Deodorizing fiber structure

Abstract

To provide a deodorant fiber structure having high washing resistance in spite of being bleached.SOLUTION: A deodorant fiber structure comprises deodorant fibers obtained by mixing an inorganic layered deodorant with a polymer, wherein the inorganic layered deodorant has an interlayer distance of 0.1 nm or more and 0.9 nm or less and a crystallite size of 1 nm or more and 30 nm or less, and the deodorant fiber structure has an ammonia gas reduction rate of 70% or more after 0 and 10 home washings. The inorganic layered deodorant is preferably at least one selected from α-zirconium phosphate, α-hafnium phosphate, and α-titanium phosphate.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a deodorant fiber structure having high deodorizing performance and high wash resistance.

Background Art

[0002] Deodorant fibers are used in carpets, curtains, bedding, underwear, diapers, sanitary products, etc. In particular, clothing that comes into direct contact with the skin may cause discomfort due to odors such as sweat and body odor, and there is a high demand for fiber products having a deodorizing function. In Patent Document 1, it is proposed to use an elastic fiber and a knitted fabric using a crosslinked acrylate yarn containing a carboxyl group and crosslinked by hydrazine treatment as a deodorant fiber. In Patent Document 2, an elastic fiber containing zinc oxide and zirconium phosphate is proposed. In Patent Document 3, a synthetic fiber containing α-zirconium phosphate and / or α-titanium phosphate is proposed.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Disclosure of the Invention

Problems to be Solved by the Invention

[0004] However, cross-linked acrylate yarns like those in Patent Document 1 have the problem of being highly hygroscopic, and once they absorb moisture, they lose their deodorizing function. Furthermore, the fibers in Patent Documents 2 and 3 have the problem of losing their deodorizing function when subjected to alkaline treatment. Alkali treatment is used in alkaline weight reduction processing for polyester fibers, and in scouring, bleaching, and mercerizing for cotton fibers, linen fibers, etc., and the loss of deodorizing function is problematic.

[0005] The present invention solves the problems of the conventional technology described above and provides a deodorizing fiber structure that is bleached yet highly washable. [Means for solving the problem]

[0006] The deodorizing fiber structure of the present invention comprises a first fiber which is at least one selected from synthetic fibers and regenerated fibers, and a second fiber which is a natural fiber, and is bleached. condition Deodorizing fiber structure, The aforementioned The first fiber contains an inorganic layer deodorant on the polymer. α-Zirconium phosphate It is a deodorizing fiber made by mixing, The second fiber contains cotton, The inorganic layered deodorant has an interlayer distance of 0.1 nm or more and 0.9 nm or less, and a crystallite size of 1 nm or more and 30 nm or less. The aforementioned deodorizing fiber structure is characterized by a reduction rate of 70% or more in ammonia gas after 0 and 10 washes at home. [Effects of the Invention]

[0007] The present invention provides a deodorizing fiber structure containing deodorizing fibers in which an inorganic layered deodorant is mixed with a polymer, wherein the inorganic layered deodorant 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 exhibits an ammonia gas reduction rate of 70% or more after 0 and 10 washes, thereby providing a deodorizing fiber structure with high deodorizing performance and high washability. Specifically, when an unbleached deodorizing fiber structure containing deodorizing fibers mixed with an inorganic layered deodorant is treated with alkali, the interlayer distance exceeds 0.9 nm and the deodorizing function is significantly reduced. However, when treated with organic acid, the interlayer distance of the deodorant becomes 0.9 nm or less, and a bleached deodorizing fiber structure with restored deodorizing function is obtained. The deodorizing function of this deodorizing fiber structure also has good washability. [Brief explanation of the drawing]

[0008] [Figure 1] Figure 1 is a wide-angle X-ray diffraction pattern multiplexing graph of an inorganic layered deodorant used in one embodiment of the present invention, and is an enlarged view of the area around 2θ = 10°. [Modes for carrying out the invention]

[0009] The inventors encountered a problem in which elastic fibers containing inorganic layered deodorants such as α-zirconium phosphate initially have deodorizing properties, but lose their deodorizing function upon alkaline treatment, and investigated the cause. The layered structure of α-zirconium phosphate is as shown below (Chemical Formula 1), and the interlayer distance is approximately 7.55 Å (angstroms, 0.755 nm) (Sadaaki Hasegawa et al., "On the Ion Exchange Properties of Layered Phosphate M(IV)(HPO4)2·H2O(M=Zr,Hf)", IONICS, October 1985).

[0010] [ka]

[0011] The interlayer distance of the α-zirconium phosphate can incorporate substances smaller than the ammonia molecule size, and it is presumed that the incorporated gas is neutralized and deodorized by forming an ionic bond with the functional group of the α-zirconium phosphate crystal. However, when the fibrous structure is placed under strong alkaline conditions such as alkaline treatment, the interlayer distance exceeds 0.9 nm due to ion exchange with alkali metals, etc., allowing substances other than ammonia to be incorporated, reducing the active functional groups, and deactivating the deodorizing function. Therefore, various studies were conducted to revive the deodorizing function, and it was found that treating with an organic acid after alkaline treatment can restore the interlayer distance of the inorganic layered deodorant to its original state and revive the deodorizing function. The experimental conditions and results will be described later, but the important 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 scouring and bleaching treatment, but by treating with an organic acid, the interlayer distance returns to its original state and the crystallite size becomes smaller than the original state. This is a new finding. The present invention has been completed based on the above concepts and problems.

[0014] The present invention is a deodorant fibrous structure containing deodorant fibers obtained by mixing an inorganic layered deodorant with a polymer. As an example, fibers obtained by adding and mixing an inorganic layered deodorant to a spinning solution are used. The spinning can be melt spinning or wet spinning. The deodorant fibrous structure has been alkali-treated. The alkali treatment is used in alkali weight reduction processing in the case of polyester fibers. In the case of cotton fibers, hemp fibers, etc., it is used in scouring, bleaching, mercerizing, and silkette processing (mercerizing). The addition amount of the inorganic layered deodorant in the deodorant fiber is preferably 0.5 to 10% by mass, more preferably 1 to 7% by mass, based on the deodorant fiber. Within the above range, the deodorizing property can be maintained at a high level.

[0015] After the fiber structure is alkali-treated, it is then treated with an organic acid. The interlayer distance of the deodorant is 0.9 nm or less, and the ammonia deodorizing property after 0 and 10 times of home washing is both 70% or more. The preferable interlayer distance of the deodorant is 0.70 to 0.85 nm, and more preferably 0.72 to 0.80 nm. Thereby, a deodorant fiber structure having high deodorizing performance and high washing resistance is obtained. Further, when treated with an organic acid, the alkali metal bonds such as sodium and potassium in the deodorant disappear, and the deodorant restores its deodorizing function. At least one selected from zirconium α-phosphate, hafnium α-phosphate, and titanium α-phosphate is preferable as the deodorant. The deodorizing effect of zirconium α-phosphate and titanium α-phosphate has been recognized in the above Patent Document 3. The interlayer distance of hafnium α-phosphate is described as being equivalent to that of zirconium α-phosphate in the cited document of the above (Chemical Formula 1). Among these, zirconium α-phosphate is preferable.

[0016] At least one selected from synthetic fibers and regenerated fibers is preferable as the deodorant fiber. The polymer constituting the deodorant fiber may be a thermoplastic resin such as polyester, polyamide, polyolefin, polyurethane, etc., or a thermosetting resin such as regenerated cellulose, acrylic polymer, etc. These resins can be mixed with the inorganic layered deodorant in a spinning solution. The regenerated fibers include rayon, cupra, polynosic, lyocell (registered trademark), etc. Any spinning solution capable of mixing the inorganic layered deodorant can be used.

[0017] The fiber structure contains 100% by mass of the deodorant fiber or includes the deodorant fiber and other fibers. When other fibers are included, when the fiber structure is taken as the base number, the deodorant fiber is preferably 1 to 99% by mass. More preferably, the deodorant fiber is 2 to 50% by mass, and even more preferably, the deodorant fiber is 5 to 30% by mass. Deodorizing performance can be exhibited within the above range. The other fibers are preferably at least one selected from natural fibers, synthetic fibers, and regenerated fibers. The natural fibers include cotton, hemp, wool, silk, etc.

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

[0019] The pH of the aforementioned fiber structure is preferably 4.0 to 5.8, and more preferably 4.1 to 5.5. Having a slightly acidic pH like this is gentle on the skin and does not cause adverse effects. The pH of the fabric is measured according to the "Test Methods for Woven and Knitted Fabrics" specified in JIS L1096:2010 8.37.

[0020] The ammonia deodorization performance of the aforementioned fiber structure after 10 washes at home is preferably 70% or higher, more preferably 80% or higher, and even more preferably 90% or higher. This makes it possible to create a deodorizing fiber structure with high deodorizing performance and high washability. The home washing method and ammonia deodorization test will be described later.

[0021] In the present invention, the fibrous structure may have any structure or shape, such as a fabric, a strip, a string, or a thread. Preferably, a fabric containing a woven or knitted fabric or a nonwoven fabric is used, and a composite material containing such a fibrous structure may also be used.

[0022] The fibrous structure of one embodiment of the present invention contains elastic fibers and at least cotton, and may also contain synthetic fibers, regenerated fibers, semi-synthetic fibers, natural fibers other than cotton, etc. When the fibrous structure is used as the base, the ratio of elastic fibers to cotton is preferably 1 to 30% by mass of elastic fibers and 70 to 99% by mass of cotton. When cotton is used as the base, it is preferable that the ratio is 10 to 90% by mass of cotton and 10 to 90% by mass of fibers other than cotton.

[0023] Examples of synthetic fibers include polyester fibers, polyamide fibers, polyethylene fibers, polypropylene fibers, polyvinyl alcohol fibers, polyvinyl chloride fibers, and polyacrylonitrile fibers. Examples of polyester fibers include polyethylene terephthalate, polybutylene terephthalate, and polytrimethylene terephthalate, as well as copolymers of these with a third component such as isophthalic acid. Examples of regenerated and semi-synthetic fibers include rayon and acetate, while examples of natural fibers include hemp, wool, and silk. These fibers may be short or long fibers and can be used alone or in blends of two or more types as composite yarns. They can also be used as composite yarns such as covering, air entanglement, twisting, composite false twist, and core-spun yarn with elastic fibers made of polyurethane.

[0024] The aforementioned fibrous structure is preferably a knitted fabric, a woven fabric, or clothing sewn from these. In particular, knitted fabrics are suitable for stretchy clothing such as legwear, innerwear, sportswear, and socks. They can also be applied to diapers, sanitary products, and the like. These materials are required to have high deodorizing properties and high washability.

[0025] The present invention provides a method for producing a deodorizing fiber structure, comprising an alkaline treatment step of treating the fiber structure with an aqueous solution containing an alkaline substance, and an organic acid treatment step of subsequently immersing and heating the fiber structure in an aqueous solution containing an organic acid. The alkaline treatment step is preferably at least one selected from bleaching and alkaline weight reduction. Bleaching can be done using conventional methods, and treatment with an oxygen-based bleach such as an aqueous solution of hydrogen peroxide is preferred. Chlorine-based bleaches such as aqueous solutions containing sodium hypochlorite are undesirable because they damage polyurethane elastic fibers. The organic acid treatment is preferably performed before or after dyeing. Particularly preferably, dyeing is performed after the organic acid treatment. This allows for vivid dyeing.

[0026] If the deodorizing fiber structure includes natural fibers such as cotton or hemp, it is preferable to include the following steps. (1) Scouring process (2) Bleaching process (3) Dyeing process (4) Flexibility process (5) Processing step of immersion and heating in an aqueous solution containing organic acids Of the above steps, (1) to (4) can be performed using conventional methods. The scouring and bleaching steps may be performed in the same step. In the dyeing step, various shades of color can be achieved. In the processing step (5), padding treatment is also possible in addition to immersion heating, but batch immersion heating 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 mentioned above, it is preferable to perform the dyeing after the organic acid treatment.

[0027] Next, we will describe the case where the deodorizing fiber containing the inorganic layered deodorizer is an elastic fiber. Examples of such elastic fibers include polyester elastic fibers, polyamide elastic fibers, polyolefin elastic fibers, and polyurethane elastic fibers, but polyurethane elastic fibers are preferred. The deodorizer is mixed into the elastic fiber.

[0028] In the present invention, the polyurethane used in 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 not particularly limited. That is, for example, it may be a polyurethane urea made from a polymer diol, a diisocyanate and a low molecular weight diamine, or it may be a polyurethane urethane made from a polymer diol, a diisocyanate and a low molecular weight diol.

[0029] In this invention, a polymer diol compound refers to a diol compound with a number-average molecular weight (hereinafter sometimes abbreviated as molecular weight) of 200 or more, and a diol compound with a molecular weight of less than 200 is called a low molecular weight diol compound. Furthermore, the molecular weight of the polymer diol is preferably between 1000 and 8000, and more preferably between 1500 and 6000. A polyurethane urea containing a compound with hydroxyl and amino groups in its molecule may also be used as a chain extender. It is also preferable to use trifunctional or polyfunctional glycols or isocyanates, etc., within a range that does not hinder the effects of this invention.

[0030] Preferred polymer diols include polyether glycols, polyester glycols, and polycarbonate diols. Polyether glycols are particularly preferred from the viewpoint of imparting flexibility and elongation to the yarn. 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. One of these polyether glycols may be used, or two or more may be used. Among these, PTMG or modified PTMG is preferred. Next, as diisocyanates, aromatic diisocyanates such as diphenylmethane diisocyanate (hereinafter abbreviated as MDI), tolylene diisocyanate, 1,4-diisocyanatebenzene, xylylene diisocyanate, and 2,6-naphthalene diisocyanate are particularly suitable because they can produce elastic yarns made of polyurethane with high heat resistance and strength. Furthermore, as alicyclic diisocyanates, for example, 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 are preferred. Aliphatic diisocyanates can be used particularly effectively to suppress yellowing of elastic yarns made of polyurethane. These diisocyanates may be used individually or in combination of two or more.

[0031] Next, the chain extender used in polyurethane is preferably at least one of low molecular weight diamines and low molecular weight diols. It may also be a substance having both a hydroxyl group and an amino group in its 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. By using ethylenediamine, yarns with excellent elongation, elastic recovery, and heat resistance can be easily obtained. Triamine compounds capable of forming crosslinked structures, such as diethylenetriamine, may be added to these chain elongators in an amount that does not impair their effectiveness. Typical examples of 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 that one or more of these be used. Particularly preferred are ethylene glycol, 1,3-propanediol, and 1,4-butanediol. Using these results in a polyurethane with higher heat resistance and a higher strength, making it possible to obtain an elastic yarn made of polyurethane.

[0032] It is also preferable that one or more end-capping agents be used in combination with the polyurethane. Preferred end-capping 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 isocyanates.

[0033] The content of the deodorant is preferably in the range of 0.5% by mass or more and 10% by mass or less relative to the total mass of the elastic fibers made of polyurethane. A content of 0.5% by mass or more of the deodorant is preferable because it provides even higher ammonia gas deodorizing properties when the fabric is made. More preferably 1.0% by mass or more. On the other hand, a content exceeding 10% by mass is undesirable in terms of deterioration of stretchability and cost. More preferably 7.0% by mass or less. 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 preferred.

[0034] From the viewpoint of suppressing clogging of the spinning solution into the spinneret, the deodorant is preferably one with an average primary particle diameter of 3.0 μm or less. More preferably, it is 1.5 μm or less. Furthermore, from the viewpoint of dispersibility, if the average primary particle diameter is smaller than 0.05 μm, the cohesive force increases and it becomes difficult to uniformly mix it into the spinning solution. Therefore, it is preferable that the deodorant has an average primary particle diameter of 0.05 μm or more. More preferably, it is 0.15 μm or more.

[0035] Furthermore, the elastic fibers made of polyurethane may contain various stabilizers and pigments. For example, it is preferable that these contain lightfasteners and antioxidants such as BHT and hindered phenol-based agents such as "Sumilyzer" (registered trademark) GA-80 manufactured by Sumitomo Chemical Co., Ltd., various benzotriazole-based and benzophenone-based agents such as "Tinuvin" (registered trademark) manufactured by Ciba-Geigy, phosphorus-based agents such as "Sumilyzer" (registered trademark) P-16 manufactured by Sumitomo Chemical Co., Ltd., various hindered amine-based agents, various pigments such as iron oxide and titanium dioxide, inorganic substances such as zinc oxide, cerium oxide, magnesium oxide, calcium carbonate, and carbon black, fluorine-based or silicone-based resin powders, metal soaps such as magnesium stearate, lubricants such as silicone and mineral oil, and various antistatic agents such as cerium oxide, betaine, and phosphoric acid-based agents, and that these also bond with the polyurethane. Furthermore, to further enhance durability against light and various nitrogen oxides, it is preferable to include, for example, 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., and a light stabilizer such as "SumiSorb" (registered trademark) 300#622 manufactured by Sumitomo Chemical Co., Ltd. The concentration of the polyurethane spinning solution obtained in this way is usually preferably in the range of 30% by mass or more and 80% by mass or less. The deodorant is mixed into this spinning solution.

[0036] The polyurethane elastic fiber of the present invention can be obtained by, for example, dry spinning, wet spinning, or melt spinning the spinning solution configured as described above and then winding it up. Among these, dry spinning is preferred from the viewpoint of being able to stably spin fibers of all finenesses, from thin to thick.

[0037] The fineness, cross-sectional shape, etc., of the polyurethane elastic fiber of the present invention are not particularly limited. For example, the cross-sectional shape of the yarn may be circular or flat. Furthermore, there are no particular restrictions on the dry spinning method; spinning should be performed by appropriately selecting spinning conditions that match the desired characteristics and spinning equipment. For example, the permanent strain rate 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 winding machine, so it is preferable to determine them appropriately according to the intended use of the yarn. In other words, from the viewpoint of obtaining polyurethane elastic fibers having a desired permanent strain and stress relaxation, it is preferable to wind the Gode roller with a speed ratio of 1.10 or more and 1.65 or less. Furthermore, when obtaining polyurethane elastic fibers with a particularly low permanent strain and low stress relaxation, it is more preferable to wind the Gode roller with a speed ratio of 1.15 or more and 1.4 or less, and even more preferable to wind the Gode roller with a speed ratio of 1.15 or more and 1.35 or less. On the other hand, when obtaining polyurethane elastic fibers with a high permanent strain and high stress relaxation, it is preferable to wind the Gode roller with a speed ratio of 1.25 or more and 1.65 or less, and more preferably to wind the Gode roller with a speed ratio of 1.35 or more and 1.65 or less.

[0038] Furthermore, the spinning speed is preferably 300 m / min or more, from the viewpoint of improving the strength of the resulting polyurethane elastic fibers.

[0039] To attach the oil to the elastic fibers, it is preferable to use so-called neat lubrication, where the oil is applied directly without dilution with a solvent or the like. The attachment process can take place in any of the following stages: after spinning until winding into a package, the process of rewinding the package, or the process of warping using a warping machine. Known methods such as roller lubrication, guide lubrication, and spray lubrication can be applied. The amount of oil attached is preferably 0.1 to 5% by mass relative to the elastic fibers. [Examples]

[0040] The present invention will be described in more detail using examples, but the present invention is not limited to these embodiments. First, the methods for evaluating various characteristics in the present invention will be described below. [Method for evaluating deodorizing properties] In accordance with the deodorizing test described in the SEK Mark Textile Product Certification Standards (established by the Product Certification Department of the Japan Textile Evaluation Technology Council, revised on April 1, 2015), the deodorizing properties of odor components were evaluated using the detector tube method. Ammonia was used as the odor component. The initial concentration of the odor component was set at 100 ppm ammonia. As a blank test, 5L sample bags (film) were filled with only the odor components, sealed, and left for 2 hours. The remaining gas concentration was measured using gas detection tubes corresponding to each component, and this was taken as the blank concentration. Next, the sample to be used for measurement (10 cm x 10 cm) was placed in a sample bag (film), filled with the odor components at the predetermined concentrations mentioned above, sealed, and the remaining gas concentration after 2 hours was measured using a gas detection tube. This was taken as the measured concentration. Three measurements were taken, and the average value was used to calculate the rate of decrease in the remaining gas concentration using the following formula, and this was expressed as the rate of decrease. Deodorizing component reduction rate (%) = ((Blank test concentration - Measured concentration of each sample) / Blank test concentration)) × 100 The evaluation criteria for the reduction rate were as follows: ammonia 70% or higher, acetic acid 70% or higher, isovaleric acid 85% or higher, and nonenal 75% or higher. [Washing Instructions] In accordance with the standard washing method described in the SEK Mark Textile Product Washing Instructions (established by: Japan Textile Evaluation Technology Council, Product Certification Department, revised April 1, 2014), a household electric washing machine as specified in Washing Method 103 of JIS L 0217: 1995. "Symbols and methods for indicating the handling of textile products" was used. JAFET standard detergent (containing polyoxyethylene alkyl ether and sodium alpha-olefin sulfonate) was added at a ratio of 40 mL to 30 L of 40°C water to create a washing solution. The sample and, if necessary, the load fabric were added to the bath to achieve a bath ratio of 1:30. The process consisted of washing for 5 minutes, spinning, rinsing for 2 minutes, spinning, rinsing for 2 minutes, and spinning, which was repeated 10 times, after which the samples were dried by hanging. [Dough pH] The measurement was performed according to the "Test Method for Woven and Knitted Fabrics" specified in JIS L1096:2010 8.37. 50 ml of distilled water was placed in a glass flask and boiled for 2 minutes. Then, 5.0 g of finely chopped fabric test pieces were added, the flask was sealed, and left 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 processing stage of the fibrous structure> α-Zirconium phosphate powder (elementary) was subjected to scouring and 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. In addition, the interlayer distance and deodorizing function of α-zirconium phosphate powder (elementary) at each treatment stage of the fiber structure were also analyzed. Specifically, α-zirconium phosphate powder (elementary) was extracted from the fiber structure at each treatment stage (scouring and bleaching, dyeing with reactive dyes, organic acid treatment using citric acid), and the interlayer distance, crystallite size, and ammonia gas reduction rate were investigated. The method for extracting the organic components from the fibrous structure involved using the treated fabrics of Example 1 and Example 3, dissolving the organic components completely with a solvent capable of dissolving the fibers constituting the fibrous structure, and then separating the residue by centrifugation. <Inorganic layered deodorant> α-Zirconium phosphate powder (average particle size 0.8 μm, volume-based particle size distribution measured by laser diffraction scattering method, cumulative particle size distribution D50 median diameter) (single element) was used. <Powder refining and bleaching treatment> In a flask, 2.5 g / L of sodium hydroxide aqueous solution, 3.0 g / L of "WX-HC" (manufactured by Nikka Chemical Co., Ltd.) as a scouring agent, 0.5 g / L of a chelating agent, and 5 g / L of 35% hydrogen peroxide aqueous solution as a bleaching agent were measured out to make a total volume of 1000 mL of aqueous solution. 10 g of α-zirconium phosphate powder was added to this solution and mixed while raising the temperature from 20°C to 95°C for 30 minutes to perform the scouring and bleaching treatment. Next, the treated water was centrifuged in a centrifuge to remove the scouring and bleaching treatment of α-zirconium phosphate powder. <Dyeing treatment of powders> Fluorescent whitening was performed using reactive dyes under the following components and conditions. • Fluorescent whitening agent: 2g / L of "UVITEX BHT LIQ" manufactured by Huntsman Japan. ·Buffer: Glauber's salt (sodium sulfate) 10g / L • Dyeing agent: 0.5 g / L of "Newbon" manufactured by Nikka Chemical Co., Ltd. was measured and mixed to make a 1000 mL aqueous solution. The scouring and bleaching-treated α-zirconium phosphate was then added to this aqueous solution and mixed. Conditions: After staining at 80°C for 60 minutes, the stained α-zirconium phosphate powder was extracted by centrifugation. <Organic acid treatment of powder with citric acid> A 1000 mL aqueous solution of citric acid at a concentration of 10 g / L was mixed with the stained α-zirconium phosphate, treated at 70°C for 20 minutes, and then centrifuged to obtain the organic acid-treated α-zirconium phosphate powder. In addition to untreated α-zirconium phosphate powder, the deodorizing properties of α-zirconium phosphate powder obtained as described above (after scouring and bleaching), dyed α-zirconium phosphate powder (after dyeing), and organic acid treated α-zirconium phosphate powder (after organic acid treatment) were evaluated. <Interlayer distance, crystallite size> Interlayer distance and crystallite size were measured using Cu-Kα radiation, and powder X-ray diffraction analysis was performed using a Ni plate as a filter. The resulting diffraction patterns were then compared with ASTM cards or existing literature to identify the crystal structure. Interlayer distances were analyzed by wide-angle X-ray diffraction. The results are summarized in Figure 1 and Tables 2-4. The horizontal axis of Figure 1 is a multi-plot (overlay) of the wide-angle X-ray diffraction patterns for each sample, and is an enlarged view around 2θ = 10°. In Figure 1, 2θ = 9° corresponds to 1.0 nm, and 2θ = 11.7° corresponds to 0.75 nm. Table 2 shows the analysis results of the powder treatment, Table 3 shows the analysis results of the deodorant extracted from the treated cloth of Example 1, and Table 4 shows the analysis results of the deodorant extracted from the treated cloth of Example 3.

[0042] [Table 2]

[0043] [Table 3]

[0044] [Table 4]

[0045] As is clear from Tables 2-4, the deodorizing function of the α-zirconium phosphate powder used as a deodorant was significantly reduced after scouring and bleaching, but it was confirmed that it could be restored by organic acid treatment. Furthermore, the interlayer distance, which was approximately 1.0 nm after scouring and bleaching, was confirmed to return to 0.75 nm after organic acid treatment. Next, the deodorants were identified after staining and organic acid treatment using standard data from wide-angle X-ray diffraction. 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 staining treatment. Furthermore, in the inorganic layered deodorant after organic acid treatment, the sodium and potassium were eliminated, and the original zirconium phosphate was identified. From the above, it was found that inorganic layered deodorants without sodium and potassium bonded to them have high ammonia deodorizing function, while inorganic layered deodorants with sodium and potassium bonded to them have reduced ammonia deodorizing function. From the experiments using the inorganic layered deodorant powder described above, it can be seen that any spinning solution that can be mixed with the inorganic layered deodorant can be used.

[0048] (Example 1) <Textile materials> • Cotton yarn: Commercially available spun cotton yarn (40 count per meter, single yarn) was used. • The polyurethane elastic fiber used was 33decitex, an elastic yarn made of polyurethane containing 4% by mass of α-zirconium phosphate as an inorganic layered deodorant. <Knitting patterns> Using the cotton yarn and elastic yarn mentioned above, a knitted fabric was produced on a circular knitting machine with a gauge of 28. The resulting fabric had a weight of 165 g / m². 2 The mass ratio was 91.1% cotton yarn and 8.9% elastic yarn. The resulting knitted fabric is called raw fabric. <Scouring and bleaching treatment> In a dyeing machine, 2.5 g / L of sodium hydroxide aqueous solution, 3.0 g / L of "WX-HC" (manufactured by Nikka Chemical Co., Ltd.) as a scouring agent, 0.5 g / L of a chelating agent, and 5 g / L of 35% hydrogen peroxide aqueous solution as a bleaching agent were added to a total volume of 20 L. 1000 g of knitted fabric was immersed in this solution, and the liquid temperature was raised from 20°C to 95°C for 30 minutes for scouring and bleaching. Next, the treated water was drained, clean water was added, and the temperature was raised to 50°C for 5 minutes for rinsing. Then the water was drained, 0.25 g / L of 90% acetic acid water was added, the temperature was raised to 40°C for 5 minutes for mixing, the acetic acid water was drained, clean water was added again, the temperature was raised to 50°C for 5 minutes for rinsing, and the fabric was dehydrated and dried. <Dyeing> Fluorescent whitening was performed using reactive dyes under the following components and conditions. • Fluorescent whitening agent: Huntsman Japan Co., Ltd. product name "UVITEX BHT LIQ" 0.15% owf ·Buffer: Glauber's salt (sodium sulfate) 10g / L • Dyeing agent: "Newbon" manufactured by Nikka Chemical Co., Ltd., 0.5g / L Conditions: After dyeing at 80°C for 60 minutes, the product was neutralized at 60°C for 10 minutes, soaped at 60°C for 10 minutes, rinsed with hot water at 60°C for 10 minutes, and then dehydrated and dried. <Softening treatment> The fabric was treated with a softening agent by adding 1.5 owf% of "Softex A-1017S" manufactured by Kitahiro Chemical Co., Ltd. to an aqueous solution at 40°C for 20 minutes, then rinsed with water at 20°C for 5 minutes, and finally dehydrated and dried. <Organic acid treatment with citric acid> The dyed knitted garment was immersed in a 10g / L aqueous solution of citric acid in a dyeing machine, treated at 70°C for 20 minutes, then washed, dehydrated, and dried. The knitted fabrics obtained after treatment with citric acid as described above were evaluated.

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

[0050] (Comparative Example 1) The above raw materials 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 dyeing treatment described above was evaluated.

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

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

[0055] [Table 6]

[0056] [Table 7]

[0057] Comparative Examples 1 and 2 in Table 6 show that when knitted fabrics made of elastic fibers and cotton yarn are scoured and bleached, the deodorizing performance of the elastic fibers decreases, and this decreases further with fluorescent whitening treatment and softening treatment. However, it was confirmed that fabrics treated with citric acid immersion and heat treatment have high deodorizing performance and high wash durability.

[0058] (Example 3) <Textile materials> The procedure was the same as in Example 1, except that a blended spun yarn (meter count 40, single yarn) consisting of 30% by mass of acrylic fiber and 70% by mass of cotton fiber was used instead of cotton yarn. The mass ratio of the knitted fabric was 27% by mass of acrylic fiber, 62% by mass of cotton fiber, and 11% by mass of elastic fiber. <Dyeing> In addition to the results of Example 1, fluorescent whitening was performed using a cationic dye. • Fluorescent whitening agent: Huntsman Japan Co., Ltd. product name "UVITEX AC LIQ" 0.3% owf • Dyeing agent: Nichilon Salt C-25, manufactured by Nissei Kasei Co., Ltd., 0.5% owf Acid: 0.5 g / L aqueous acetic acid solution Conditions: After dyeing at 40°C for 10 minutes, 75°C for 15 minutes, and 100°C for 45 minutes, the material was soaped at 60°C for 10 minutes, rinsed with hot water at 60°C for 10 minutes, and then dehydrated and dried. After treating the acrylic with fluorescent whitening treatment, the cotton was treated with fluorescent whitening treatment in the same manner as in Example 1. All other treatments were carried out in the same manner as in Example 1.

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

[0060] (Comparative Example 5) The knitted fabrics after the above scouring and bleaching treatments were evaluated.

[0061] (Comparative Example 6) The knitted fabric after the softening treatment described above 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 from elastic fibers and blended acrylic / cotton fibers that were bleached and treated with citric acid showed high deodorizing performance and high wash durability.

[0064] (Examples 5-8) (1) The raw materials used were as follows: • Cotton yarn: Commercially available spun cotton yarn (40 count per meter, single yarn) was used. • The polyurethane elastic fiber used was 22decitex, an elastic yarn made of polyurethane containing 4% by mass of α-zirconium phosphate as an inorganic layered deodorant. (2) The fabric was as follows: • Using the cotton yarn and elastic yarn mentioned above, a knitted fabric was produced on a circular knitting machine with a gauge of 28. • The resulting fabric had a weight of 160 g / m². 2 The mass ratio was 94.4% by mass for cotton yarn and 5.6% by mass for elastic yarn. (3) Post-processing Except as shown in Table 9, the procedure was carried out in the same manner as in Example 1. The conditions and results are summarized in Table 9.

[0065] [Table 9]

[0066] As is clear from Table 9, acetic acid, malic acid, citric acid, and maleic acid were also used as organic acids to produce washable deodorizing treatments.

[0067] (Example 9) (1) The raw materials used were as follows: • Cotton yarn: Commercially available spun cotton yarn (40 count per meter, single yarn) was used. • The polyurethane elastic fiber used was 22decitex, an elastic yarn made of polyurethane containing 4% by mass of α-zirconium phosphate as an inorganic layered deodorant. (2) The fabric was as follows: • Using the cotton yarn and elastic yarn mentioned above, a knitted fabric was produced on a circular knitting machine with a gauge of 28. • The resulting fabric had a weight of 160 g / m². 2 The mass ratio was 93.1% cotton yarn and 6.9% elastic yarn. (3) Post-processing Except as shown in Table 10, the procedure was carried out in the same manner as in Example 1. 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 (KONICA MINOLTA, model: CM-3700d, D65 light source) and calculating the whiteness according to JIS Z 8715-1999. A higher value indicates a whiter fabric.

[0068] [Table 10]

[0069] (Example 10) The procedure was carried out in the same manner as in Example 9, except that the order of staining and organic acid treatment was changed, with the organic acid treatment performed first and the staining 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 whiteness is higher when organic acid treatment is performed first and staining is performed afterward. Furthermore, Table 12 shows that the deodorizing function of the α-zirconium phosphate powder deodorant is significantly reduced after scouring and bleaching, but the deodorizing function is restored even if organic acid treatment is performed first and dyeing is done afterward. [Industrial applicability]

[0073] The odor-eliminating fiber structure of the present invention is excellent at eliminating sweat odor and age-related odor, and is suitable for carpets, curtains, bedding, underwear, diapers, sanitary products, etc. It is particularly suitable for stretchy clothing such as legwear, innerwear, sportswear, and socks.

Claims

1. A deodorizing fiber structure in a bleached state, comprising a first fiber which is at least one selected from synthetic fibers and regenerated fibers, and a second fiber which is a natural fiber, The first fiber is a deodorizing fiber obtained by mixing a polymer with an inorganic layered deodorant, which is α-zirconium phosphate, and the second fiber contains cotton. The inorganic layered deodorant has an interlayer distance of 0.1 nm or more and 0.9 nm or less, and a crystallite size of 1 nm or more and 30 nm or less. The aforementioned deodorizing fiber structure is characterized in that the ammonia gas reduction rate after 0 and 10 washes at home is 70% or more.

2. The odor-eliminating fiber structure according to claim 1, wherein the fiber structure, when the fiber structure is considered as the base, contains 1 to 99% by mass of the odor-eliminating fibers.

3. The odor-eliminating fiber structure according to claim 1 or 2, wherein the fiber structure is a knitted fabric, a woven fabric, or a garment sewn from the same.

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