Method for producing deodorizing fiber structure

Abstract

To provide a deodorant fiber structure having a deodorizing function restored even after being treated with an alkali and having high washing resistance, and a method of manufacturing the same.SOLUTION: There is provided a deodorant fiber structure containing deodorant fibers in which a layer-shape inorganic deodorant is mixed with a polymer, in which in the layer-shape inorganic deodorant, an interlayer distance is 0.1 nm or more and 0.9 nm or less, and a crystallite size is 1 nm or more and 30 nm or less, and in the deodorant fiber structure, either an ammonia gas reduction rate of home washing on 0 time washing or that after 10 times washing is 70% or more. There is also provided a method of manufacturing the deodorant fiber structure, comprising: a process of alkaline treatment of the fiber structures; and a processing process of dipping and heating in an aqueous solution containing an organic acid.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention provides a deodorizing fiber structure that has high deodorizing performance and high washability. thing Regarding the manufacturing method. [Background technology]

[0002] Deodorizing fibers are used in carpets, curtains, bedding, underwear, diapers, sanitary products, etc., and since clothing that comes into direct contact with the skin can cause discomfort due to odors such as sweat and body odor, there is a high demand for textile products with deodorizing properties. Patent Document 1 proposes knitting fabrics using elastic fibers and deodorizing fibers made of crosslinked acrylate yarns containing carboxyl groups and crosslinked by hydrazine treatment. Patent Document 2 proposes elastic fibers containing zinc oxide and zirconium phosphate. Patent Document 3 proposes synthetic fibers containing α-zirconium phosphate and / or α-titanium phosphate. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2002-000659 [Patent Document 2] Japanese Patent Application Laid-Open No. 2006-028453 [Patent Document 3] Japanese Patent Application Laid-Open No. 2018-178313 DISCLOSURE OF THE INVENTION [Problem to be solved by the invention]

[0004] However, cross-linked acrylate yarns such as those described in Patent Document 1 are highly hygroscopic, and there is a problem in that they do not exhibit their deodorizing function when they absorb moisture or water. Furthermore, the fibers described in Patent Documents 2 and 3 have the problem that their deodorizing function is lost when they are treated with alkali. Alkali treatment is used in the case of polyester fibers in an alkali weight loss process, and in the case of cotton fibers, hemp fibers, etc. in refining, bleaching, bleaching, and mercerizing processes, and the loss of deodorizing function is a problem.

[0005] The present invention solves the above-mentioned problems of the prior art, and provides a deodorizing fiber structure that restores its deodorizing function even after alkali treatment and has high washability. thing A method of manufacture is provided. [Means for solving the problem]

[0006] The method for producing a deodorizing fiber structure of the present invention is a method for producing a deodorizing fiber structure including a deodorizing fiber in which an inorganic layered deodorizer is mixed with a polymer, comprising the steps of: The inorganic layered deodorant is α-zirconium phosphate, (1) Fiber Fiber structures a step of alkali treatment with an aqueous solution containing an alkaline substance; (2) Then, by including a step of immersion and heat treatment in an aqueous solution containing an organic acid having 2 to 6 carbon atoms and a carboxyl group. , The interlayer distance of the α-zirconium phosphate but 0.1 nm to 0.9 nm, and crystallite size but 1 nm or more and 30 nm or less, The ammonia gas reduction rate after 0 and 10 home washes was over 70%. Manufacturing deodorizing fiber structures It is characterized by: [Effects of the Invention]

[0008] The present invention provides a deodorizing fiber structure including a deodorizing fiber in which a polymer is mixed with an inorganic layered deodorizer, wherein the inorganic layered deodorizer has an interlayer distance of 0.1 nm to 0.9 nm and a crystallite size of 1 nm to 30 nm, and the deodorizing fiber structure has an ammonia gas reduction rate of 70% or more after both 0 and 10 home washes, thereby providing a deodorizing fiber structure with high deodorizing performance and high washability, and a method for producing the same. Specifically, when a deodorizing fiber structure including a deodorizing fiber in which an inorganic layered deodorizer is mixed is treated with alkali, the interlayer distance exceeds 0.9 nm, significantly reducing the deodorizing function. However, when treated with an organic acid, the interlayer distance of the deodorizer becomes 0.9 nm or less, restoring the deodorizing function. This deodorizing function also has good washability. [Brief explanation of the drawings]

[0009] [Figure 1] FIG. 1 is a multi-plot graph of the wide-angle X-ray diffraction pattern of the inorganic layered deodorant used in one embodiment of the present invention, and is an enlarged view of the vicinity of 2θ=10°. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present inventors have encountered the problem that elastic fibers containing inorganic layered deodorizers such as α-zirconium phosphate initially have deodorizing properties, but when treated with alkali, the deodorizing properties are lost, and they have investigated the cause. The layer structure of α-zirconium phosphate is shown below (Chemical Formula 1), and the interlayer distance is approximately 7.55 Å (angstroms, 0.755 nm) (Hasegawa Yoshinori et al., "On the Ion Exchange Properties of Layered Phosphate M(IV)(HPO4)2·H2O (M=Zr, Hf)," IONICS, October 1985 issue). [ka]

[0011] The interlayer distance of the α-zirconium phosphate is such that it can capture substances smaller than the size of an ammonia molecule, and it is presumed that the captured gas is neutralized and deodorized by ionic bonding with the functional groups of the α-zirconium phosphate crystals. However, it was found that when a fiber structure is placed under strong alkaline conditions such as alkali treatment, the interlayer distance expands beyond 0.9 nm due to ion exchange with alkali metals, etc., and substances other than ammonia are incorporated, reducing the active functional groups and causing the deodorizing function to be inactivated. Therefore, various studies were conducted to restore the deodorizing function, and it was found that if the inorganic layered deodorizer is treated with an organic acid after alkali treatment, the interlayer distance can be restored to its original state, and the deodorizing function can also be restored. The experimental conditions and results will be explained later, but the key points are as shown in Table 1 below.

[0012] [Table 1]

[0013] As is clear from Table 1, the interlayer distance and crystallite size of α-zirconium phosphate increase after refining and bleaching treatment, but the interlayer distance returns to its original state and the crystallite size becomes smaller than the original state by organic acid treatment. This is a novel finding. The present invention was completed based on the above ideas and problems.

[0014] The present invention relates to a deodorizing fiber structure including a deodorizing fiber in which an inorganic layered deodorizer is mixed with a polymer. One example is a fiber obtained by adding and mixing an inorganic layered deodorizer with a spinning solution. Spinning may be performed by melt spinning or wet spinning. The deodorizing fiber structure has been alkali-treated. In the case of polyester fibers, alkali treatment is performed by alkali weight reduction processing. In the case of cotton fibers, hemp fibers, and the like, alkali treatment is performed by scouring, bleaching, bleaching, and mercerizing (mercerizing) processing. The amount of inorganic layered deodorizer added to the deodorizing fiber is preferably 0.5 to 10% by mass, and more preferably 1 to 7% by mass, based on the deodorizing fiber as a parameter. High deodorizing properties can be maintained within this range.

[0015] The fiber structure is treated with an alkali and then an organic acid, and the deodorizer has an interlayer distance of 0.9 nm or less, and the ammonia deodorizing ability after both 0 and 10 home washes is 70% or more. The deodorizer preferably has an interlayer distance of 0.70 to 0.85 nm, more preferably 0.72 to 0.80 nm. This results in a deodorizing fiber structure with high deodorizing performance and high washability. Furthermore, when treated with an organic acid, the deodorizer loses bonds with alkali metals such as sodium and potassium, restoring the deodorizing function of the deodorizer. The deodorant is preferably at least one selected from α-zirconium phosphate, α-hafnium phosphate, and α-titanium phosphate. The deodorant effects of α-zirconium phosphate and α-titanium phosphate are recognized in Patent Document 3. The source document of Chemical Formula 1 states that the interlayer distance of α-hafnium phosphate is equivalent to that of α-zirconium phosphate. Of these, α-zirconium phosphate is preferred.

[0016] The deodorizing fiber is preferably at least one selected from synthetic fibers and recycled fibers. The polymer constituting the deodorizing fiber may be a thermoplastic resin such as polyester, polyamide, polyolefin, or polyurethane, or a thermosetting resin such as regenerated cellulose or acrylic polymer. These resins can be mixed with the inorganic layered deodorizer in a spinning solution. Regenerated fibers include rayon, cupra, Polynosic, Lyocell (registered trademark), etc. Any spinning solution that can be mixed with the inorganic layered deodorizer can be used.

[0017] The textile structure contains 100% by mass of the deodorizing fiber or the deodorizing fiber and other fibers. When the other fibers are contained, the deodorizing fiber preferably accounts for 1 to 99% by mass of the textile structure as a parameter. More preferably, the deodorizing fiber accounts for 2 to 50% by mass, and even more preferably, the deodorizing fiber accounts for 5 to 30% by mass. Within these ranges, deodorizing properties can be exhibited. The other fibers are preferably at least one selected from natural fibers, synthetic fibers, and recycled fibers. Natural fibers include cotton, linen, wool, silk, etc.

[0018] The organic acid is preferably a carboxyl group-containing organic acid having 2 to 6 carbon atoms. The organic acid is effective in restoring the deodorant. It can also be made into an aqueous solution, which makes it convenient for processing. The carboxyl group-containing organic acid having 2 to 6 carbon atoms is preferably at least one selected from citric acid, maleic acid, malic acid, acetic acid, and succinic acid. Optical isomers, if any, are also included. Citric acid has the structure shown below (Chemical Formula 2). [ka] Maleic acid has the structure shown below (Chemical Formula 3). [ka] Malic acid has the structure shown below (Chemical Formula 4). [ka] Acetic acid has the structure shown below (Chemical Formula 5). [ka] Succinic acid has the structure shown below (Chemical Formula 6). [ka]

[0019] The fabric pH of the fiber structure is preferably 4.0 to 5.8, and more preferably 4.1 to 5.5. A fabric pH on the weakly acidic side is gentle on the skin and does not have any adverse effects. The fabric pH is measured according to the "Testing Method for Woven and Knit Fabrics" specified in JIS L1096:2010 8.37.

[0020] The ammonia deodorizing property of the fiber structure after 10 home launderings is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. This allows for a deodorizing fiber structure with high deodorizing performance and high washability. The home laundering method and ammonia deodorizing property test will be described later.

[0021] In the present invention, the fiber structure may have any structure or shape, for example, a fabric-like material, a belt-like material, a string-like material, a thread-like material, etc. Preferably, a material containing a fabric-like woven or knitted fabric or a nonwoven fabric is used, and the fiber structure may also be a material containing a composite material containing such a fiber structure.

[0022] A fiber structure according to one embodiment of the present invention contains elastic fiber and at least cotton, and may contain other fibers such as synthetic fiber, regenerated fiber, semi-synthetic fiber, and natural fibers other than cotton. When the fiber structure is used as a parameter, the ratio of elastic fiber to cotton is preferably 1 to 30% by mass of elastic fiber and 70 to 99% by mass of cotton. Furthermore, when cotton is used as a parameter, it is preferable that the ratio be 10 to 90% by mass of cotton and 10 to 90% by mass of fibers other than cotton.

[0023] Synthetic fibers include polyester fibers, polyamide fibers, polyethylene fibers, polypropylene fibers, polyvinyl alcohol fibers, polyvinyl chloride fibers, and polyacrylonitrile fibers. Polyester fibers include polyethylene terephthalate, polybutylene terephthalate, and polytrimethylene terephthalate, including those copolymerized with a third component such as isophthalic acid. Regenerated and semi-synthetic fibers include rayon and acetate, while natural fibers include hemp, wool, and silk. These fibers may be either staple or filamentary fibers, and can be used alone or in combination as blends, blended yarns, or composite textured yarns. These synthetic or natural fibers can also be used with elastic polyurethane fibers to create composite textured yarns, such as covered yarns, air entangled yarns, ply-twisted yarns, composite false twisted yarns, and core-spun yarns.

[0024] The fiber structure is preferably a knitted fabric, a woven fabric, or a garment sewn from these. Knitted fabrics are particularly suitable for stretchable garments such as legwear, underwear, sportswear, and socks. They can also be used in diapers, sanitary napkins, and the like. These are required to have high deodorizing performance and high washability.

[0025] The method for producing a deodorizing fiber structure of the present invention includes an alkali treatment step in which the fiber structure is treated with an aqueous solution containing an alkaline substance, and a subsequent organic acid treatment step in which the fiber structure is immersed in an aqueous solution containing an organic acid and heated. The alkali treatment step is preferably at least one selected from a bleaching treatment and an alkali weight loss treatment. Conventional bleaching methods can be used, and treatment with an oxygen-based bleach such as an aqueous solution of hydrogen peroxide is preferred. Chlorine-based bleach such as an aqueous solution containing sodium hypochlorite is not preferred because it damages polyurethane elastic fibers. The organic acid treatment is preferably carried out before or after dyeing. Dyeing after the organic acid treatment is particularly preferred. This allows for vivid dyeing.

[0026] When the deodorizing fiber structure contains natural fibers such as cotton and hemp, it is preferable to include the following steps. (1) Scouring process (2) Bleaching process (3) Dyeing process (4) Flexibility process (5) A processing step in which the solution is immersed in and heated with an organic acid. Of the above steps, (1) to (4) can be performed by conventional methods. The scouring and bleaching steps may be performed in the same step. In the dyeing step, various colors can be dyed. In the processing step (5), padding treatment is also possible in addition to immersion heating, but immersion heating in a batch process is preferred from the viewpoint of deodorizing performance. The concentration of the organic acid in the aqueous solution containing the organic acid is preferably 0.5 to 10 g / L. As described above, it is preferable to dye the fabric after the organic acid treatment.

[0027] Next, we will explain the case where the deodorizing fiber containing the inorganic layered deodorizer is an elastic fiber. Examples of the elastic fiber include polyester-based elastic fiber, polyamide-based elastic fiber, polyolefin-based elastic fiber, and polyurethane-based elastic fiber, with polyurethane-based elastic fiber being preferred. The deodorizing agent is mixed into the elastic fiber.

[0028] In the present invention, the polyurethane used for the polyurethane constituting the elastic fiber may be any polyurethane containing a structure in which the starting materials are a polymer diol and a diisocyanate, and is not particularly limited. Furthermore, the synthesis method is also not particularly limited. For example, the polyurethane may be a polyurethane urea made from a polymer diol, a diisocyanate, and a low-molecular-weight diamine, or a polyurethane urethane made from a polymer diol, a diisocyanate, and a low-molecular-weight diol.

[0029] In the present invention, a polymer diol compound refers to a diol compound having a number average molecular weight (hereinafter sometimes abbreviated as molecular weight) of 200 or more, and a diol compound having a molecular weight of less than 200 is called a low molecular weight diol compound. The molecular weight of the polymer diol is preferably 1,000 to 8,000, more preferably 1,500 to 6,000. Polyurethane urea may also be used as a chain extender, using a compound having a hydroxyl group and an amino group in the molecule. It is also preferable to use trifunctional or higher polyfunctional glycols, isocyanates, etc., within a range that does not impair the effects of the present invention.

[0030] The polymer diol is preferably a polyether glycol, a polyester glycol, a polycarbonate diol, etc. In particular, from the viewpoint of imparting flexibility and elongation to the yarn, it is preferable to use a polyether glycol. Specific examples of polyether glycols include polyethylene glycol, modified polyethylene glycol, polypropylene glycol, polytrimethylene ether glycol, polytetramethylene ether glycol (hereinafter abbreviated as PTMG), modified PTMG, which is a copolymer of tetrahydrofuran (hereinafter abbreviated as THF) and 3-methyl-THF, modified PTMG, which is a copolymer of THF and 2,3-dimethyl-THF, modified PTMG, which is a copolymer of THF and neopentyl glycol, and random copolymers in which THF and ethylene oxide and / or propylene oxide are irregularly arranged. These polyether glycols may be used alone or in combination of two or more. Among these, PTMG or modified PTMG is preferred. Next, aromatic diisocyanates such as diphenylmethane diisocyanate (hereinafter abbreviated as MDI), tolylene diisocyanate, 1,4-diisocyanatobenzene, xylylene diisocyanate, and 2,6-naphthalene diisocyanate are preferred as they can produce elastic polyurethane yarns with particularly high heat resistance and strength. Furthermore, preferred alicyclic diisocyanates include methylenebis(cyclohexyl isocyanate), isophorone diisocyanate, methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate, cyclohexane-1,4-diisocyanate, hexahydroxylylene diisocyanate, hexahydrotolylene diisocyanate, and octahydro-1,5-naphthalene diisocyanate. Aliphatic diisocyanates are particularly effective in preventing yellowing of elastic polyurethane yarns. These diisocyanates may be used alone or in combination of two or more.

[0031] The chain extender used in the polyurethane is preferably at least one of low molecular weight diamines and low molecular weight diols, including those having a hydroxyl group and an amino group in the molecule, such as ethanolamine. Examples of low-molecular-weight diamines include ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, hexamethylenediamine, p-phenylenediamine, p-xylylenediamine, m-xylylenediamine, p,p'-methylenedianiline, 1,3-cyclohexyldiamine, hexahydrometaphenylenediamine, 2-methylpentamethylenediamine, and bis(4-aminophenyl)phosphine oxide. It is preferable to use one or more of these. Ethylenediamine is particularly preferred. The use of ethylenediamine facilitates the production of yarns with excellent elongation, elastic recovery, and heat resistance. A triamine compound capable of forming a crosslinked structure, such as diethylenetriamine, may be added to these chain extenders to the extent that the effect is not lost. Representative low-molecular-weight diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, bishydroxyethoxybenzene, bishydroxyethylene terephthalate, and 1-methyl-1,2-ethanediol. It is preferable to use one or more of these. Ethylene glycol, 1,3-propanediol, and 1,4-butanediol are particularly preferred. Use of these diol-extended polyurethanes increases the heat resistance and allows for the production of elastic threads made of polyurethane with higher strength.

[0032] It is also preferable to use one or more types of terminal blocking agents in combination for the polyurethane. Preferred terminal blocking agents include monoamines such as dimethylamine, diisopropylamine, ethylmethylamine, diethylamine, methylpropylamine, isopropylmethylamine, diisopropylamine, butylmethylamine, isobutylmethylamine, isopentylmethylamine, dibutylamine, and diamylamine, monools such as ethanol, propanol, butanol, isopropanol, allyl alcohol, and cyclopentanol, and monoisocyanates such as phenyl isocyanate.

[0033] The content of the deodorant is preferably in the range of 0.5% by mass or more and 10% by mass or less, based on the total mass of the elastic fiber made of polyurethane. By making the content of the deodorant 0.5% by mass or more, even higher ammonia gas deodorizing properties can be obtained when the fabric is made, which is preferable. A content of 1.0% by mass or more is more preferable. On the other hand, a content of more than 10% by mass is undesirable in terms of deterioration of stretch properties and cost. A content of 7.0% by mass or less is more preferable. Considering the balance between deodorizing properties, physical properties, and cost, a range of 1.5% by mass or more and 5.0% by mass or less is particularly preferable.

[0034] From the viewpoint of preventing clogging of the spinning dope in the spinneret, the deodorant preferably has an average primary particle size of 3.0 μm or less, more preferably 1.5 μm or less. Furthermore, from the viewpoint of dispersibility, if the average primary particle size is less than 0.05 μm, the cohesion force increases, making it difficult to mix the deodorant uniformly in the spinning dope, so the average primary particle size is preferably 0.05 μm or more, more preferably 0.15 μm or more.

[0035] Furthermore, polyurethane elastic fibers may contain various stabilizers, pigments, etc. For example, light stabilizers, antioxidants, etc., preferably include hindered phenol-based agents such as BHT and Sumitomo Chemical Co., Ltd.'s "Sumilizer" (registered trademark) GA-80, various benzotriazole-based and benzophenone-based agents such as Ciba-Geigy's "Tinuvin" (registered trademark), phosphorus-based agents such as Sumitomo Chemical Co., Ltd.'s "Sumilizer" (registered trademark P-16), various hindered amine-based agents, various pigments such as iron oxide and titanium oxide, inorganic substances such as zinc oxide, cerium oxide, magnesium oxide, calcium carbonate, and carbon black, fluorine-based or silicone-based resin powder, metal soaps such as magnesium stearate, lubricants such as silicone and mineral oil, and various antistatic agents such as cerium oxide, betaine, and phosphate-based agents, and it is also preferable for these to be bonded to the polyurethane. In order to further enhance durability, particularly against light and various nitrogen oxides, it is also preferable to contain a nitrogen oxide scavenger such as HN-150 manufactured by Nippon Hydrazine Co., Ltd., a thermal oxidation stabilizer such as Sumilizer (registered trademark) GA-80 manufactured by Sumitomo Chemical Co., Ltd., or a light stabilizer such as Sumisorb (registered trademark) 300#622 manufactured by Sumitomo Chemical Co., Ltd. The concentration of the polyurethane spinning solution thus obtained is usually preferably in the range of 30% by mass to 80% by mass.The deodorant is mixed into this spinning solution.

[0036] The polyurethane elastic fiber of the present invention can be obtained by dry spinning, wet spinning, or melt spinning the spinning solution prepared as described above, followed by winding. Among these, dry spinning is preferred from the viewpoint of enabling stable spinning of fibers of any fineness, from fine to thick.

[0037] The polyurethane elastic fiber of the present invention is not particularly limited in fineness, cross-sectional shape, etc. For example, the cross-sectional shape of the yarn may be circular or flat. The dry spinning method is not particularly limited, and spinning conditions may be appropriately selected to suit the desired properties and spinning equipment. For example, the permanent set and stress relaxation of the polyurethane elastic fiber of the present invention are particularly susceptible to the influence of the speed ratio between the godet roller and the winder, and therefore it is preferable to determine these appropriately depending on the intended use of the yarn. That is, from the viewpoint of obtaining a polyurethane elastic fiber having a desired permanent set and stress relaxation, it is preferable to wind the fiber with a speed ratio of 1.10 to 1.65 between the godet roller and the winder. To obtain a polyurethane elastic fiber having a particularly low permanent set and stress relaxation, it is more preferable to wind the fiber with a speed ratio of 1.15 to 1.4, and even more preferable to wind the fiber with a speed ratio of 1.15 to 1.35. To obtain a polyurethane elastic fiber having a high permanent set and stress relaxation, it is preferable to wind the fiber with a speed ratio of 1.25 to 1.65, and even more preferable to wind the fiber with a speed ratio of 1.35 to 1.65.

[0038] In addition, the spinning speed is preferably 300 m / min or more from the viewpoint of improving the strength of the polyurethane elastic fiber obtained.

[0039] To apply an oil to the elastic fiber, it is preferable to apply the oil as is without diluting it with a solvent or the like, i.e., so-called neat oil application. Examples of the application process include the process after spinning and before winding onto a package, the process of rewinding the wound package, and the process of warping with a warper, but any of these processes may be used, and known methods such as roller oil application, guide oil application, and spray oil application can be used. The amount of oil applied is preferably 0.1 to 5% by mass of the elastic fiber. [Example]

[0040] The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. First, methods for evaluating various properties in the present invention will be described below. [Method for evaluating deodorizing properties] The odor eliminating ability of odorous components was evaluated using the detector tube method in accordance with the deodorizing test described in the SEK Mark Textile Product Certification Standards (established by: Textile Evaluation Technology Council, Product Certification Department, revised on April 1, 2015). Ammonia was used as the odorous component. The initial concentration of odorous components was 100 ppm ammonia. For the blank test, 5 L sample bags (made of film) were filled with only the odorous components for each component, sealed, and left for 2 hours. The remaining gas concentration was measured using a gas detector tube for each component, and this was used as the blank test concentration. Next, the sample to be used for measurement (10 cm x 10 cm) was placed in a sample bag (made of film), filled with the odorous components at the specified concentrations described above, and sealed. The remaining gas concentration after 2 hours was measured using a gas detector tube, and this was used as the measured concentration. The measurement was performed three times, and the average value was used to calculate the reduction rate of the remaining gas concentration using the following formula, and this was expressed as the reduction rate. Deodorizing component reduction rate (%) = ((blank test concentration - measured concentration of each sample) / blank test concentration)) × 100 The evaluation criteria for the reduction rate were 70% or more for ammonia, 70% or more for acetic acid, 85% or more for isovaleric acid, and 75% or more for nonenal, which were considered to be passing. [Washing Instructions] The washing was carried out in accordance with the standard washing method described in the SEK Mark Textile Product Washing Method (established by: Japan Textile Evaluation Technology Council, Product Certification Department, revised on April 1, 2014), using a household electric washing machine as specified in washing method 103 of JIS L 0217: 1995. "Symbols and their labeling methods for handling textile products." JAFET's standard detergent blend (a blend of polyoxyethylene alkyl ether and sodium alpha-olefin sulfonate) was added at a ratio of 40 mL to 30 L of water at 40°C to make a wash solution. The sample and, if necessary, a load of fabric were added so that the bath ratio was 1:30. One cycle consisted of washing for 5 minutes, spin-drying, rinsing for 2 minutes, spin-drying, rinsing for 2 minutes, and spin-drying. This cycle was repeated 10 times, and the product was then hung to dry. [Dough pH] Measurements were performed according to the "Testing Methods for Woven and Knit Fabrics" specified in JIS L1096:2010 8.37. 50 ml of distilled water was placed in a glass flask and boiled for 2 minutes, after which 5.0 g of finely chopped fabric test pieces were placed in the flask, the flask was stoppered, and the flask was left to stand for 30 minutes. After 30 minutes, the extract was adjusted to 25°C ± 2°C, and the pH of the extract was measured using a pH meter.

[0041] <Interlayer distance, crystallite size and ammonia gas reduction rate of the deodorant at each treatment stage of the fiber structure> Alpha-zirconium phosphate powder (single substance) was subjected to scouring, bleaching, dyeing with reactive dyes, and organic acid treatment using citric acid, and the interlayer distance, crystallite size, and ammonia gas reduction rate were investigated at each treatment stage. The interlayer distance and deodorizing function of alpha-zirconium phosphate powder (single substance) at each treatment stage of textile structures were also analyzed. Specifically, alpha-zirconium phosphate powder (single substance) was removed from textile structures at each treatment stage: scouring, bleaching, dyeing with reactive dyes, and organic acid treatment using citric acid, and the interlayer distance, crystallite size, and ammonia gas reduction rate were investigated. The method for removing the organic components from the fiber structure was to use the treated fabrics of Examples 1 and 3, and to completely dissolve the organic components using a solvent capable of dissolving the fibers that make up the fiber structure, and then separate the residue by centrifugation. <Inorganic layered deodorant> α-zirconium phosphate powder (average particle size 0.8 μm, volume basis by particle size distribution measurement using laser diffraction light scattering method, cumulative particle size distribution D50 median diameter) (single substance) was used. <Powder refining and bleaching treatment> A flask was charged with 2.5g / L of aqueous sodium hydroxide, 3.0g / L of Nicca Chemical's "WX-HC" scouring agent, 0.5g / L of a chelating agent, and 5g / L of a 35% aqueous hydrogen peroxide solution as a bleaching agent, to make a total of 1000mL of aqueous solution. 10g of α-zirconium phosphate powder was added to this solution, and while mixing, the liquid temperature was raised from 20°C to 95°C, and the solution was subjected to a scouring and bleaching treatment for 30 minutes. The treated water was then centrifuged in a centrifuge, and the scouring and bleaching-treated α-zirconium phosphate powder was removed. <Dyeing process of powder> Fluorescent whitening was carried out using a reactive dye under the following conditions and ingredients. Fluorescent whitening agent: Huntsman Japan's UVITEX BHT LIQ, 2g / L ·Buffer: Glauber's salt (sodium sulfate) 10g / L Leveling agent: 0.5g / L of "Newborn" (trade name, manufactured by Nicca Chemical Co., Ltd.) was measured out to make a 1000mL solution, and the above-mentioned scouring and bleached α-zirconium phosphate was added to this solution and mixed. Conditions: After dyeing at 80°C for 60 minutes, the mixture was centrifuged in a centrifuge to extract the dyed α-zirconium phosphate powder. <Organic acid treatment of powder with citric acid> The dyed α-zirconium phosphate was added to 1000 mL of a 10 g / L aqueous solution of citric acid, mixed, and treated at 70°C for 20 minutes. After that, the mixture was centrifuged in a centrifuge to extract the organic acid-treated α-zirconium phosphate powder. The deodorizing properties of untreated α-zirconium phosphate powder, as well as the refined and bleached α-zirconium phosphate powder (after refined and bleached treatment), dyed α-zirconium phosphate powder (after dyeing treatment), and organic acid-treated α-zirconium phosphate powder (after organic acid treatment) obtained as described above were evaluated. <Interlayer distance, crystallite size> The interlayer distance and crystallite size were measured by powder X-ray diffraction analysis using Cu-Kα radiation and a Ni plate as a filter. The obtained diffraction pattern was compared with ASTM cards or existing literature to identify the crystal structure. The interlayer distance was analyzed by wide-angle X-ray diffraction. The results are summarized in Figure 1 and Tables 2 to 4. The horizontal axis of Figure 1 is a multiple plot (overlapping) of the wide-angle X-ray diffraction patterns of each sample, and is an enlarged view of the area around 2θ = 10°. In Figure 1, 2θ of 9° is 1.0 nm, and 2θ of 11.7° is 0.75 nm. Table 2 shows the analysis results of the powder treatment, Table 3 shows the analysis results of the deodorant removed from the treated fabric of Example 1, and Table 4 shows the analysis results of the deodorant removed from the treated fabric of Example 3.

[0042] [Table 2]

[0043] [Table 3]

[0044] [Table 4]

[0045] As is clear from Tables 2 to 4, the deodorizing function of the α-zirconium phosphate powder deodorant was significantly reduced after scouring and bleaching treatment, but it was confirmed that this was restored by organic acid treatment. It was also confirmed that the interlayer distance was approximately 1.0 nm after scouring and bleaching treatment, but returned to 0.75 nm by organic acid treatment. Next, the deodorants after dyeing and organic acid treatment were identified using standard wide-angle X-ray diffraction data. The results are shown in Table 5.

[0046] [Table 5]

[0047] As is clear from Table 5, sodium and potassium compounds were identified in the inorganic layered deodorant after dyeing treatment. In addition, sodium and potassium disappeared from the inorganic layered deodorant after organic acid treatment, and the original zirconium phosphate was identified. From the above, it was found that inorganic layered deodorants that do not have sodium or potassium bound to them have a high ammonia deodorizing function, while inorganic layered deodorants that do have sodium or potassium bound to them have a lower ammonia deodorizing function. From the above experiments using the inorganic layered deodorant powder, it is clear that any spinning solution can be used as long as it can be mixed with the inorganic layered deodorant.

[0048] Example 1 <Fiber material> Cotton yarn: Commercially available cotton spun yarn (metric count 40, single yarn) was used. The polyurethane elastic fiber used was 33decitex, an elastic thread made of polyurethane containing 4% by mass of α-zirconium phosphate as an inorganic layered deodorant. <Knitting> Using the above cotton yarn and elastic yarn, a knitted fabric was knitted on a circular knitting machine with a gauge of 28. The weight of the knitted fabric obtained was 165 g / m 2 The mass proportions were 91.1 mass% cotton yarn and 8.9 mass% elastic yarn. The obtained knitted fabric is called a greige. <Scouring and bleaching treatment> A 20-liter solution of 2.5 g / L sodium hydroxide solution, 3.0 g / L "WX-HC" (manufactured by Nicca Chemical Co., Ltd.) as a scouring agent, 0.5 g / L chelating agent, and 5 g / L 35% hydrogen peroxide solution as a bleaching agent was added to the dyeing machine. 1,000 g of knitted fabric was immersed in this solution, and the temperature was raised from 20°C to 95°C for 30 minutes for scouring and bleaching. The treated water was then drained, clean water was added, and the fabric was heated to 50°C and washed for 5 minutes. The hot water was then drained, and 0.25 g / L 90% acetic acid was added, heated to 40°C, and mixed for 5 minutes. The acetic acid solution was then drained, clean water was added again, and the fabric was heated to 50°C and washed for 5 minutes, followed by dehydration and drying. <Dyeing process> Fluorescent whitening was carried out using a reactive dye under the following conditions and ingredients. Fluorescent whitening agent: Huntsman Japan product name "UVITEX BHT LIQ" 0.15% owf ·Buffer: Glauber's salt (sodium sulfate) 10g / L Leveling agent: Nicca Chemical Co., Ltd. "Newbon" 0.5g / L Conditions: Dyeing process at 80°C for 60 minutes, neutralization process at 60°C for 10 minutes, soaping process at 60°C for 10 minutes, washing process at 60°C for 10 minutes, and then dehydration and drying. <Soft processing> The fabric was softened in an aqueous solution containing 1.5 owf% of "Softex A-1017S" manufactured by Kitahiro Chemical Co., Ltd. as a softener at 40°C for 20 minutes, washed with water at 20°C for 5 minutes, and then dehydrated and dried. <Organic acid treatment with citric acid> The dyed knitted fabric was immersed in a dyeing machine in a 10 g / L aqueous solution of citric acid, treated at 70°C for 20 minutes, washed, dehydrated and dried. The knitted fabrics thus obtained after treatment with citric acid were evaluated.

[0049] Example 2 The same procedure as in Example 1 was carried out except that a 5 g / L aqueous solution of citric acid was used.

[0050] (Comparative Example 1) The above greige fabrics were evaluated.

[0051] (Comparative Example 2) The knitted fabrics after the above scouring and bleaching treatments were evaluated.

[0052] (Comparative Example 3) The knitted fabric after the above dyeing treatment was evaluated.

[0053] Comparative Example 4 The knitted fabric after the softening treatment was evaluated.

[0054] The above conditions and results are summarized in Tables 6 and 7.

[0055] [Table 6]

[0056] [Table 7]

[0057] From Comparative Examples 1 and 2 in Table 6, it was confirmed that when knitted fabrics made of elastic fiber and cotton yarn are scoured and bleached, the deodorizing performance of the elastic fiber is reduced, and that this is further reduced by fluorescent whitening treatment and softening treatment. However, it was confirmed that fabrics soaked in citric acid and heated have high deodorizing performance and also have high washing durability.

[0058] Example 3 <Fiber material> The procedure was the same as in Example 1, except that a blended spun yarn (metric count 40, single yarn) consisting of 30% by mass of acrylic fiber and 70% by mass of cotton fiber was used instead of the cotton yarn. The mass proportions of the knitted fabric were 27% by mass of acrylic fiber, 62% by mass of cotton fiber, and 11% by mass of elastic fiber. <Dyeing process> In addition to Example 1, fluorescent whitening dyeing was carried out using a cationic dye. Fluorescent whitening agent: Huntsman Japan product name "UVITEX AC LIQ" 0.3% owf Leveling agent: Nissei Chemical Co., Ltd. product name "Nichilon Salt C-25" 0.5% owf Acid: 0.5g / L acetic acid solution Conditions: Dyeing was performed for 10 minutes at 40°C, 15 minutes at 75°C, and 45 minutes at 100°C, followed by soaping for 10 minutes at 60°C, washing with hot water for 10 minutes at 60°C, and then dehydrating and drying. After the acrylic was subjected to fluorescent whitening treatment, the cotton was subjected to fluorescent whitening treatment in the same manner as in Example 1. Other than the above, the same treatment as in Example 1 was carried out.

[0059] Example 4 The same procedure as in Example 3 was carried out except that a 5 g / L aqueous solution of citric acid was used.

[0060] (Comparative Example 5) The knitted fabric after the above scouring and bleaching treatment was evaluated.

[0061] (Comparative Example 6) The knitted fabric after the softening treatment was evaluated. The above conditions and results are summarized in Table 8.

[0062] [Table 8]

[0063] As is clear from Table 8, knitted fabrics made of blended spun yarns of elastic fiber and acrylic fiber / cotton fiber that were bleached and treated with citric acid had high deodorizing performance and also had high washing durability.

[0064] (Examples 5 to 8) (1) The raw yarns used were as follows: Cotton yarn: Commercially available cotton spun yarn (metric count 40, single yarn) was used. The polyurethane elastic fiber used was 22decitex, an elastic thread made of polyurethane containing 4% by mass of α-zirconium phosphate as an inorganic layered deodorant. (2) The fabric was as follows: The above cotton yarn and elastic yarn were used to knit a garment on a 28 gauge circular knitting machine. The weight of the resulting knitted fabric is 160g / m 2 The mass ratio was 94.4 mass% cotton yarn and 5.6 mass% elastic yarn. (3) Post-processing The same procedure as in Example 1 was carried out except for the conditions shown in Table 9. The conditions and results are summarized in Table 9.

[0065] [Table 9]

[0066] As is clear from Table 9, the organic acids acetic acid, malic acid, citric acid, and maleic acid were also able to provide a deodorizing treatment that was durable to washing.

[0067] Example 9 (1) The raw yarns used were as follows: Cotton yarn: Commercially available cotton spun yarn (metric count 40, single yarn) was used. The polyurethane elastic fiber used was 22decitex, an elastic thread made of polyurethane containing 4% by mass of α-zirconium phosphate as an inorganic layered deodorant. (2) The fabric was as follows: The above cotton yarn and elastic yarn were used to knit a garment on a 28 gauge circular knitting machine. The weight of the resulting knitted fabric is 160g / m 2 The mass ratio was 93.1 mass% cotton yarn and 6.9 mass% elastic yarn. (3) Post-processing The same procedures as in Example 1 were carried out except as shown in Table 10. The conditions and results are summarized in Table 10. The whiteness was determined by measuring X, Y, Z, x, and y of the dyed fabric using a spectrophotometer (manufactured by KONICA MINOLTA, model: CM-3700d, D65 light source) in accordance with JIS Z 8715-1999. A higher value indicates a whiter fabric.

[0068] [Table 10]

[0069] Example 10 The same procedures as in Example 9 were carried out except that the order of dyeing and organic acid treatment was reversed, with the organic acid treatment being carried out first and the dyeing being carried out second. The conditions and results are summarized in Tables 10 and 11.

[0070] [Table 11]

[0071] [Table 12]

[0072] As is clear from Examples 9 and 10, it was confirmed that the whiteness was higher when the organic acid treatment was carried out first and the dyeing was carried out later. Furthermore, Table 12 confirms that the deodorizing function of the deodorizing agent α-zirconium phosphate powder is significantly reduced after scouring and bleaching treatments, but that the deodorizing function is restored even if the organic acid treatment is performed first and the dyeing is performed later. [Industrial Applicability]

[0073] The deodorizing fiber structure of the present invention is excellent in deodorizing sweat odor and aging odor, and is suitable for carpets, curtains, bedding, underwear, diapers, sanitary products, etc. It is particularly suitable for stretchable clothing such as leg wear, innerwear, sportswear, and socks.

Claims

1. A method for producing a deodorizing fiber structure including a deodorizing fiber in which an inorganic layered deodorizer is mixed with a polymer, comprising: the inorganic layered deodorant is α-zirconium phosphate, (1) a step of alkali treating a fiber structure with an aqueous solution containing an alkaline substance; (2) Thereafter, a step of immersion and heat treatment is carried out in an aqueous solution containing an organic acid having 2 to 6 carbon atoms and a carboxyl group, the interlayer distance of the α-zirconium phosphate is 0.1 nm or more and 0.9 nm or less, and the crystallite size is 1 nm or more and 30 nm or less; A method for producing a deodorizing fiber structure, characterized by producing a deodorizing fiber structure in which the ammonia gas reduction rate after both 0 and 10 home washings is 70% or more.

2. 2. The method for producing a deodorizing fiber structure according to claim 1, wherein the organic acid is at least one selected from the group consisting of citric acid, maleic acid, malic acid, acetic acid, and succinic acid.

3. 3. The method for producing a deodorizing fiber structure according to claim 1, wherein the deodorizing fiber is at least one selected from synthetic fibers and regenerated fibers.

4. The method for producing a deodorizing fiber structure according to any one of claims 1 to 3, wherein the fiber structure contains 100% by mass of the deodorizing fiber or the deodorizing fiber and other fibers, and when other fibers are contained, the deodorizing fiber accounts for 1 to 99% by mass of the fiber structure as a parameter.

5. The method for producing a deodorizing fiber structure according to claim 4, wherein the other fiber is at least one selected from the group consisting of natural fiber, synthetic fiber, and regenerated fiber.

6. The method for producing a deodorizing fiber structure according to any one of claims 1 to 5, wherein the fiber structure is a knitted fabric, a woven fabric, or a garment sewn from the same.

7. The method for producing a deodorizing fiber structure according to any one of claims 1 to 6, wherein the alkali treatment step is at least one selected from a bleaching treatment and an alkali weight reduction treatment.

8. The method for producing a deodorizing fiber structure according to any one of claims 1 to 7, wherein the organic acid treatment is carried out before or after dyeing.

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