor both before and after washing.

[0082] [Comparative Example 8] The same procedure as in Example 6 was carried out, except that 0.002 mass % of oxolinic acid was added. The fiber structure obtained through the above steps had an antibacterial activity index (A0-F) of -0.4 before washing and an antibacterial activity index (A0-F) of -0.4 after 10 standard washings. 10 -F) was -0.7, and the antibacterial properties were poor both before and after washing.

[0083] [Table 1]

[0084] [Table 2] [Industrial Applicability]

[0085] The fiber structure of the present invention has excellent antibacterial properties even after 10 standard washes. Such a fiber structure can be used for various applications requiring high antibacterial properties, such as fabrics for clothing, bedding, towels, rugs, curtains, sheets, etc.

Claims

1. A fiber structure comprising a dye, a quinoline-based compound, and a phenol derivative, and having polyamide fibers, The quinoline-based compound is contained in an amount of 0.04% by mass or more relative to the mass of the fiber structure, and, even after 10 standard washings in accordance with the "SEK Mark Textile Product Washing Method," the quinoline-based compound is contained in an amount of 0.04% by mass or more relative to the mass of the textile structure; and a fiber structure containing the phenol derivative in an amount of 0.20 mass % or more and 4.00 mass % or less relative to the mass of the fiber structure.

2. 2. The fiber structure according to claim 1, wherein the quinoline-based compound is at least one compound selected from the group consisting of oxolinic acid, ciprofloxacin, levofloxacin, moxifloxacin, garenoxacin, and sitafloxacin.

3. The fiber structure according to claim 1 or 2, wherein the quinoline-based compound is oxolinic acid.

4. 3. The fiber structure according to claim 1, wherein the mass ratio of the quinoline compound to the phenol derivative contained in the fiber structure is 1:1 to 1:

30.

5. a processing solution preparation step of preparing a processing solution containing a dye and a quinoline-based compound; a chemical solution treatment step of immersing a fiber substrate having polyamide fibers in the treatment solution and heat-treating the fiber substrate in a bath at a temperature of 80°C or higher and 110°C or lower under normal pressure or pressure; a phenol derivative treatment step of immersing a fiber substrate having polyamide fibers treated with the chemical solution in a treatment solution containing a phenol derivative and heat-treating the fiber substrate in a bath at 60°C or higher and 90°C or lower under normal pressure; a post-heat treatment step of performing dry heat treatment at an atmospheric temperature of 130°C or higher and 190°C or lower; A method for producing a fiber structure comprising the steps of:

6. The method for producing a fiber structure according to claim 5 , wherein the phenol derivative treatment step uses a treatment liquid containing the phenol derivative in an amount of 0.020 mass % or more and 0.400 mass % or less relative to the mass of the treatment liquid containing the phenol derivative.

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