Fiber structures and their manufacturing methods

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] This invention relates to a fiber structure that is excellent in antibacterial properties and wash durability, and to a method for producing the same. [Background technology]

[0002] In recent years, due to increased awareness of hygiene and health, many textile products around us, including medical uniforms such as white coats worn by healthcare workers in hospitals and clinics, as well as casual clothing and underwear worn by general consumers, are treated with antibacterial properties. These antibacterial textile products are washed regularly for repeated use. Therefore, there is a demand for antibacterial textile products that can withstand washing.

[0003] While the mainstream antibacterial processing technology for synthetic fiber products involves applying antibacterial agents after the product has been made into fabric or other materials, from a productivity standpoint, this method generally suffers from the problem of low antibacterial properties after washing, as the antibacterial agent is washed away during washing.

[0004] In response to this problem, studies have been conducted to improve the antibacterial properties after washing. For example, Patent Document 1 proposes a 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 pyrithione zinc), a type of pyridine-based 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 pyrithione zinc onto the polyamide fibers, resulting in a polyamide fiber structure that exhibits good antibacterial and antifungal properties even after 10 washes at 40°C.

[0005] In addition, Patent Document 2 proposes applying zinc 2-pyridylthiol-1-oxide to a fibrous structure by heat-treating it at a specific temperature under normal pressure or pressure. It is described that by doing so, a fibrous structure having excellent antibacterial properties with respect to industrial washing durability at a temperature of 85 ± 2°C can be obtained.

[0006] Furthermore, Patent Document 3 proposes immersing fibers in an antibacterial treatment liquid containing oxolinic acid or a salt thereof and heat-treating them in a treatment bath at a specific temperature under pressure. Thereby, an antibacterial agent and a treatment method for high-pressure processing with excellent antibacterial properties are described.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0008] In the methods disclosed in Patent Documents 1 and 2, although imparting antibacterial properties and washing durability has been achieved, since an antibacterial agent containing zinc ions is used, there is a problem that it is difficult to treat the wastewater generated after imparting the antibacterial agent. There is also a problem that it may affect the dyeability.

[0009] In the method disclosed in Patent Document 3, since oxolinic acid, which is an organic carboxylic acid compound, is used, there is no problem of wastewater treatment, which is an issue in Patent Documents 1 and 2. However, according to the study by the present inventors, when the fibrous substrate to be used has polyamide fibers, depending on the amount of the agent used and the processing steps, it may not be possible to obtain the desired antibacterial properties after washing.

[0010] The present invention was made to solve the above problems, and aims to provide a fiber structure and a method for producing the same that exhibits excellent antibacterial properties even after 10 standard washes, when using a fiber base material having polyamide fibers without using antibacterial agents such as zinc ions. [Means for solving the problem]

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

[0012] Furthermore, we found that in order to achieve the above effects, it is important to chemically treat the polyamide fiber substrate with dyes and quinoline compounds in the same bath, and then add phenol derivatives in a separate bath for phenol derivative treatment.

[0013] In other words, the present invention has the following configuration in order to solve the above problems. (1) A fibrous structure comprising a dye, a quinoline compound and a phenol derivative, and having polyamide fibers, The quinoline compound is contained in an amount of 0.04% by mass or more relative to the mass of the fibrous structure. Furthermore, even after performing 10 standard washes in accordance with the "Washing Instructions for SEK Mark Textile Products," the quinoline compound remains present at a concentration of 0.04% by mass or more relative to the mass of the textile structure. A fiber structure comprising the phenol derivative in an amount of 0.20% by mass or more and 4.00% by 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 compound is an 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 process to prepare a treatment solution containing dyes and quinoline compounds, A chemical treatment step involves immersing a fibrous substrate having polyamide fibers in the aforementioned treatment solution and heat-treating it in a bath at a temperature of 80°C to 110°C under normal pressure or pressurized conditions. A phenol derivative treatment step involves immersing a fiber substrate having polyamide fibers that have been treated with the chemical solution in a treatment solution containing a phenol derivative, and then heat-treating it in a bath at 60°C to 90°C under normal pressure. A post-heat treatment process involves dry heat treatment at an ambient temperature of 130°C to 190°C, A method for manufacturing a fibrous structure containing [a specific material]. (6) The method for producing a fiber structure according to (5), wherein in the phenol derivative treatment step, a treatment solution containing the phenol derivative in an amount of 0.020% by mass or more and 0.400% by mass or less relative to the mass of the treatment solution containing the phenol derivative is used. [Effects of the Invention]

[0014] According to the present invention, it is possible to provide a fiber structure that exhibits excellent antibacterial properties after 10 standard washes, when it contains dyes and quinoline compounds, and a method for producing the same. [Modes for carrying out the invention]

[0015] [Textile structures] The present invention will be described in detail below along with preferred embodiments, but is not limited to these embodiments. The fiber structure of the present invention comprises a dye, a quinoline compound, and a phenol derivative, comprising 0.04% by mass or more of the quinoline compound relative to the mass of the fiber structure, and even after 10 standard washes in accordance with the "Washing Method for SEK Mark Textile Products", it still contains 0.04% by mass or more of the quinoline compound relative to the mass of the fiber structure, and the phenol derivative is comprising 0.20% by mass or more and 4.00% by mass or less relative to the mass of the fiber structure.

[0016] The fiber structure of the present invention exhibits 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 It has the characteristic of being greater than the standard fabric growth value F. Furthermore, the antibacterial activity value A after 50 high-temperature accelerated washes. 50 It also has the characteristic of being greater than the standard fabric growth value F.

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

[0018] <Textile substrate containing polyamide fibers> The fibrous base material having polyamide fibers constituting the fibrous structure of the present invention can preferably be a fabric such as a woven fabric, knitted fabric, or nonwoven fabric. Furthermore, the polyamide fibers may be in the form of filament yarn or spun yarn, and are not limited to these. Additionally, if necessary, synthetic fibers other than polyamide fibers, such as polyester and acrylic, natural fibers such as cotton, wool, and silk, or semi-synthetic fibers such as rayon and acetate may be combined and used in forms such as interwoven fabrics, interknitted fabrics, blended fabrics, and blended fibers.

[0019] The proportion of polyamide fibers in the fiber base material is not limited, but a higher proportion improves the antibacterial properties after 10 standard washes and 50 high-temperature accelerated washes in the present invention. Therefore, the polyamide fibers are preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 80% by mass or more, relative to the total mass of the fiber base material.

[0020] The polyamide fibers described above are fibers obtained by melt-spinning a resin consisting of a polymer having amide bonds. Examples of polyamide fibers used include nylon 6, synthesized by the ring-opening polymerization reaction of caprolactam, and nylon 66, synthesized by the polycondensation reaction of adipic acid and hexamethylenediamine. In addition, other known polyamide fibers such as nylon 8, nylon 6-10, and nylon 11 can also be used.

[0021] Furthermore, while there are no particular restrictions on the fineness of the polyamide fibers, it is preferable that the single fiber fineness be between 0.04 dtex and 5.00 dtex, as this allows the effects of the present invention to be remarkably demonstrated.

[0022] The fiber structure of the present invention may contain, in addition to the dyes, quinoline compounds, and phenol derivatives described later, other agents such as water absorbents and fluorescent whitening agents in any amount.

[0023] <dye> The fiber structure of the present invention contains a dye. The dye, as used herein, is a water-soluble organic compound used for coloring 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] Furthermore, the type of dye used in this invention is not particularly limited. When considering the coloring of polyamide fibers, suitable dyes include acid dyes having sulfo groups or carboxyl groups within the dye molecule, metal complex salt dyes bonded to metal atoms such as chromium, cobalt, or copper, and fluorescent whitening agents used to further enhance the white color. Moreover, the amount of dye attached to the fiber substrate having polyamide fibers is not limited; it is sufficient if the dye necessary to produce the desired hue is attached.

[0025] <Quinoline compounds> The above 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), and moxifloxacin ((1S,6S)-1-cyclopropyl-7-(2,8-diazabicyclo[4.3.0]non-8-I It is preferable that the compound is at least one compound selected from the group consisting of (1-(1R,2S)-2-fluorocyclopropyl)-6-fluoro-8-methoxy-4-oxo-1,4-dihydroquinoline-3-carboxylic acid), galenoxacin (1-cyclopropyl-8-(difluoromethoxy)-7-[(1R)-1-methyl-2,3-dihydro-1H-isoindole-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, it is more preferable that the quinoline compound is an oxolinic acid.

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

[0027] The quinoline compound content 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. A content of 0.04% by mass or more relative to the mass of the fiber structure makes it possible to exhibit good antibacterial properties. On the other hand, if the mass of the quinoline compound is too high, a large amount of white quinoline compound will adhere to the surface of the fiber structure, causing the fiber structure to whiten (i.e., lightness L * (The concentration increases), and there is a tendency for the hue of the fiber structure to change. For this reason, the amount of quinoline compound is preferably 0.50% by mass or less, and more preferably 0.30% by mass or less, relative to the mass of the fiber structure. Here, the ratio of the mass of the quinoline 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 washes in accordance with the "Washing Method for SEK Mark Textile Products," the content of quinoline compounds 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. The antibacterial effect achieved in this invention is obtained when the content of quinoline compounds in the fiber structure is 0.04% by mass or more relative to the mass of the fiber structure after 10 standard washes.

[0029] <Phenol derivatives> The fibrous structure of the present invention contains a phenol derivative. In addition to suppressing dye shedding by binding to dyes present in the fibrous substrate having polyamide fibers or by coating the fiber surface, the phenol derivative in the present invention also plays a role in suppressing the shedding of quinoline compounds present in the fibrous substrate having polyamide fibers.

[0030] Examples of phenol derivatives used in the present invention include phenol sulfonic acid formaldehyde resin, novolac-type resin sulfonates, resol-type resin methanesulfonic acid, and other phenol-type synthetic tannins, thiophenol-type synthetic tannins, and dihydroxydiphenylsulfone-type synthetic tannins, which are 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.

[0031] It is important that the fiber structure of the present invention contains 0.20% by mass or more of a 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 compound on the fiber structure is weakened, resulting in a decrease in antibacterial properties after washing, and the antibacterial properties of the present invention cannot be obtained. 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 makes it difficult for the quinoline compound and fungi to come into contact, and thus the antibacterial performance achieved in the present invention may not be exhibited. Therefore, it is important that the phenol derivative is contained at 4.00% by mass or less, preferably 2.00% by mass or less. Here, the ratio of the mass of the phenol derivative to the mass of the fiber structure of the present invention is measured by the method described in the examples.

[0032] Furthermore, in order to exhibit 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 fibrous structures> The fiber structure of the present invention, according to the antibacterial evaluation method described in the SEK Mark Textile Product Certification Standards established by the Japan Textile Evaluation Technology Council, achieves an antibacterial activity value of A after 10 standard washes. 10The antibacterial activity value A becomes greater than the standard fabric growth value F. In addition, the antibacterial activity value A after 50 high-temperature accelerated washes is greater than F. 50 The value becomes greater than the standard fabric growth value F. Standard washing, high-temperature accelerated washing, and antibacterial testing will be evaluated using the methods described later.

[0034] [Application] The fibrous structures provided by the present invention can be applied to various uses requiring high antibacterial properties, and can be used, for example, as fabrics for clothing, bedding, towels, rugs, curtains, sheets, and the like.

[0035] As clothing, it can be used for general clothing, uniforms, formal and business attire, work clothes, sportswear, and more.

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

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

[0038] Furthermore, the quinoline compound is added to the treatment solution in an amount of 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, relative to the mass of the treatment solution.

[0039] <Chemical treatment process> In the chemical treatment process, a bath processing method is employed. Bath processing, as defined here, is a method in which a fibrous substrate containing polyamide fibers is immersed in a bath containing a treatment solution and heated, thereby causing the treatment solution to adhere to the fibrous substrate containing polyamide fibers.

[0040] In this process, first, the polyamide fiber substrate is added to the processing solution prepared in the processing solution preparation step under a bath ratio (mass of polyamide fiber substrate:mass of processing solution) of 1:5 to 1:30. Subsequently, a heat treatment is performed in a sealed container under atmospheric pressure or pressurized conditions in a bath at a temperature of 80°C to 110°C.

[0041] Furthermore, if the quinoline compound is treated with a chemical solution in the phenol derivative treatment step described later, or in the padding step, the antibacterial performance after washing according to the present invention will not be exhibited. The padding step referred to here is a step in which a fiber substrate having polyamide fibers is immersed in a treatment solution, pressed with a mangle roller or the like so that a certain amount of treatment solution adheres to it, and then the treatment solution is attached to the fiber substrate having polyamide fibers by dry heat treatment in a dryer or moist heat treatment under saturated steam at 100°C.

[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 in an amount of preferably 0.020% to 0.400% by mass, more preferably 0.100% to 0.200% by mass, relative to the mass of the treatment solution. Then, the fiber substrate having polyamide fibers is added to the treatment solution containing the phenol derivative under a bath ratio (mass of fiber substrate having polyamide fibers:mass of treatment solution) of 1:5 to 1:30, and subsequently, heat treatment is performed in a sealed container under atmospheric pressure in a bath at a temperature of 60°C to 90°C. After the heat treatment, the fiber substrate having polyamide fibers is removed from the container and subsequently washed with water and air-dried.

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

[0044] <Post-processing process> The fiber structure according to the present invention is obtained through the aforementioned post-heat treatment process. However, in the manufacturing method of the fiber structure according to the present invention, various finishing processes can be carried out, similar to those for general fiber structures. For example, calendering, which improves the light reflection of the surface of the fiber structure and gives it a glossy appearance by compressing and smoothing it using rollers, and napping, which creates a fluffy surface and provides heat retention and flexibility by scratching or abrading the surface of the fiber structure using needles or abrasive cloth. Of course, in the present invention, the fiber structure obtained by carrying out these finishing processes is also considered to be the fiber structure of the present invention. [Examples]

[0045] Next, the invention will be described in more detail with reference to examples, but the method for manufacturing the fiber structure of the present invention is not limited to these examples. The washing method and various test methods in the examples were carried out according to the following methods.

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

[0047] For standard washing, a fully automatic washing machine conforming to the Type C standard washing machine - vertical axis, top-loading type (pulsator type) specified in the equipment and materials section of JIS L 1930:2014 "Test Methods for Home Laundry of Textile Products" was used. The detergent used was "JAFET Standard Formula Detergent," and 40 mL of "JAFET Standard Formula Detergent" was added to 30 L of water to prepare the washing solution. Subsequently, the washing conditions of the washing machine were set to washing method C4G specified in Annex F of JIS L 1930:2014 "Test Methods for Home Laundry of Textile Products." Specifically, the washing conditions were: water temperature: 40±3℃, indicated water volume: 40 L, washing time: 3 minutes, spin-drying time: 3 minutes; and the rinsing conditions were: indicated water volume: 40 L, rinsing time: 2 minutes, spin-drying time: 3 minutes. This constituted one cycle. After repeated washing, drying was performed at a drying temperature of 80℃ or lower. The garments were hung to dry or laid flat in a place where they were not exposed to direct sunlight.

[0048] Next, for high-temperature accelerated washing, a washer washing machine was used, and 120 mL of "JAFET standard blend detergent" was added to 90 L of water to create the washing solution. Then, the textile structure and, if necessary, load fabric were added to this washing solution so that the bath ratio (mass of textile structure:mass of washing solution) was 1:30, and the total mass of the textile structure and load fabric was adjusted to 3 kg. After that, 1) Wash at 80°C for 120 minutes. 2) Drainage The following was done, and rinsing was performed using a standard washing machine with a centrifugal wringing device, standard washing capacity, and standard water volume, which conforms to the JIS C 9606:2007 (electric washing machine) standard, as specified in "Appendix 1 Test Methods by Symbol - Washing Method (Water Washing), No. 103" of JIS L 0217:1995 "Symbols and Methods of Displaying for Handling Textile Products". That is, 3) Thoroughly dehydrate the fibrous structure and load fabric for 3 to 5 minutes. 4) 15-minute overflow rinse (aim for 3-5 replacement water volumes) 5) Dehydrate using the same method as in 4). This was done. Then, 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 washer washing machine and a standard washing machine. Finally, only the fiber structure was removed. 6) Use a standard washing machine for 5 - minute overflow rinsing (aim for 3 - 5 times the replacement water volume). 7) Dehydrate in the same way as in 3). 8) Dry under the condition that the drying temperature is 80°C or lower. This was carried out. Regarding the step in 8), hanging or laying flat drying was performed in a state not affected by direct sunlight.

[0049] (Antibacterial test) 1) Test method: It was carried out by the bacterial liquid absorption method based on JIS L 1902:2015 "Test Method for Antibacterial Property and Antibacterial Effect of Textile Products". In addition, it was carried out under the condition that 0.050 mass% of the non - ionic surfactant "Tween" (registered trademark) 80 was added to the mass of the fiber structure in the test bacterial suspension. 2) Test strain: Staphylococcus aureus 3) Judgment method: It was in accordance with the evaluation criteria for bacteriostatic processing (specific use: red) in "18.3 Evaluation Criteria for Bacterial Liquid Absorption Method" of the above "SEK Mark Fiber Product Certification Criteria". That is, the antibacterial activity value after subjecting the fiber structure after antibacterial processing to 10 standard washes was A 10、 The antibacterial activity value after subjecting it to 50 high - temperature accelerated washes was A 50 , and taking the growth value of the unwashed standard cloth as F, when A 10 > F, that is, when A 10 - F> 0.0, it was considered that the antibacterial property was good after 10 standard washes, and when A 10 - F≤0.0, it was judged that the antibacterial property was poor. Also, when A 50 > F, that is, when A 50 - F> 0.0, it was considered that the antibacterial property was good after 50 high - temperature accelerated washes, and when A 50 - F≤0.0, it was judged that the antibacterial property was poor. The standard cloth refers to the JIS L 0803 attached white cloth (cotton 3 - 1) described in "3.1 Test Specimen (control specimen)" of JIS L 1902:2015 "Test Method for Antibacterial Property and Antibacterial Effect of Textile Products", which is sold by the Textile Evaluation Technology Council as a standard cloth for antibacterial tests (cotton) and has been subjected to water washing treatment.

[0050] Here, the antibacterial activity value A after n washes. n The growth values ​​F for the standard fabric were 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 : The common logarithm of the arithmetic mean of the number of viable bacteria in three samples of standard cloth immediately after inoculation with the test bacteria. log C t : Common logarithm of the arithmetic mean of viable bacterial counts in three samples after 18 hours of incubation on a standard cloth. log T o : The common logarithm of the arithmetic mean of the number of viable bacteria in three samples immediately after inoculation of the test bacteria in the obtained fiber structure. log T t : The common logarithm of the arithmetic mean of the number of viable bacteria in three samples after 18 hours of incubation in the obtained fibrous structure. Furthermore, the antimicrobial activity value A0 of the fibrous structure before washing was also evaluated using the method described above.

[0051] (Color measurement) Using a spectrophotometer model CM-3700d (manufactured by Konica Minolta, Inc.), the diffuse reflectance of a fiber structure was measured with a D65 light source and a 10-degree field of view, and the brightness L was calculated. * The brightness L was measured here. * This is JIS Z8781-4:2013 (Colorimetry - Part IV: CIE 1976 L * a * b * L is defined in the "3.3 CIE1976 Lightness Index" of the color space. * It refers to a value.

[0052] (Ratio of the mass of quinoline compounds to the mass of the fibrous structure) 1.00 g of the fibrous structure was weighed out and immersed in a solution of methanol and sodium hydroxide aqueous solution. The solution was then filtered. Next, the mass of the quinoline compound attached to the fibrous structure was measured using high-performance liquid chromatography. Finally, the ratio (mass %) of the mass of the quinoline compound to the accurately weighed mass of the fibrous structure was calculated.

[0053] In addition, in the column for fiber structures in Table 2, the "ratio of the mass of quinoline compounds to the mass of fiber structures" is written as "amount of quinoline compounds present".

[0054] (Ratio of the mass of the phenol derivative to the mass of the fibrous structure) As described above, the same method was used to calculate the ratio of the mass of the quinoline 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 sodium hydroxide aqueous solution. Then, the solution was filtered. Subsequently, the mass of the phenol derivative attached to the fiber structure was measured by high-performance liquid chromatography. After that, the ratio (mass %) of the mass of the phenol derivative to the mass of the accurately weighed fiber structure was calculated.

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

[0056] [Example 1] (1) Preparation of a fiber substrate having polyamide fibers A polyamide fiber substrate was prepared by heat-setting a fabric using polyamide fibers, which consist of multifilaments of 78 dtex-26 filaments (single fiber fineness 3.00 dtex) made of nylon 66 synthesized by the polycondensation reaction of adipic acid and hexamethylenediamine, as both warp and weft threads, at 180°C for 0.5 minutes using dry heat.

[0057] (2) Preparation of processing solution A treatment solution consisting of an acid dye, a quinoline compound, and a dyeing acid was prepared. The following chemicals were used, and the mass ratio of each chemical to the mass of the treatment solution was adjusted as follows. • Acid dye: Kayacryl Miling Blue BW (manufactured by Nippon Kayaku Co., Ltd.), 0.200% by mass • Quinoline compound: Oxolinic acid, 0.004% by mass • Staining acid: Mixed aqueous solution of 70% by mass acetic acid / 30% by mass sodium acetate, 0.005% by mass In addition, in the "Manufacturing Method" column of Table 1, "the ratio of the mass of the quinoline compound to the mass of the processing solution" is written as "quinoline compound".

[0058] (3) Chemical treatment process A fibrous substrate containing polyamide fibers was immersed in the treatment solution prepared above and subjected to chemical treatment under pressure at 100°C for 30 minutes in a bath processing machine. Afterward, the fibrous substrate containing polyamide fibers was removed from the bath processing machine and washed and dewatered. The bath processing machine used was the following apparatus, and the bath ratio was as follows. Bath processing machine: 12-color rotary pot dyeing test machine (MINI-COLOUR 12EL model: manufactured by Texam Giken Co., Ltd.) Bath ratio (mass of polyamide fiber substrate:mass of treatment solution): 1:10 (4) Phenol derivative treatment process A treatment solution consisting of a phenol derivative was prepared. The following chemicals were used, and the mass ratio of the phenol derivative to the treatment solution was adjusted as follows. • Phenol derivatives: Thiophenol-type synthetic tannins containing bisphenol S, 0.100% by mass In addition, in the "Manufacturing Method" column of Table 1, "the ratio of the mass of the phenol derivative to the mass of the processing solution" is written as "phenol derivative".

[0059] A fibrous substrate containing polyamide fibers that had been treated with a chemical solution was immersed in a treatment solution consisting of the phenol derivative prepared above, and treated with the phenol derivative in a bath processing machine at atmospheric pressure and 80°C for 20 minutes. After that, the fibrous substrate containing polyamide fibers was removed from the bath processing machine and washed and dewatered. The bath processing machine used was the following apparatus, and the bath ratio was as follows. • Bath processing machine: 12-color rotary pot dyeing test machine (MINI-COLOUR 12EL model: manufactured by Texam Giken Co., Ltd.) • Bath ratio (mass of polyamide fiber substrate:mass of treatment solution): 1:10 (5) Post-heat treatment process A fiber substrate having polyamide fibers treated with a phenol derivative was set in a pin tenter, and a dry heat setting was performed at 170°C for 1 minute to obtain a fiber structure. The results are shown in Tables 1 and 2. In the column for fiber structure in Table 2, the "antibacterial activity value after 10 standard washes" is set to "A 10 "Antibacterial activity value after 50 high-temperature accelerated washes" is "A 50 It was written as "".

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

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

[0062] [Example 3] In Example 1, the procedure was carried out in the same manner as in Example 1, 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 process had an antibacterial activity index (A0-F) of 1.0 before washing, and an antibacterial activity index (A0-F) after 10 standard washes. 10 -F) was 0.9, indicating good antibacterial properties both before and after washing.

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

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

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

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

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

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

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

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

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

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

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

[0074] [Comparative Example 1] In Example 6, the procedure was carried out in the same manner as in Example 6, except that the phenol derivative treatment step was omitted. 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. However, the antibacterial activity index (A0-F) after 10 standard washes was lower.10 -F) was -0.6, indicating poor antibacterial properties after washing.

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

[0076] [Comparative Example 3] In Example 6, the procedure was carried out in the same manner as in Example 6, except that oxolinic acid was added in the phenol derivative treatment step instead of the chemical 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) after 10 standard washes. 10 -F) was -0.2, indicating poor antibacterial properties after washing.

[0077] [Comparative Example 4] In Example 6, the procedure was carried out in the same manner as in Example 6, except that oxolinic acid was added in the padding step after the phenol derivative treatment step, rather than in the chemical treatment step. In the padding process, the fiber substrate having polyamide fibers was immersed in a treatment solution containing a quinoline compound, and then compressed with a mangle roller to ensure the treatment solution adhered to it. After that, the fiber substrate having polyamide fibers was set in a pin tenter and subjected to moist 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, indicating good antibacterial properties. However, the antibacterial activity index (A0-F) after 10 standard washes was lower. 10 -F) was -0.5, indicating poor antibacterial properties after washing.

[0079] [Comparative Example 5] In Example 6, the procedure was carried out in the same manner as in Example 6, except that 0.010% by mass of thiophenol-type synthetic tannin containing bisphenol S was used. The fiber structure obtained through the above process 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... 10 -F) was -0.9, indicating poor antibacterial properties after washing.

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

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

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

[0083] [Table 1]

[0084] [Table 2] [Industrial applicability]

[0085] The fibrous structure of the present invention exhibits excellent antibacterial properties even after 10 standard washes. Such a fibrous structure can be applied to various uses where high antibacterial properties are required, and can be used, for example, as fabric for clothing, bedding, towels, rugs, curtains, sheets, and the like.

Claims

1. A fibrous structure comprising a dye, a quinoline compound, and a phenol derivative, and having polyamide fibers, The quinoline compound is contained in an amount of 0.04% by mass or more relative to the mass of the fibrous structure. Furthermore, even after performing 10 standard washes in accordance with the "Washing Method for SEK Mark Textile Products," the quinoline compound remains present at a concentration of 0.04% by mass or more relative to the mass of the textile structure. The quinoline compound is oxolinic acid, Furthermore, the phenol derivative is contained in an amount of 0.20% by mass or more and 4.00% by mass or less relative to the mass of the fibrous structure. The phenol derivative is a thiophenol-type synthetic tannin containing bisphenol S, The mass ratio of the quinoline compound and the phenol derivative contained in the fibrous structure is 1:1 to 1:

30. Fiber structure.

2. A process for preparing a treatment solution containing dyes and quinoline compounds, A chemical treatment step involves immersing a fibrous substrate having polyamide fibers in the aforementioned treatment solution and heat-treating it in a bath at a temperature of 80°C to 110°C under normal pressure or pressurized conditions. A phenol derivative treatment step involves immersing a fiber substrate having polyamide fibers that have been treated with the chemical solution in a treatment solution containing a phenol derivative, and then heat-treating it in a bath at 60°C to 90°C under normal pressure. A post-heat treatment process involves dry heat treatment at an ambient temperature of 130°C to 190°C, Includes, The quinoline compound is oxolinic acid, The phenol derivative is a thiophenol-type synthetic tannin containing bisphenol S. A method for producing a fibrous structure according to claim 1.

3. The method for producing a fiber structure according to claim 2, wherein in the phenol derivative treatment step, a treatment solution containing the phenol derivative in an amount of 0.020% by mass or more and 0.400% by mass or less relative to the mass of the treatment solution containing the phenol derivative is used.

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