Polyurethane fiber

Abstract

We provide polyurethane fibers. [Solution] The polyurethane fiber comprises a portion (A) containing a silver component and polyurethane, and a portion (B) (a portion (B)) containing a zirconium component and polyurethane (a portion (B) that is different from portion (A)).

Description

Technical Field

[0001] The present invention relates to polyurethane fibers and the like.

Background Art

[0002] Polyurethane fibers are used in various applications such as clothing and sanitary applications (diapers, napkins, etc.). And attempts are being made to impart antibacterial and deodorizing properties to such polyurethane fibers [molded products (products) containing polyurethane fibers] (Patent Document 1). For example, Patent Document 1 discloses an elastic yarn made of polyurethane having a polymer diol and a diisocyanate as starting materials, containing a metal phosphate, and having a diffusion amount of a monoamine compound having a molecular weight of 120 or less of 100 μg / m 2 or more, which is excellent in antibacterial and deodorizing properties.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] An object of the present invention is to provide polyurethane fibers (threads) and the like.

Means for Solving the Problems

[0005] As described above, attempts are being made to impart antibacterial and deodorizing properties to polyurethane fibers. Under these circumstances, the inventors, after diligent research, discovered that by incorporating specific components into polyurethane fibers in a specific manner, antibacterial and deodorizing properties (e.g., deodorizing properties against ammonia) can be efficiently expressed (especially both simultaneously), and that such antibacterial and deodorizing properties can be efficiently maintained (e.g., maintained even after repeated washing), thus completing the present invention.

[0006] In other words, the present invention relates to the following inventions, etc. [1] A polyurethane fiber (yarn) comprising a portion (A) containing silver and polyurethane, and a portion (B) (a portion different from portion (A)) containing zirconium and polyurethane. [2] The polyurethane fiber according to [1], wherein the silver component contains a silver compound. [3] A polyurethane fiber according to [1] or [2], wherein the median diameter of the silver component is 0.01 to 10 μm. [4] A polyurethane fiber according to any one of [1] to [3], wherein the proportion of silver in part (A) is 0.0001 to 5% by mass. [5] A polyurethane fiber according to any one of [1] to [4], wherein in part (A), the ratio of zirconium to 1 part by mass of silver is less than 25 parts by mass. [6] A polyurethane fiber according to any one of [1] to [5], wherein the zirconium component contains zirconium phosphate. [7] A polyurethane fiber according to any one of [1] to [6], wherein the median diameter of the zirconium component is 0.01 to 10 μm. [8] A polyurethane fiber according to any one of [1] to [7], wherein the proportion of zirconium in part (B) is 0.01 to 15% by mass. [9] A polyurethane fiber according to any one of [1] to [8], wherein in part (B), the ratio of silver to 1 part by mass of zirconium is less than 0.01 parts by mass.

[10] In part (B), the proportion of at least one metal M selected from Zn, Mg, Ca, Al, Ti, Cu, and Ag to 1 part by mass of zirconium is less than 0.01 parts by mass of the polyurethane fiber according to any one of [1] to [9].

[11] A polyurethane fiber according to any one of [1] to

[10] , wherein part (A) and part (B) are fibrous (polyurethane fibers).

[12] A polyurethane fiber according to any one of [1] to

[11] , which is a composite (conjugated) fiber (yarn) comprising a fibrous portion (A) and a fibrous portion (B).

[13] A polyurethane fiber according to any one of [1] to

[12] , wherein at least a portion (especially all) of portion (A) is exposed to at least a portion (especially all) of the fiber surface.

[14] A polyurethane fiber according to any one of [1] to

[13] , wherein at least a portion (especially all) of portion (B) is located inside the fiber more than at least a portion (especially all) of portion (A).

[15] A polyurethane fiber according to any one of [1] to

[14] , comprising a fibrous portion (A) and a fibrous portion (B), wherein at least a portion (especially all) of the fibrous portion (A) is exposed to at least a portion (especially all) of the fiber surface, and at least a portion (especially all) of the fibrous portion (B) is located inside the fiber more than at least a portion (especially all) of the fibrous portion (A).

[16] A polyurethane fiber according to any one of [1] to

[15] , wherein the ratio of part (A) to the total amount of part (A) and part (B) is 0.1 to 99.5% by mass.

[17] A polyurethane fiber as described in any of [1] to

[16] , wherein the silver content is 0.00001 to 3% by mass.

[18] The polyurethane fiber according to any one of [1] to

[17] , wherein the proportion of zirconium is 0.01 to 15% by mass.

[19] A fabric containing the polyurethane fiber according to any one of [1] to

[18] .

[20] A molded article containing the polyurethane fiber according to any one of [1] to

[18] . [Effects of the Invention]

[0007] According to the present invention, a polyurethane fiber (such as an elastic fiber) can be provided. In one aspect of the fiber (thread) of the present invention, it contains specific components in a specific aspect and can efficiently exhibit (particularly simultaneously exhibit) antibacterial and deodorizing properties.

[0008] In another aspect of the fiber (thread) of the present invention, such antibacterial and deodorizing properties can be efficiently maintained or sustained (for example, the antibacterial and deodorizing properties can be maintained or sustained even after repeated washing, and excellent durability can be achieved for antibacterial and deodorizing properties).

[0009] In another aspect of the present invention, the above-described fiber (thread) can be provided without impairing the moldability (such as spinnability) [or with excellent moldability (such as spinnability)]. [Modes for Carrying Out the Invention]

[0010] The polyurethane fiber (thread) of the present invention is a fiber containing polyurethane [at least polyurethane as a resin (resin component)] and includes a specific part (A) and a specific part (B).

[0011] Specifically, the polyurethane fiber (thread) includes a part (region) (A) containing a silver component and polyurethane, and a part (region) (B) containing a zirconium component and polyurethane (part (B) different from part (A)).

[0012] Furthermore, the polyurethane fiber only needs to contain at least part (A) and part (B), may consist only of part (A) and part (B), and may have parts (regions) different from part (A) and part (B) (for example, parts that do not contain either the silver component or the zirconium component).

[0013] The details are explained below. [Part (A)] The silver component (silver source) can be any component containing the element silver (Ag), such as elemental silver, silver alloys, and silver compounds (silver-containing compounds, Ag-containing compounds).

[0014] The silver component only needs to contain at least silver (as a metal / element), and may also contain non-silver metals (elements).

[0015] Examples of non-silver metals (elements) include typical metals (elements) and transition metals (transition elements). These include alkali metals (e.g., sodium, potassium), alkaline earth metals (e.g., magnesium, calcium), metals (elements) of groups 3-12 of the periodic table (e.g., scandium, yttrium, lanthanum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, gold, zinc, cadmium, etc.), and metals (elements) of groups 1-17 of the periodic table, such as metals of groups 13-16 (e.g., aluminum, gallium, indium, thallium, tin, lead, antimony, bismuth, etc.). Non-silver metals may be included in the silver component, either individually or in combination of two or more.

[0016] Furthermore, the silver component may also contain nonmetallic elements [for example, hydrogen, elements from groups 13 to 17 of the periodic table (for example, boron, carbon, silicon, nitrogen, phosphorus, arsenic, oxygen, sulfur, fluorine, chlorine, bromine, iodine)]. Nonmetallic elements may be included in the silver component individually or in combination of two or more elements.

[0017] Non-silver metals (elements) and nonmetallic elements may be included in the silver component in the form of compounds (e.g., hydrides, oxides, hydroxides, halides, alkoxides, complexes, salts).

[0018] Specific examples of compounds include copper oxide, titanium oxide, magnesium oxide, complex oxides containing zinc and zirconium, complex oxides containing silicon and zirconium, zeolites, glass (such as borosilicate glass), zirconium phosphate, sodium hydride, and compounds combining these.

[0019] The silver component may typically contain elements such as boron (B), carbon (C), oxygen (O), sodium (Na), magnesium (Mg), calcium (Ca), silicon (Si), titanium (Ti), zirconium (Zr), copper (Cu), zinc (Zn), aluminum (Al), phosphorus (P), and sulfur (S).

[0020] In particular, the silver component is preferably a silver component (e.g., a composite metal oxide) that contains at least one element selected from B, Na, Al, Si, and Zr (especially Na and Zr) along with Ag.

[0021] In the silver component, silver (element) may constitute a compound together with non-silver metals (elements) or nonmetallic elements, or it may be supported on a compound containing non-silver metals (elements) or nonmetallic elements, or it may be included in the silver component in both of these forms.

[0022] Typically, the silver component may be a silver compound. Therefore, the silver component may contain a silver compound.

[0023] Specific examples of silver-containing components [for example, silver components containing silver in a supported form (silver compounds, etc.)] include, for example, silver-supported (containing) zirconium phosphate (compounds), silver-supported (containing) zeolite, and silver-supported (containing) glass (borosilicate glass, etc.).

[0024] The median diameter of the silver component may be, from the viewpoint of spinnability and dispersibility, for example, 10 μm or less (e.g., 0.01 to 8 μm or less), preferably 5 μm or less (e.g., 0.05 to 4 μm or less), and more preferably 3 μm or less (e.g., 0.1 to 2.5 μm, 0.15 to 2.2 μm), or 2 μm or less (e.g., 1.8 μm or less, 1.5 μm or less, 1.2 μm or less, 1 μm or less, 0.9 μm or less, 0.8 μm or less, 0.7 μm or less).

[0025] The median diameter is not particularly limited, but can be measured, for example, by a particle size analyzer, and may be measured by the method described later.

[0026] In part (A), the proportion of silver (element) (proportion in terms of elemental silver) may be selected from a range of, for example, 0.00001% by mass or more (e.g., 0.00005% by mass or more), preferably 0.0001% by mass or more (e.g., 0.0005% by mass or more), more preferably 0.001% by mass or more (e.g., 0.005% by mass or more), and particularly 0.01% by mass or more (e.g., 0.012% by mass or more), and may also be 0.015% by mass or more (e.g., 0.018% by mass or more, 0.02% by mass or more, 0.025% by mass or more, 0.03% by mass or more, 0.05% by mass or more, 0.08% by mass or more, 0.1% by mass or more, 0.12% by mass or more, 0.15% by mass or more), etc.

[0027] In part (A), the proportion of silver (element) (upper limit of the proportion of silver element) is not particularly limited, but it may be selected from a range that is not too large from the viewpoint of moldability and fiber quality, for example, 20% by mass or less (for example, 15% by mass or less), preferably 10% by mass or less (for example, 8% by mass or less), more preferably 5% by mass or less (for example, 3% by mass or less), and especially 2% by mass or less (for example, 1.5% by mass or less), and it may also be 1% by mass or less (for example, 0.9% by mass or less, 0.8% by mass or less, 0.7% by mass or less, 0.6% by mass or less, 0.5% by mass or less, 0.4% by mass or less, 0.3% by mass or less, 0.2% by mass or less, 0.15% by mass or less, 0.1% by mass or less), etc.

[0028] In part (A), the proportion of silver component (silver source) may be selected from a range of, for example, 0.00001% by mass or more (e.g., 0.0001% by mass or more), preferably 0.001% by mass or more (e.g., 0.005% by mass or more), more preferably 0.01% by mass or more (e.g., 0.05% by mass or more), and particularly 0.1% by mass or more (e.g., 0.12% by mass or more, 0.15% by mass or more, 0.2% by mass or more), and may also be 0.3% by mass or more (e.g., 0.35% by mass or more, 0.45% by mass or more, 0.5% by mass or more, 0.6% by mass or more, 0.8% by mass or more, 1% by mass or more, 1.2% by mass or more, 1.5% by mass or more, 1.8% by mass or more, 2% by mass or more, 2.2% by mass or more, 2.5% by mass or more, 2.8% by mass or more, 3% by mass or more), etc.

[0029] In part (A), the proportion of silver component (silver source) can be selected from a range that is not too large from the viewpoint of moldability and fiber quality, for example, 30% by mass or less (for example, 25% by mass or less), preferably 20% by mass or less (for example, 18% by mass or less), more preferably 15% by mass or less (for example, 12% by mass or less), and particularly 10% by mass or less (for example, 9% by mass or less), and can also be 8% by mass or less (for example, 7.8% by mass or less, 7.5% by mass or less, 7.2% by mass or less, 7% by mass or less, 6.8% by mass or less, 6.5% by mass or less, 6.2% by mass or less, 5.8% by mass or less, 5.5% by mass or less, 5.2% by mass or less, 5% by mass or less), etc.

[0030] Furthermore, part (A) may or may not contain metals (elements) other than silver [non-silver metals (elements)].

[0031] Such non-silver metals (elements) may be included in the silver component as described above, or they may be included in part (A) in the form of elemental metals, alloys, compounds (e.g., phosphates), etc. Furthermore, non-silver metals (elements) may also be included (as non-silver metals) as other components, etc., as described later.

[0032] If part (A) contains non-silver metals (elements), the proportion is not limited, but in particular, with respect to zirconium (element), it is preferable that it is not included in a high proportion (large excess proportion) relative to silver, from the viewpoint of efficient expression of the effects and functions of silver in part (A).

[0033] For example, in part (A), the ratio of zirconium (element) to 1 part by mass of silver (silver constituting the silver component) (ratio in terms of metallic elements) may be less than 25 parts by mass (for example, 24 parts by mass or less, 22 parts by mass or less), preferably 20 parts by mass or less (for example, 18 parts by mass or less, 16 parts by mass or less), and more preferably 15 parts by mass or less (for example, 14 parts by mass or less, 12 parts by mass or less), and may also be 10 parts by mass or less (for example, 9 parts by mass or less, 8 parts by mass or less, 7 parts by mass or less, 6 parts by mass or less), etc.

[0034] When part (A) contains zirconium (element), the lower limit of the ratio of zirconium (element) to 1 part by mass of silver (silver constituting the silver component) (ratio in terms of metallic elements) is not particularly limited, but may be, for example, 0.01 parts by mass, 0.1 parts by mass, 0.2 parts by mass, 0.3 parts by mass, 0.5 parts by mass, 0.8 parts by mass, 1 part by mass, 1.2 parts by mass, 1.5 parts by mass, 1.8 parts by mass, 2 parts by mass, 2.2 parts by mass, 2.5 parts by mass, 2.8 parts by mass, 3 parts by mass, 3.2 parts by mass, 3.5 parts by mass, 3.8 parts by mass, 4 parts by mass, 4.2 parts by mass, 4.5 parts by mass, 4.8 parts by mass, 5 parts by mass, 5.2 parts by mass, 5.5 parts by mass, etc.

[0035] The proportion of non-silver metals (such as zirconium) relative to silver, the proportion of silver (element) in the silver component, and the proportion of silver and non-silver metals in part (A) or the fiber are not particularly limited, but can be measured, for example, by ICP emission spectrometry, and may be measured specifically by the method described below.

[0036] The polyurethane [polyurethane constituting (contained in part (A)) (polyurethane as a resin component)] is not particularly limited and may be, for example, polyurethane (any structure) made from polymer polyols (usually at least polymer diols) and isocyanate compounds (usually at least diisocyanates) as raw materials (polymerization components, monomers, starting materials). The raw materials may also typically contain chain extenders.

[0037] Furthermore, the synthesis method is not particularly limited. For example, it may be a polyurethane urea composed of a polymer diol, a diisocyanate, and a low molecular weight diamine as a chain extender, or a polyurethane urethane composed of a polymer diol, a diisocyanate, and a low molecular weight diol as a chain extender. It may also be a polyurethane urea using a compound having hydroxyl and amino groups in its molecule as a chain extender. If necessary (within the limits that do not hinder the effects of the present invention), it is also preferable to use a polyfunctional glycol or isocyanate with three or more functions.

[0038] Polyurethanes typically include polyurethane urea and polyurethane urethane. Of these, polyurethane urea is preferred.

[0039] Examples of polyurethane ureas include those made from polymer polyols (usually at least polymer diols) and isocyanate compounds (usually at least diisocyanates), and from polyamines [usually at least diamines (low molecular weight diamines)] or compounds having a hydroxyl group and an amino group [usually compounds having one hydroxyl group and one amino group (bifunctional compounds)] as chain elongators.

[0040] Examples of polyurethane urethanes include those made from polymer polyols (usually at least polymer diols) and isocyanate compounds (usually at least diisocyanates), and a polyol [usually at least diol (low molecular weight diol)] as a chain extender.

[0041] As mentioned above, polyurethane is typically made from bifunctional compounds such as polymer diols, diisocyanates, diamines, and diols, but may also contain trifunctional or higher-functioning compounds (such as polyols and polyisocyanates) as raw materials if necessary.

[0042] The polymer diols are preferably polyether-based, polyester-based, or polycarbonate-based. From the viewpoint of imparting flexibility and elongation to the fibers (yarns), the use of polyether-based diols is preferable.

[0043] Preferably used polyether diols include, for example, polyethylene oxide, polyethylene glycol, derivatives of polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol (hereinafter sometimes abbreviated as PTMG), modified PTMG which is a copolymer of tetrahydrofuran (hereinafter sometimes abbreviated as THF) and 3-methyltetrahydrofuran, modified PTMG which is a copolymer of THF and 2-methyltetrahydrofuran, modified PTMG which is a copolymer of THF and 2,3-dimethyl THF, polyols having side chains on both sides as disclosed in Japanese Patent Publication No. 2615131, and random copolymers in which THF and ethylene oxide and / or propylene oxide are irregularly arranged. These polyether diols may be used individually or in mixtures or copolymers of two or more types.

[0044] Furthermore, from the viewpoint of obtaining abrasion resistance and light resistance as polyurethane elastic fibers, polyester diols such as butylene adipate, polycaprolactone diol, polyester polyols having side chains disclosed in Japanese Patent Publication No. 61-26612, etc., and polycarbonate diols disclosed in Japanese Patent Publication No. 10-226921, etc., are preferably used.

[0045] Furthermore, these polymer diols may be used individually, or two or more may be used in mixture or copolymerization.

[0046] From the viewpoint of obtaining elongation, strength, and heat resistance when made into yarn, the molecular weight (number average molecular weight) of the polymer diol is preferably between 1000 and 8000, and more preferably between 1500 and 6000. By using polyols with a molecular weight in this range, fibers (yarns, elastic yarns) with excellent elongation, strength, elastic recovery, and heat resistance can be easily obtained. The molecular weight can be measured, for example, by GPC and converted to polystyrene.

[0047] Next, as diisocyanates, aromatic diisocyanates such as diphenylmethane diisocyanate (hereinafter sometimes abbreviated as MDI), tolylene diisocyanate, 1,4-diisocyanatebenzene, xylylene diisocyanate, and 2,6-naphthalene diisocyanate are particularly suitable for synthesizing polyurethanes 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. Alicyclic diisocyanates can be used particularly effectively in suppressing yellowing of polyurethane elastic yarns. These diisocyanates may be used individually or in combination of two or more.

[0048] Next, when synthesizing polyurethane, it is preferable to use at least one of low molecular weight diamines and low molecular weight diols as the chain elongator. Alternatively, a substance containing both a hydroxyl group and an amino group in a single molecule, such as ethanolamine, may also be used.

[0049] Preferred low molecular weight diamines include, for example, 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 effect.

[0050] Furthermore, typical 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. Particularly preferred are ethylene glycol, 1,3-propanediol, and 1,4-butanediol. Using these diols results in a polyurethane with higher heat resistance and a stronger yarn.

[0051] 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.

[0052] From the viewpoint of obtaining highly durable and strong fibers, the molecular weight (number average molecular weight) of polyurethane is preferably in the range of 10,000 to 200,000 (for example, 15,000 to 180,000, 20,000 to 150,000, and 30,000 to 150,000). The molecular weight can be measured, for example, by GPC and converted to polystyrene.

[0053] The proportion of polyurethane in part (A) may be selected from a range of, for example, 5% by mass or more (e.g., 10% by mass or more), 20% by mass or more (e.g., 25% by mass or more), preferably 30% by mass or more (e.g., 35% by mass or more), more preferably 40% by mass or more (e.g., 45% by mass or more), particularly 50% by mass or more (e.g., 55% by mass or more), and may also be 60% by mass or more (e.g., 65% by mass or more, 70% by mass or more, 75% by mass or more, 80% by mass or more, 85% by mass or more, 88% by mass or more, 90% by mass or more, 92% by mass or more, 95% by mass or more), etc.

[0054] Part (A) may contain other components (other than silver and polyurethane) as needed.

[0055] Other components include, for example, metal soaps, surfactants, antioxidants, tertiary amine compounds, crosslinking structure modifiers, silicones (e.g., silicone oil, modified silicone), fine particles (e.g., talc, silica, alumina, zinc oxide, titanium dioxide), higher aliphatic alcohols, waxes, colorants, rosin, dyes, pigments, oils (mineral oil, silicone oil, etc.), inorganic materials and inorganic porous materials (e.g., bamboo charcoal, wood charcoal, carbon black, porous mud, clay, diatomaceous earth, coconut shell activated carbon, coal-based activated carbon, zeolite, perlite, etc.), catalysts (catalytic components, e.g., polyurethane amine-based catalysts, organometallic catalysts), and resin components (resin components other than polyurethane).

[0056] Other specific components may include lightfasteners and antioxidants such as BHT and hindered phenol-based agents such as Sumitomo Chemical Co., Ltd.'s "Sumilyzer" (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 "Sumilyzer" (registered trademark) P-16, various hindered amine-based agents, 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. It is also preferable that these be reacted with the polymer (polyurethane). Furthermore, to further enhance durability against light and various nitrogen oxides, it is preferable to use nitrogen oxide scavengers such as HN-150 manufactured by Nippon Hydrazine Co., Ltd., thermal oxidation stabilizers such as "SumiLizer" (registered trademark) GA-80 manufactured by Sumitomo Chemical Co., Ltd., and light stabilizers such as "SumiSorb" (registered trademark) 300#622 manufactured by Sumitomo Chemical Co., Ltd.

[0057] Other specific components include resins. Examples of resins include cellulose resins (e.g., cellulose esters such as cellulose acetate, cellulose acetate propionate, and cellulose acetate butyrate; cellulose ethers such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, and sodium carboxymethylcellulose), styrene resins (e.g., polystyrene), polyester resins (e.g., polyethylene terephthalate, polybutylene terephthalate), polycarbonate resins, olefin resins (e.g., polyethylene, polypropylene, and cyclic olefin resins), halogenated resins (e.g., polyvinyl chloride), acrylic resins, and polyamide resins.

[0058] If part (A) contains such a resin (cellulose resin, etc.), the proportion of the resin in part (A) may be, for example, 30% by mass or less (e.g., 20% by mass or less, 15% by mass or less, 10% by mass or less, 8% by mass or less, 5% by mass or less), or 0.00001% by mass or more (e.g., 0.0001% by mass or more, 0.001% by mass or more, 0.01% by mass or more, 0.1% by mass or more).

[0059] Furthermore, as described later, such resins may be incorporated during the manufacturing of fibers in the form of a dispersion containing silver components.

[0060] Furthermore, non-silver metals (elements) may be included in part (A) as other components as described above.

[0061] Other components may be included in part (A) individually or in combination of two or more.

[0062] [Part (B)] The zirconium component (zirconium source) can be any component containing the element zirconium (Zr), such as elemental zirconium, zirconium alloys, and zirconium compounds (zirconium-containing compounds, Zr-containing compounds).

[0063] The zirconium component only needs to contain at least zirconium (element) as a metal (element), and may also contain non-zirconium metals (elements).

[0064] Examples of non-zirconium metals (elements) include typical metals (elements) and transition metals (transition elements), such as alkali metals (e.g., sodium, potassium), alkaline earth metals (e.g., magnesium, calcium), metals (elements) of groups 3-12 of the periodic table (e.g., scandium, yttrium, lanthanum, titanium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc, cadmium, etc.), and metals (elements) of groups 1-17 of the periodic table, such as metals of groups 13-16 (e.g., aluminum, gallium, indium, thallium, tin, lead, antimony, bismuth, etc.).

[0065] Non-zirconium metals may be included in the zirconium component, either individually or in combination of two or more.

[0066] Furthermore, the zirconium component may also contain nonmetallic elements [for example, hydrogen, elements from groups 13 to 17 of the periodic table (for example, boron, carbon, silicon, nitrogen, phosphorus, arsenic, oxygen, sulfur, fluorine, chlorine, bromine, iodine)].

[0067] Nonmetallic elements may be included in the zirconium component individually or in combination of two or more elements.

[0068] Non-zirconium metals (elements) and nonmetallic elements may be included in the zirconium component in the form of compounds (e.g., oxides, hydroxides, halides, alkoxides, complexes, salts).

[0069] In the zirconium component, zirconium (element) may constitute a compound together with non-zirconium metals (elements) or nonmetallic elements, or it may be supported on a compound containing non-zirconium metals (elements) or nonmetallic elements, or it may be included in the zirconium component in both of these forms.

[0070] Specific zirconium components include, for example, oxides, hydroxides, halides (e.g., fluorides, chlorides, bromides, iodides), salts [e.g., salts with inorganic acids (e.g., sulfuric acid, nitric acid, phosphoric acid), salts with organic acids (e.g., carboxylic acids such as acetic acid and oxalic acid (e.g., fatty acids); sulfonic acids such as methanesulfonic acid and trifluoromethanesulfonic acid)].

[0071] Preferred zirconium components include zirconium phosphate. The crystal structure of zirconium phosphate is not limited and may be α-type, β-type, γ-type, plate-like (flat), etc. Zirconium phosphate may have a multilayer structure (such as a two-layer or three-layer structure). Furthermore, the zirconium component (such as zirconium phosphate) may be in hydrate form.

[0072] The median diameter of the zirconium component (such as zirconium phosphate) may be, for example, 10 μm or less (e.g., 0.01 to 8 μm), preferably 5 μm or less (e.g., 0.05 to 4 μm), and more preferably 3 μm or less (e.g., 0.1 to 2.5 μm, 0.15 to 2.2 μm), or 2 μm or less (e.g., 1.8 μm or less, 1.5 μm or less, 1.2 μm or less, 1 μm or less, 0.9 μm or less, 0.8 μm or less, 0.7 μm or less), from the viewpoint of spinnability and dispersibility.

[0073] The median diameter is not particularly limited, but can be measured, for example, by a particle size analyzer, and may be measured by the method described later.

[0074] In part (B), the proportion of zirconium (element) (proportion in terms of zirconium element) may be selected from a range of, for example, 0.0001% by mass or more (e.g., 0.0005% by mass or more), preferably 0.001% by mass or more (e.g., 0.005% by mass or more), more preferably 0.01% by mass or more (e.g., 0.05% by mass or more), and particularly 0.1% by mass or more (e.g., 0.12% by mass or more), and 0.15% by mass or more (e.g., 0.18% by mass or more). It can also be set to 0.2% by mass or more, 0.25% by mass or more, 0.35% by mass or more, 0.4% by mass or more, 0.45% by mass or more, 0.5% by mass or more, 0.55% by mass or more, 0.6% by mass or more, 0.65% by mass or more, 0.7% by mass or more, 0.75% by mass or more, 0.8% by mass or more, 0.85% by mass or more, 0.9% by mass or more, 0.95% by mass or more, 1% by mass or more, 1.05% by mass or more, 1.1% by mass or more, 1.15% by mass or more, 1.2% by mass or more, etc.

[0075] In part (B), the proportion of zirconium (element) (upper limit of the proportion of zirconium element) is not particularly limited, but may be selected from a range that is not too large from the viewpoint of moldability and fiber quality, for example, 30% by mass or less (for example, 25% by mass or less), preferably 20% by mass or less (for example, 18% by mass or less), more preferably 15% by mass or less (for example, 12% by mass or less), and especially 10% by mass or less (for example, 8% by mass or less), and can also be 7% by mass or less (for example, 6.5% by mass or less, 6% by mass or less, 5.5% by mass or less, 5% by mass or less, 4.5% by mass or less, 4% by mass or less, 3.5% by mass or less, 3% by mass or less, 2.5% by mass or less, 2% by mass or less, 1.8% by mass or less).

[0076] In part (B), the proportion of the zirconium component (zirconium source) may be selected from a range of approximately 0.0001% by mass or more (e.g., 0.0005% by mass or more), preferably 0.001% by mass or more (e.g., 0.01% by mass or more), more preferably 0.03% by mass or more (e.g., 0.05% by mass or more), and particularly 0.1% by mass or more (e.g., 0.15% by mass or more), and 0.2% by mass or more (e.g., 0.3% by mass or more, 0.4% by mass or more, 0.5% by mass or more, 0.6% by mass or more, 0.7% by mass or more, 0.8% by mass or more, 0.9% by mass or more). % or more, 1% by mass or more, 1.1% by mass or more, 1.2% by mass or more, 1.3% by mass or more, 1.4% by mass or more, 1.5% by mass or more, 1.6% by mass or more, 1.7% by mass or more, 1.8% by mass or more, 1.9% by mass or more, 2% by mass or more, 2.1% by mass or more, 2.2% by mass or more, 2. (3 mass% or more, 2.4 mass% or more, 2.5 mass% or more, 2.8 mass% or more, 3 mass% or more, 3.2 mass% or more, 3.5 mass% or more, 3.8 mass% or more, 4 mass% or more, 4.2 mass% or more, 4.5 mass% or more, 4.8 mass% or more, 5 mass% or more), etc.

[0077] In part (B), the proportion of zirconium (upper limit of the proportion of zirconium) is not particularly limited, but may be selected from a range that is not too large from the viewpoint of moldability and fiber quality, for example, 30% by mass or less (for example, 28% by mass or less), preferably 25% by mass or less (for example, 22% by mass or less), more preferably 20% by mass or less (for example, 18% by mass or less), and particularly 16% by mass or less, and may also be 15% by mass or less (for example, 14% by mass or less, 13% by mass or less, 12% by mass or less, 11% by mass or less, 10% by mass or less, 9.5% by mass or less, 9% by mass or less, 8.5% by mass or less, 8% by mass or less, 7.5% by mass or less, 7% by mass or less, 6.5% by mass or less, 6% by mass or less, 5.5% by mass or less, 5% by mass or less, 4.5% by mass or less).

[0078] Furthermore, part (B) may or may not contain metals (elements) other than zirconium [non-zirconium metals (elements)].

[0079] Such non-zirconium metals (elements) may be included in the zirconium component as described above, or they may be included in part (B) in the form of elemental metals, alloys, compounds (e.g., phosphates), etc. Furthermore, non-zirconium metals (elements) may also be included as other components (as non-zirconium metals) as described later.

[0080] If part (B) contains a non-zirconium metal (element), the proportion is not limited, but in particular, with respect to silver (element), it is preferable that it is not contained in a high proportion relative to zirconium, from the viewpoint of efficient expression of the action and function of the zirconium component in part (B). For example, in part (B), the ratio of silver (element) to 1 part by mass of zirconium (zirconium constituting the zirconium component) (ratio in terms of metallic elements) may be less than 0.01 parts by mass (e.g., 0.009 parts by mass or less, 0.008 parts by mass or less), preferably 0.005 parts by mass or less (e.g., 0.004 parts by mass or less), and more preferably 0.003 parts by mass or less (e.g., 0.0025 parts by mass or less), and may also be 0.002 parts by mass or less (e.g., 0.0015 parts by mass or less, 0.001 parts by mass or less, 0.0005 parts by mass or less, 0.0001 parts by mass or less), etc.

[0081] Furthermore, in part (B), it is preferable that not only silver, but also certain metals, are not contained in a high proportion relative to zirconium, from the viewpoint of efficiently expressing the action and function of the zirconium component in part (B). For example, in part (B), the ratio (ratio in terms of metal elements) of at least one metal (element) M selected from Zn, Mg, Ca, Al, Ti, Cu, and Ag to 1 part by mass of zirconium (zirconium constituting the zirconium component) may be less than 0.01 parts by mass (e.g., 0.009 parts by mass or less, 0.008 parts by mass or less), preferably 0.005 parts by mass or less (e.g., 0.004 parts by mass or less), and more preferably around 0.003 parts by mass or less (e.g., 0.0025 parts by mass or less), and may also be 0.002 parts by mass or less (e.g., 0.0015 parts by mass or less, 0.001 parts by mass or less, 0.0005 parts by mass or less, 0.0001 parts by mass or less), etc.

[0082] The ratio of non-zirconium metals (Ag, metal M, etc.) to zirconium, the proportion of zirconium (element) in the zirconium component, and the proportion of zirconium and non-zirconium metals in the portion (B) and fibers are not particularly limited, but can be measured, for example, by ICP emission spectrometry, and may be measured specifically by the method described below.

[0083] The polyurethane [polyurethane constituting (contained in part (B)) (polyurethane as a resin component)] is not particularly limited and may be, for example, polyurethane (any structure) made from polymer polyols (usually at least polymer diols) and isocyanate compounds (usually at least diisocyanates) as raw materials (polymerization components, monomers, starting materials). The raw materials may also typically contain chain extenders.

[0084] Furthermore, the synthesis method is not particularly limited. For example, it may be a polyurethane urea composed of a polymer diol, a diisocyanate, and a low molecular weight diamine as a chain extender, or a polyurethane urethane composed of a polymer diol, a diisocyanate, and a low molecular weight diol as a chain extender. It may also be a polyurethane urea using a compound having hydroxyl and amino groups in its molecule as a chain extender. If necessary (within the limits that do not hinder the effects of the present invention), it is also preferable to use a polyfunctional glycol or isocyanate with three or more functions.

[0085] Polyurethanes typically include polyurethane urea and polyurethane urethane. Of these, polyurethane urea is preferred.

[0086] Examples of polyurethane ureas include those made from polymer polyols (usually at least polymer diols) and isocyanate compounds (usually at least diisocyanates), and from polyamines [usually at least diamines (low molecular weight diamines)] or compounds having a hydroxyl group and an amino group [usually compounds having one hydroxyl group and one amino group (bifunctional compounds)] as chain elongators.

[0087] Examples of polyurethane urethanes include those made from polymer polyols (usually at least polymer diols) and isocyanate compounds (usually at least diisocyanates), and a polyol [usually at least diol (low molecular weight diol)] as a chain extender.

[0088] As mentioned above, polyurethane is typically made from bifunctional compounds such as polymer diols, diisocyanates, diamines, and diols, but may also contain trifunctional or higher-functioning compounds (such as polyols and polyisocyanates) as raw materials if necessary.

[0089] The polymer diols are preferably polyether-based, polyester-based, or polycarbonate-based. From the viewpoint of imparting flexibility and elongation to the fibers (yarns), the use of polyether-based diols is preferable.

[0090] Preferably used polyether diols include, for example, polyethylene oxide, polyethylene glycol, derivatives of polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol (hereinafter sometimes abbreviated as PTMG), modified PTMG which is a copolymer of tetrahydrofuran (hereinafter sometimes abbreviated as THF) and 3-methyltetrahydrofuran, modified PTMG which is a copolymer of THF and 2-methyltetrahydrofuran, modified PTMG which is a copolymer of THF and 2,3-dimethyl THF, polyols having side chains on both sides as disclosed in Japanese Patent Publication No. 2615131, and random copolymers in which THF and ethylene oxide and / or propylene oxide are irregularly arranged. These polyether diols may be used individually or in mixtures or copolymers of two or more types.

[0091] Furthermore, from the viewpoint of obtaining abrasion resistance and light resistance as polyurethane fibers, polyester diols such as butylene adipate, polycaprolactone diol, polyester polyols having side chains as disclosed in Japanese Patent Publication No. 61-26612, and polycarbonate diols as disclosed in Japanese Patent Publication No. 10-226921 are preferably used.

[0092] Furthermore, these polymer diols may be used individually, or two or more may be used in mixture or copolymerization.

[0093] From the viewpoint of obtaining elongation, strength, and heat resistance when made into yarn, the molecular weight (number average molecular weight) of the polymer diol is preferably between 1000 and 8000, and more preferably between 1500 and 6000. By using polyols with a molecular weight in this range, fibers (yarns, elastic yarns) with excellent elongation, strength, elastic recovery, and heat resistance can be easily obtained. The molecular weight can be measured, for example, by GPC and converted to polystyrene.

[0094] Next, as diisocyanates, aromatic diisocyanates such as diphenylmethane diisocyanate (hereinafter sometimes abbreviated as MDI), tolylene diisocyanate, 1,4-diisocyanatebenzene, xylylene diisocyanate, and 2,6-naphthalene diisocyanate are particularly suitable for synthesizing polyurethanes 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. Alicyclic diisocyanates can be used particularly effectively in suppressing yellowing of polyurethane elastic yarns. These diisocyanates may be used individually or in combination of two or more.

[0095] Next, when synthesizing polyurethane, it is preferable to use at least one of low molecular weight diamines and low molecular weight diols as the chain elongator. Alternatively, a substance containing both a hydroxyl group and an amino group in a single molecule, such as ethanolamine, may also be used.

[0096] Preferred low molecular weight diamines include, for example, 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 effect.

[0097] Furthermore, typical 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. Particularly preferred are ethylene glycol, 1,3-propanediol, and 1,4-butanediol. Using these diols results in a polyurethane with higher heat resistance and a stronger yarn.

[0098] 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.

[0099] From the viewpoint of obtaining highly durable and strong fibers, the molecular weight (number average molecular weight) of polyurethane is preferably in the range of 10,000 to 200,000 (for example, 15,000 to 180,000, 20,000 to 150,000, and 30,000 to 150,000). The molecular weight can be measured, for example, by GPC and converted to polystyrene.

[0100] The polyurethane contained in part (B) may be the same as or different from the polyurethane contained in part (A).

[0101] The proportion of polyurethane in part (B) may be selected from a range of, for example, 5% by mass or more (e.g., 10% by mass or more), 20% by mass or more (e.g., 25% by mass or more), preferably 30% by mass or more (e.g., 35% by mass or more), more preferably 40% by mass or more (e.g., 45% by mass or more), particularly 50% by mass or more (e.g., 55% by mass or more), and may also be 60% by mass or more (e.g., 65% by mass or more, 70% by mass or more, 75% by mass or more, 80% by mass or more, 85% by mass or more, 88% by mass or more, 90% by mass or more, 92% by mass or more, 95% by mass or more), etc.

[0102] Part (B) may contain other components (components other than zirconium and polyurethane) as needed.

[0103] Other components include, for example, metal soaps, surfactants, antioxidants, tertiary amine compounds, crosslinking structure modifiers, silicones (e.g., silicone oil, modified silicone), fine particles (e.g., talc, silica, alumina, zinc oxide, titanium dioxide), higher aliphatic alcohols, waxes, colorants, rosin, dyes, pigments, oils (mineral oil, silicone oil, etc.), inorganic materials and inorganic porous materials (e.g., bamboo charcoal, wood charcoal, carbon black, porous mud, clay, diatomaceous earth, coconut shell activated carbon, coal-based activated carbon, zeolite, perlite, etc.), catalysts (catalytic components, e.g., polyurethane amine-based catalysts, organometallic catalysts), and resin components (resin components other than polyurethane).

[0104] Other specific components may include lightfasteners and antioxidants such as BHT and hindered phenol-based agents such as Sumitomo Chemical Co., Ltd.'s "Sumilyzer" (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 "Sumilyzer" (registered trademark) P-16, various hindered amine-based agents, 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. It is also preferable that these be reacted with the polymer (polyurethane). Furthermore, to further enhance durability against light and various nitrogen oxides, it is preferable to use nitrogen oxide scavengers such as HN-150 manufactured by Nippon Hydrazine Co., Ltd., thermal oxidation stabilizers such as "SumiLizer" (registered trademark) GA-80 manufactured by Sumitomo Chemical Co., Ltd., and light stabilizers such as "SumiSorb" (registered trademark) 300#622 manufactured by Sumitomo Chemical Co., Ltd.

[0105] Other specific components include resins. Examples of resins include cellulose resins (e.g., cellulose esters such as cellulose acetate, cellulose acetate propionate, and cellulose acetate butyrate; cellulose ethers such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, and sodium carboxymethylcellulose), styrene resins (e.g., polystyrene), polyester resins (e.g., polyethylene terephthalate, polybutylene terephthalate), polycarbonate resins, olefin resins (e.g., polyethylene, polypropylene, and cyclic olefin resins), halogenated resins (e.g., polyvinyl chloride), acrylic resins, and polyamide resins.

[0106] If part (B) contains such a resin (cellulose resin, etc.), the proportion of the resin in part (B) may be, for example, 30% by mass or less (e.g., 20% by mass or less, 15% by mass or less, 10% by mass or less, 8% by mass or less, 5% by mass or less), or 0.00001% by mass or more (e.g., 0.0001% by mass or more, 0.001% by mass or more, 0.01% by mass or more, 0.1% by mass or more). Furthermore, such resins may be incorporated into the fiber manufacturing process in the form of a dispersion containing zirconium components, as described later.

[0107] Furthermore, non-zirconium metals (elements) may be included in part (B) as other components as described above.

[0108] Other components may be included in part (B) individually or in combination of two or more.

[0109] [Shape and form of part (A) and part (B)] In polyurethane fibers, the shape (structure, content form) of parts (A) and (B) is not particularly limited and may be spot-like (dot-like), but from the viewpoint of more efficient expression and maintenance of antibacterial and deodorizing properties and ease of manufacture, it is preferable that they be in a shape that extends in the longitudinal direction of the polyurethane fiber (continuous shape).

[0110] Typical forms include fibers (fibrous, polyurethane fibers).

[0111] In polyurethane fibers, the positional relationship (relative positional relationship, arrangement) of part (A) and part (B) is not particularly limited. For example, part (A) may be located inside or outside part (B) [for example, inside or outside from the fiber surface (or when viewed in cross-section of the fiber)], or it may be located both inside and outside.

[0112] In particular, from the viewpoint of efficient expression of antibacterial properties, it is preferable that at least a part (especially all) of part (A) is exposed to at least a part (especially all) of the fiber surface [constitutes at least a part (especially all) of the fiber surface].

[0113] Furthermore, from the viewpoint of efficiently exhibiting deodorizing properties, it is preferable that at least a part (especially all) of part (B) is located (arranged) further inside the fibers than at least a part (especially all) of part (A).

[0114] Typically, a polyurethane fiber may be a conjugated fiber (yarn) comprising a fibrous portion (A) and a fibrous portion (B) [in particular, a conjugated fiber (yarn) in which at least a part of portion (A) constitutes at least a part (especially all) of the fiber surface].

[0115] Examples of such fibers (composite fibers) include side-by-side fibers (yarns), core-sheath fibers (yarns), sea-island fibers (yarns), and split fibers.

[0116] Furthermore, the polyurethane fiber may or may not contain other parts other than parts (A) and (B) [parts that do not contain either the silver component or the zirconium component, for example, fibers that do not contain either the silver component or the zirconium component (polyurethane fiber)].

[0117] When such other parts are included, the proportion of these other parts in the polyurethane fiber may be, for example, 80% by mass or less (e.g., 70% by mass or less), preferably 60% by mass or less (e.g., 50% by mass or less), and more preferably 40% by mass or less (e.g., 30% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less), from the viewpoint of efficiently exhibiting antibacterial and deodorizing properties.

[0118] In polyurethane fibers, the ratio of part (A) to part (B) depends on the proportion of silver and zirconium components contained in each part, but for example, the ratio of part (A) to the total amount of part (A) and part (B) may be 0.01% by mass or more (for example, 0.05% by mass or more), preferably 0.1% by mass or more (for example, 0.3% by mass or more), and more preferably 0.5% by mass or more (for example, 0.8% by mass or more), and may also be 1% by mass or more (for example, 1.5% by mass or more, 2% by mass or more, 3% by mass or more, 4% by mass or more, 5% by mass or more, 6% by mass or more, 7% by mass or more, 8% by mass or more, 9% by mass or more, 10% by mass or more), etc.

[0119] In polyurethane fibers, the ratio of part (A) to the total amount of part (A) and part (B) (upper limit ratio) may be 99.99% by mass or less (for example, 99.95% by mass or less), preferably 99.5% by mass or less (for example, 99% by mass or less, 98% by mass or less, 97% by mass or less, 96% by mass or less), and even more preferably 95% by mass or less (for example, 94% by mass or less, 93% by mass or less, 92% by mass or less, 91% by mass or less), and 90% by mass or less (for example, 88% by mass or less). % or less, 85% by mass or less, 82% by mass or less, 80% by mass or less, 78% by mass or less, 75% by mass or less, 72% by mass or less, 70% by mass or less, 68% by mass or less, 65% by mass or less, 62% by mass or less, 60% by mass or less, 58% by mass or less, 55 mass% or less, 52 mass% or less, 50 mass% or less, less than 50 mass%, 48 mass% or less, 45 mass% or less, 42 mass% or less, 40 mass% or less, 38 mass% or less, 35 mass% or less, 32 mass% or less, 30 mass% or less).

[0120] In polyurethane fibers, the proportion of silver (element) (percentage in terms of elemental silver) can be selected from a range of approximately 0.0000001% by mass or more (e.g., 0.0000005% by mass or more), preferably 0.000001% by mass or more (e.g., 0.000005% by mass or more), more preferably 0.00001% by mass or more (e.g., 0.00005% by mass or more), and particularly 0.0001% by mass or more (e.g., 0.00012% by mass or more). It can also be 0.00015% by mass or more (for example, 0.00018% by mass or more, 0.0002% by mass or more, 0.00025% by mass or more, 0.0003% by mass or more, 0.0005% by mass or more, 0.0008% by mass or more, 0.001% by mass or more, 0.0012% by mass or more, 0.0015% by mass or more, 0.002% by mass or more, 0.003% by mass or more, 0.005% by mass or more, 0.008% by mass or more, 0.01% by mass or more), etc.

[0121] In polyurethane fibers, the proportion of silver (element) (upper limit of the proportion of silver element) can be selected from a range of, for example, 20% by mass or less (e.g., 15% by mass or less), preferably 10% by mass or less (e.g., 5% by mass or less), more preferably 3% by mass or less (e.g., 2% by mass or less), and particularly 1% by mass or less (e.g., 0.5% by mass or less), and can also be 0.3% by mass or less (e.g., 0.2% by mass or less, 0.15% by mass or less, 0.1% by mass or less, 0.08% by mass or less, 0.05% by mass or less, 0.03% by mass or less, 0.01% by mass or less), etc.

[0122] In polyurethane fibers, the proportion of silver component (silver source) can be selected from a range of approximately 0.00001% by mass or more (e.g., 0.00005% by mass or more), preferably 0.0001% by mass or more (e.g., 0.0005% by mass or more), more preferably 0.001% by mass or more (e.g., 0.002% by mass or more), and particularly 0.003% by mass or more (e.g., 0.004% by mass or more), and can also be 0.005% by mass or more (e.g., 0.008% by mass or more, 0.01% by mass or more, 0.012% by mass or more, 0.015% by mass or more, 0.02% by mass or more, 0.03% by mass or more, 0.05% by mass or more, 0.08% by mass or more, 0.1% by mass or more), etc.

[0123] In polyurethane fibers, the proportion of silver component (silver source) can be selected from a range of approximately 30% by mass or less (e.g., 25% by mass or less), preferably 20% by mass or less (e.g., 18% by mass or less), more preferably 15% by mass or less (e.g., 12% by mass or less), and particularly 10% by mass or less (e.g., 9% by mass or less), and can also be 8% by mass or less (e.g., 7.5% by mass or less, 7% by mass or less, 6.5% by mass or less, 6% by mass or less, 5.5% by mass or less, 5% by mass or less, 4.5% by mass or less, 4% by mass or less, 3.5% by mass or less, 3% by mass or less, 2.5% by mass or less, 2% by mass or less, 1.5% by mass or less, 1% by mass or less, 0.8% by mass or less, 0.5% by mass or less), etc.

[0124] In polyurethane fibers, the proportion of zirconium (element) (percentage in terms of elemental zirconium) is, for example, 0.0001% by mass or more (e.g., 0.0005% by mass or more), preferably 0.001% by mass or more (e.g., 0.005% by mass or more), more preferably 0.01% by mass or more (e.g., 0.05% by mass or more), and particularly 0.1% by mass or more (e.g., 0.12% by mass or more, 0.15% by mass or more, 0.2% by mass or more, 0.25% by mass or more). The amount can be selected from a range of approximately the above, and can also be 0.3 mass% or more (for example, 0.35 mass% or more, 0.4 mass% or more, 0.45 mass% or more, 0.5 mass% or more, 0.55 mass% or more, 0.6 mass% or more, 0.65 mass% or more, 0.7 mass% or more, 0.75 mass% or more, 0.8 mass% or more, 0.85 mass% or more, 0.9 mass% or more, 0.95 mass% or more, 1 mass% or more, 1.05 mass% or more, 1.1 mass% or more), etc.

[0125] In polyurethane fibers, the proportion of zirconium (element) (upper limit of the proportion of zirconium element) is not particularly limited, but it may be selected from a range that is not too high from the viewpoint of moldability and fiber quality, for example, 30% by mass or less (for example, 25% by mass or less), preferably 20% by mass or less (for example, 18% by mass or less), more preferably 15% by mass or less (for example, 12% by mass or less), and particularly 10% by mass or less (for example, 8% by mass or less, 7% by mass or less, 6% by mass or less), and it may also be 5% by mass or less (for example, 4.5% by mass or less, 4% by mass or less, 3.5% by mass or less, 3% by mass or less, 2.5% by mass or less, 2% by mass or less, 1.8% by mass or less, 1.5% by mass or less, 1.2% by mass or less, 1% by mass or less), etc.

[0126] In polyurethane fibers, the proportion of zirconium component (zirconium source) may be selected from a range of approximately 0.0001% by mass or more (e.g., 0.0005% by mass or more), preferably 0.001% by mass or more (e.g., 0.01% by mass or more), more preferably 0.03% by mass or more (e.g., 0.05% by mass or more), and particularly 0.1% by mass or more (e.g., 0.15% by mass or more, 0.2% by mass or more, 0.3% by mass or more, 0.4% by mass or more), and 0.5% by mass or more. (For example, it can be 0.6% by mass or more, 0.7% by mass or more, 0.8% by mass or more, 0.9% by mass or more, 1% by mass or more, 1.1% by mass or more, 1.2% by mass or more, 1.3% by mass or more, 1.4% by mass or more, 1.5% by mass or more, 1.6% by mass or more, 1.7% by mass or more, 1.8% by mass or more, 1.9% by mass or more, 2% by mass or more, 2.1% by mass or more, 2.2% by mass or more, 2.3% by mass or more, 2.4% by mass or more, 2.5% by mass or more, 2.8% by mass or more, 3% by mass or more), etc.

[0127] In polyurethane fibers, the proportion of zirconium (the upper limit of the proportion of zirconium) is not particularly limited, but it can be selected from a range that is not too large from the viewpoint of moldability and fiber quality, for example, 30% by mass or less (for example, 28% by mass or less), preferably 25% by mass or less (for example, 22% by mass or less), more preferably 20% by mass or less (for example, 18% by mass or less), and especially 16% by mass or less. It can also be 15% by mass or less (for example, 14% by mass or less, 13% by mass or less, 12% by mass or less, 11% by mass or less, 10% by mass or less, 9.5% by mass or less, 9% by mass or less, 8.5% by mass or less, 8% by mass or less, 7.5% by mass or less, 7% by mass or less, 6.5% by mass or less, 6% by mass or less, 5.5% by mass or less, 5% by mass or less, 4.5% by mass or less, 4% by mass or less, 3.5% by mass or less, 3% by mass or less).

[0128] In polyurethane fibers, the total proportion of silver component (silver source) and zirconium component (zirconium source) may be selected from a range of approximately 0.0001% by mass or more (e.g., 0.0005% by mass or more), preferably 0.001% by mass or more (e.g., 0.01% by mass or more), more preferably 0.03% by mass or more (e.g., 0.05% by mass or more), and particularly 0.1% by mass or more (e.g., 0.15% by mass or more, 0.2% by mass or more, 0.3% by mass or more, 0.4% by mass or more), and 0. It can also be 5% by mass or more (for example, 0.6% by mass or more, 0.7% by mass or more, 0.8% by mass or more, 0.9% by mass or more, 1% by mass or more, 1.1% by mass or more, 1.2% by mass or more, 1.3% by mass or more, 1.4% by mass or more, 1.5% by mass or more, 1.6% by mass or more, 1.7% by mass or more, 1.8% by mass or more, 1.9% by mass or more, 2% by mass or more, 2.1% by mass or more, 2.2% by mass or more, 2.3% by mass or more, 2.4% by mass or more, 2.5% by mass or more, 2.8% by mass or more, 3% by mass or more), etc.

[0129] In polyurethane fibers, the total ratio (upper limit of the ratio) of silver component (silver source) and zirconium component (zirconium source) is not particularly limited, but a ratio that is not too large from the viewpoint of moldability and fiber quality may be selected from a range such as 30% by mass or less (e.g., 28% by mass or less), preferably 25% by mass or less (e.g., 22% by mass or less), more preferably 20% by mass or less (e.g., 18% by mass or less), and especially 16% by mass or less. It can also be 15% by mass or less (e.g., 14% by mass or less, 13% by mass or less, 12% by mass or less, 11% by mass or less, 10% by mass or less, 9.5% by mass or less, 9% by mass or less, 8.5% by mass or less, 8% by mass or less, 7.5% by mass or less, 7% by mass or less, 6.5% by mass or less, 6% by mass or less, 5.5% by mass or less, 5% by mass or less, 4.5% by mass or less, 4% by mass or less, 3.5% by mass or less, 3% by mass or less).

[0130] In polyurethane fibers, the ratio of zirconium (element) to 1 part by mass of silver (element) (ratio in terms of metallic elements) is not particularly limited, but may be, for example, 100,000 parts by mass or less (e.g., 80,000 parts by mass or less, 60,000 parts by mass or less), preferably 50,000 parts by mass or less (e.g., 40,000 parts by mass or less, 35,000 parts by mass or less), and even more preferably 30,000 parts by mass or less (e.g., 25,000 parts by mass or less, 22,000 parts by mass or less), and may also be 20,000 parts by mass or less (e.g., 15,000 parts by mass or less, 12,000 parts by mass or less, 10,000 parts by mass or less, 8,000 parts by mass or less, 6,000 parts by mass or less, 5,000 parts by mass or less, 4,000 parts by mass or less, 3,000 parts by mass or less, 2,500 parts by mass or less, 2,000 parts by mass or less), etc.

[0131] In polyurethane fibers, the ratio of zirconium (element) to 1 part by mass of silver (element) (lower limit of the ratio) is not particularly limited, but may be, for example, 0.001 parts by mass or more (e.g., 0.005 parts by mass or more), preferably 0.01 parts by mass or more (e.g., 0.05 parts by mass or more), more preferably 0.1 parts by mass or more (e.g., 0.5 parts by mass or more), and particularly preferably 1 part by mass or more (e.g., more than 1 part by mass and 3 parts by mass or more), and may also be 5 parts by mass or more (e.g., 8 parts by mass or more, 10 parts by mass or more, 15 parts by mass or more, 20 parts by mass or more, 25 parts by mass or more, 30 parts by mass or more, 35 parts by mass or more, 40 parts by mass or more, 45 parts by mass or more, 50 parts by mass or more, 55 parts by mass or more, 60 parts by mass or more, 65 parts by mass or more, 70 parts by mass or more), etc.

[0132] In polyurethane fibers, the ratio (ratio in terms of metal elements) of at least one metal (element) M selected from Zn, Mg, Ca, Al, Ti, Cu, and Ag to 1 part by mass of zirconium (element) is not particularly limited, but may be 10,000 parts by mass or less (for example, 5,000 parts by mass or less), preferably 3,000 parts by mass or less (for example, 2,000 parts by mass or less), and more preferably 1,000 parts by mass or less (for example, 500 parts by mass or less), and may also be 100 parts by mass or less (for example, 50 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less, 10 parts by mass or less, 5 parts by mass or less, 3 parts by mass or less, 2 parts by mass or less, 1 part by mass or less, 0.5 parts by mass or less, 0.3 parts by mass or less, 0.2 parts by mass or less, 0.15 parts by mass or less, 0.1 parts by mass or less), etc.

[0133] When polyurethane fibers contain a resin (such as a cellulose-based resin), the proportion of the resin in the polyurethane fibers may be, for example, 30% by mass or less (e.g., 20% by mass or less, 15% by mass or less, 10% by mass or less, 8% by mass or less, 5% by mass or less), or 0.00001% by mass or more (e.g., 0.0001% by mass or more, 0.001% by mass or more, 0.01% by mass or more, 0.1% by mass or more).

[0134] [Manufacturing method, usage, etc.] Polyurethane fibers can be manufactured using known or conventional methods, depending on the form of part (A) and part (B).

[0135] For example, by applying a coating liquid corresponding to part (A) or part (B) to the polyurethane fiber, or by partially impregnating the polyurethane fiber with the coating liquid, spot-like parts (A) or parts (B) can be incorporated into the polyurethane fiber.

[0136] As mentioned above, parts (A) and (B) are typically fibrous. Polyurethane fibers containing such fibrous portions (A) and portions (B) can be manufactured, for example, by spinning (spinning separately) a spinning solution (A) corresponding to portion (A) and a spinning solution (B) corresponding to portion (B), and then integrating or converging them (bringing them together) (for example, by composite spinning).

[0137] The following describes some typical examples (examples using spinning solution). Spinning solution (A) can be obtained by mixing polyurethane, a silver component, and a solvent (with other components as needed). Spinning solution (B) can be obtained by mixing polyurethane, a zirconium component, and a solvent (with other components as needed).

[0138] Examples of solvents include organic solvents {e.g., amide solvents [e.g., linear aliphatic amides such as N,N-dimethylformamide (DMF) and N,N-dimethylacetamide (DMAc); cyclic aliphatic amides such as N-methyl-2-pyrrolidone (NMP) and N-vinylpyrrolidone], halogenated solvents (e.g., 1,1-difluorotetrachloroethane, dichloromethane, etc.), ether solvents (e.g., cyclic ethers such as 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran, etc.), ester solvents (e.g., Examples of solvents include fatty acid esters such as ethyl acetate, ketone solvents (e.g., chain ketones such as acetone and methyl ethyl ketone; cyclic ketones such as cyclohexanone), nitrile solvents (e.g., acetonitrile), sulfur solvents (e.g., sulfone solvents such as diethyl sulfone; sulfoxide solvents such as dimethyl sulfoxide (DMSO)), alcohol solvents (e.g., alkanols such as methanol, ethanol, and isopropanol), amine oxide solvents (e.g., N-methylmorpholine N-oxide), water, etc.

[0139] The solvents may be used individually or in combination of two or more types.

[0140] The polyurethane and the silver or zirconium component may be mixed in the solvent all at once, or they may be mixed in stages.

[0141] For example, after preparing a liquid (solution, polyurethane-containing liquid) containing polyurethane (polyurethane obtained by polymerization) and a solvent, a silver component or a zirconium component may be added (mixed) to the liquid. The method for preparing the liquid containing polyurethane and solvent is not particularly limited, and conventional methods can be applied. The polyurethane, which is the solute in the solution, can be produced by either melt polymerization or solution polymerization, or by other methods. However, solution polymerization is more preferable. In the case of solution polymerization, less foreign matter such as gel is generated in the polyurethane, making it easier to spin. Also, naturally, solution polymerization has the advantage of eliminating the step of preparing the solution. Examples of polyurethanes include those mentioned above (for example, those synthesized using PTMG with a molecular weight of 1500 to 6000 as a polymer diol, MDI as a diisocyanate, and at least one of ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, and hexamethylenediamine as a chain extender).

[0142] Polyurethane can be obtained, for example, by synthesizing it using the above-mentioned raw materials (raw materials corresponding to polyurethane) in a solvent (e.g., DMAc, DMF, DMSO, NMP, etc., or solvents mainly composed of these). For example, the so-called one-shot method, in which each raw material is added to such a solvent, dissolved, and heated to an appropriate temperature to react and produce polyurethane, or a method in which a polymer diol and a diisocyanate are first melted, and then the reactant is dissolved in a solvent and reacted with the aforementioned chain extender to produce polyurethane, can be employed as particularly preferred methods.

[0143] When using a diol as a chain extender, it is preferable to adjust the high-temperature melting point of the polyurethane to a range of 200°C to 260°C from the viewpoint of obtaining a material with excellent heat resistance. Typical methods for achieving this can be achieved by controlling the type and ratio of polymer diol, MDI, and diol. When the molecular weight of the polymer diol is low, a polyurethane with a high high-temperature melting point can be obtained by relatively increasing the proportion of MDI. Similarly, when the molecular weight of the diol is low, a polyurethane with a high high-temperature melting point can be obtained by relatively decreasing the proportion of polymer diol.

[0144] Furthermore, it is preferable that one or more catalysts, such as amine-based catalysts or organometallic catalysts, be used in the synthesis of such polyurethanes.

[0145] The polyurethane concentration in the polyurethane-containing liquid obtained in this way is usually preferably in the range of 30% by mass or more and 80% by mass or less.

[0146] In the aforementioned method, silver components, zirconium components (and other components) are added to the polyurethane-containing liquid. Any method can be used to add the silver and zirconium components. Typical methods include using a static mixer, stirring, homomixer, and a twin-screw extruder.

[0147] Silver and zirconium components may be added as solvent-containing solutions (silver-containing solution, zirconium-containing solution).

[0148] There are no particular limitations on the method for obtaining a silver component-containing solution (silver component dispersion) or a zirconium component-containing solution (zirconium component dispersion), but the silver component or zirconium component may be obtained by mechanically grinding them as a wetted system to which the same solvent used in the polyurethane-containing solution (or spinning solution) is added [or further added to the polyurethane-containing solution (or spinning solution)].

[0149] For mechanical pulverization in a wet system, dispersion treatment using a ball mill is particularly preferred. This treatment can finely pulverize silver and zirconium components.

[0150] Furthermore, to prevent secondary aggregation when mixing silver and zirconium components into the polyurethane-containing solution (or spinning solution), it is preferable to pre-contain resin components (e.g., cellulose acetate butyrate, polystyrene, etc., as exemplified above) or polyurethane (e.g., the polyurethane as exemplified above) in the silver-containing solution (silver component dispersion) or zirconium-containing solution (zirconium component dispersion). Note that the polyurethane may be the same as the polyurethane contained in the polyurethane fiber [part (A) and / or part (B)], or it may be a different polyurethane. Also, when adding silver and zirconium components to the polyurethane-containing solution (or spinning solution), the aforementioned agents, such as lightfasteners and antioxidants, may be added at the same time.

[0151] Polyurethane fibers can be obtained by compound spinning (winding up as a composite fiber) the spinning solutions (each spinning solution) configured as described above. Examples of spinning methods include dry spinning, wet spinning, and melt spinning. Among these, dry spinning is preferred from the viewpoint of being able to stably spin fibers of all finenesses, from fine to thick.

[0152] The fineness and cross-sectional shape of the polyurethane fiber (yarn) are not particularly limited. For example, the cross-sectional shape of the yarn may be circular or flat.

[0153] Furthermore, there are no particular limitations regarding the dry spinning method, etc., and spinning should be performed by appropriately selecting spinning conditions that match the desired characteristics and spinning equipment.

[0154] For example, the permanent strain rate and stress relaxation of polyurethane fibers (elastic yarn) are particularly susceptible to the influence of the speed ratio between the Godet roller and the winding machine, so these may be appropriately determined depending on the intended use of the yarn. For instance, the speed ratio between the Godet roller and the winding machine may be set to a range of 1.10 to 1.65 for winding.

[0155] Furthermore, the spinning speed is preferably 250 m / min or more, from the viewpoint of improving the strength of the resulting polyurethane fibers (elastic yarn).

[0156] Polyurethane fibers (elastic fibers, yarns, elastic yarns) can be used as is or molded (as molded products).

[0157] Typically, polyurethane fibers may be used in the form of fabrics containing polyurethane fibers (e.g., woven fabrics, knitted fabrics, nonwoven fabrics). Furthermore, molded articles may contain other components (materials) as appropriate, depending on their form and other factors.

[0158] The molded articles (for example, molded articles containing at least a fabric containing polyurethane fibers) are not particularly limited, but include, for example, clothing [or garments, such as underwear, outerwear, bottoms, lingerie, socks, swimwear, etc.] and sanitary materials [for example, diapers (disposable diapers), bandages, etc.]. [Examples]

[0159] The present invention will be described in more detail below with reference to examples, but the present invention is not limited in any way by these examples.

[0160] The measurement (evaluation) methods and preparation methods for each characteristic (physical property) are shown below.

[0161] [Evaluation 1] Spinning properties Spinning was performed continuously for 48 hours, and the number of yarn breaks during that time was used as an indicator for determining spinnability. Specifically, during 48 hours of continuous spinning, a score of less than 4 yarn breaks was given as ○, and a score of 4 or more yarn breaks was given as ×.

[0162] [Evaluation 2] 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 October 1, 2024), the deodorizing properties of the following odor components were measured. The Japan Textile Evaluation Technology Council's passing standard for determining "deodorizing effect" based on the reduction rate of each odor component measured is 70% or higher. 1. A sample (0.15g of polyurethane elastic yarn) was placed in a Tedlar bag. 2. 3 liters of dry air containing 100 ppm ammonia were injected, the container was sealed, and left to stand for 2 hours. 3. The residual gas concentration (ppm) after standing for 3.2 hours was measured using a component-specific detector tube (manufactured by Gastec Co., Ltd.). 4. The same measurement was performed without using a sample to determine the blank measurement. 5. Measurements were taken three times, and the average value was used to calculate the rate of decrease in residual gas concentration according to the following formula. The percentage decrease in residual gas concentration is calculated as follows: ((Blank concentration - Measured concentration of each sample) / Blank concentration) × 100

[0163] [Laundry process] In accordance with the standard washing method described in the Washing Instructions for SEK Mark Textile Products (established by: Japan Textile Evaluation Technology Council, Product Certification Department, revised on April 1, 2022), a household electric washing machine as specified in Washing Instruction 103 of JIS L 0217: 1995 "Marking Symbols and Methods for Displaying Textile Products" was used. A washing solution was prepared by adding 40 mL of JAFET standard blended detergent (containing polyoxyethylene alkyl ether and alpha-olefin sulfonate sodium) to 30 L of 40°C water. The sample and, if necessary, the load fabric were added to the bath to achieve a bath ratio of 1:30. The washing process consisted of washing for 5 minutes, spinning, rinsing for 2 minutes, spinning, rinsing for 2 minutes, and spinning once.

[0164] [Rating 3] Deodorizing properties after washing After winding the polyurethane fibers (yarn), a sample of the yarn that had not undergone any ammonia gas deodorization test or washing treatment was used, and the washing treatment was repeated 10 times. The polyurethane fibers (yarn) after 10 washing treatments were air-dried for 24 hours and used as a measurement sample, and the reduction rate was calculated according to the evaluation of ammonia gas deodorization performance in [Evaluation 2] above, and this was used as an index for determining ammonia gas deodorization performance. Specifically, a reduction rate of 70% or more of odor components was judged as ○, and a reduction rate of less than 70% was judged as ×.

[0165] [Rating 4] Deodorizing properties after repeated washing The procedure described in items 1 and 2 of the [Evaluation 2] Deodorizing Performance evaluation above involved exposing the sample to ammonia gas, adsorbing the gas, performing the washing treatment, and then air-drying the sample at room temperature for 4 hours. This constituted one cycle of the adsorption-washing treatment. The adsorption-washing process was performed 11 times. The residual gas concentration (ppm) in the dry air after ammonia gas exposure for the samples from the 5th and 11th cycles was measured using component-specific detector tubes (manufactured by Gastec Co., Ltd.) according to items 3 to 5 of the [Evaluation 2] Deodorizing Performance evaluation, and the reduction rate for each cycle was determined. The 11th cycle sample was one that had undergone 10 washes after ammonia gas adsorption. The reduction rate, determined in the same manner as in the [Evaluation 2] Deodorizing Performance evaluation, was used as an indicator of ammonia gas deodorization performance through repeated washing. Specifically, a reduction rate of 70% or more of odor components was judged as ○, and a reduction rate of less than 70% was judged as ×.

[0166] [Rating 5] Deodorizing effect retention rate The ammonia gas deodorization retention rate was calculated according to the following formula, with the reduction rate obtained in the evaluation of gas deodorization performance in [Evaluation 2] above being defined as deodorization rate A, and the reduction rate obtained in the evaluation of ammonia gas deodorization performance by repeated washing in [Evaluation 4] above being defined as deodorization rate B. Ammonia gas deodorization retention rate = (Deodorization rate B / Deodorization rate A) × 100

[0167] [Creation of tubular knitted fabric for antibacterial evaluation] Polyurethane fibers (elastic fibers) were knitted in a 29-gauge single-hole tubular knitting machine (equipped with a rotary feed device for polyurethane elastic fibers) at 50% stretch to create a tubular knitted fabric made of 100% polyurethane fibers. The front and back selvages of the sample were knitted by joining a small amount of nylon filament (78 decitex 24 filament) manufactured by Toray Industries, Inc. to prevent fraying. Next, the created tubular knitted fabric was subjected to dry heat setting at 190°C for 60 seconds without stretching. Subsequently, the tubular knitted fabric was scouring using 0.1% by weight of a scouring agent (Nikka Chemical Co., Ltd. "Sunmall" (registered trademark) WX24) at a bath ratio of 1:20, 80°C, and 20 minutes to remove raw yarn oils and other contaminants.

[0168] [Rating 6] Antibacterial properties after washing As described above, the tubular knitted fabric prepared for evaluation was used as the antibacterial treated sample in the antibacterial test, and the antibacterial test was conducted in accordance with the antibacterial test procedure specified by the Japan Textile Evaluation Technology Council (JIS L1902:2015, bacterial liquid absorption method). Antibacterial activity was evaluated using the antibacterial activity value calculated by the following formula. A higher antibacterial activity value indicates superior antibacterial properties. Staphylococcus aureus (NBRC 12732) was used as the test bacterium. Antimicrobial activity value = (logCt - logC0) - (logTt - logT0) = FG F: Growth value of the target fabric (F = logCt - logC0) G: Growth value of antimicrobially treated sample (G = logTt - logT0) logCt: Common logarithm of the number of viable bacteria in the control cloth after 18 hours of incubation. logC0: Common logarithm of the number of viable bacteria in the target fabric immediately after vaccination. logTt: Common logarithm of the number of viable bacteria in an antimicrobially treated sample after 18 hours of incubation. logT0: Common logarithm of the number of viable bacteria in an antimicrobially treated sample immediately after inoculation. However, if logC0 > logT0 is satisfied, the antibacterial activity value is calculated by substituting logT0 with logC0. In addition, for this evaluation, the evaluation tubular knit fabric after 10 washes was used as the sample, and measurements were all performed with n=3, and the average of these n values ​​is expressed. The antibacterial activity value was used as an indicator of antibacterial activity against Staphylococcus aureus. That is, an antibacterial activity value of 4 or higher was judged as ○, and a value less than 4 was judged as ×.

[0169] [Quantitative determination of metallic elements] The sample was weighed into a Teflon® beaker and decomposed with sulfuric acid, nitric acid, perchloric acid, and hydrofluoric acid, and concentrated until sulfuric acid fumes were produced. This solution was dissolved in dilute nitric acid to a fixed volume, and quantitative analysis of metal elements in the fixed volume solution was performed by ICP emission spectrometry (measurement instrument: PerkinElmer Optima4300DV).

[0170] [Median diameter] The particle size distribution was determined in the dispersion using a Microtrac particle size analyzer (Nikkiso Co., Ltd., UPA150, MODEL No. 9340, dynamic light scattering method). The refractive index of the resin used for particle size calculation was set to 1.50.

[0171] [Molecular weight] The molecular weight (number-average molecular weight) was measured by GPC under the following conditions. Columns: SHODEX KF-806M (2 pieces) manufactured by Showa Denko Corporation Solvent: N,N-dimethylacetamide (DMAc) 1 ml / min Temperature: 40℃ Detector: Differential refractometer (RI detector) Standard material: Polystyrene

[0172] [Preparation of spinning solution (stock solution for spinning)] First, polymer solutions (A1) to (A3) were prepared as follows.

[0173] (Polymer solution (A1)) A dimethylacetamide (DMAc) solution (35% by mass) of a polyurethane urea polymer consisting of PTMG, MDI, ethylenediamine, and diethylamine as a chelating agent, with a molecular weight of 1800, was prepared. Next, as an antioxidant, a polyurethane solution produced by the reaction of t-butyldiethanolamine and methylene-bis-(4-cyclohexyl isocyanate) (DuPont's "Metachlor"® 2462) and a condensation polymer of p-cresol and divinylbenzene (DuPont's "Metachlor"® 2390) were mixed in a 2:1 (mass ratio) to prepare an antioxidant DMAc solution (concentration 35% by mass). 96 parts by mass of the DMAc solution of the polyurethane urea polymer and 4 parts by mass of the antioxidant solution were mixed to obtain polymer solution (A1).

[0174] (Polymer solution (A2)) A dimethylacetamide (DMAc) solution (35% by mass) of a polyurethane urea polymer consisting of 3-methyl-PTMG, MDI, ethylenediamine, and diethylamine as a chelating agent, with a molecular weight of 3500, was prepared. 96 parts by mass of this polyurethane urea polymer DMAc solution and 4 parts by mass of the aforementioned antioxidant DMAc solution (35% by mass) were mixed to obtain polymer solution (A2).

[0175] (Polymer solution (A3)) A dimethylacetamide (DMAc) solution (35% by mass) of a polyurethane urea polymer consisting of PTMG with a molecular weight of 1800, MDI, ethylenediamine, and diethylamine as a chelating agent was prepared and designated as polymer solution (A3).

[0176] The molecular weights (number-average molecular weights) of the polyurethane urea polymers were 21,000, 41,000, 62,000, and 84,000, among others.

[0177] Next, dispersions (B1) to (B4) were prepared.

[0178] (Dispersion (B1)) As the silver component (Ag source), silver-supported zirconium phosphate (Novaron®, registered trademark, grade: AG300, manufactured by Toagosei Co., Ltd.) was dispersed in DMAc using a homomixer. Cellulose acetate butyrate (CAB) was then dissolved as the resin component, and the mixture was mechanically ground using a horizontal mill to obtain dispersion (B1) (35% by mass of silver-supported zirconium phosphate, median diameter 0.58 μm, CAB 17.5% by mass).

[0179] (Dispersion (B2)) As the silver component (Ag source), silver-containing borosilicate glass (Ishizuka Glass Co., Ltd.'s "Ion Pure" (registered trademark)) was dispersed in DMAc using a homomixer. Cellulose acetate butyrate (CAB) was then dissolved as the resin component, and the mixture was mechanically ground using a horizontal mill to obtain dispersion (B2) (35% by mass of silver-containing borosilicate glass, median diameter 0.60 μm, CAB 17.5% by mass).

[0180] (Dispersion (B3)) As the silver component (Ag source), silver-containing zeolite (Zeomic®, manufactured by Sinanen Zeomic Co., Ltd., grade: AW10N) was dispersed in DMAc using a homomixer. Cellulose acetate butyrate (CAB) was then dissolved as the resin component, and the mixture was mechanically ground using a horizontal mill to obtain dispersion (B3) (35% by mass of silver-containing zeolite, median diameter 0.55 μm, 17.5% by mass of CAB).

[0181] (Dispersion (B4)) As the silver component (Ag source), silver-supported zirconium phosphate (Novaron®, registered trademark, grade: AG300, manufactured by Toagosei Co., Ltd.) was dispersed in DMAc using a homomixer, then a polymer solution (A3) was added, and a horizontal mill was used for mechanical grinding to obtain a dispersion (B4) (35% by mass of silver-supported zirconium phosphate, median diameter 0.59 μm, 17.5% by mass of polyurethane urea polymer).

[0182] Next, dispersions (C1) and (C2) were prepared.

[0183] (Dispersion (C1)) As the zirconium component (Zr source), zirconium phosphate (Toagosei Co., Ltd., "Kesmon" (registered trademark), grade: NS-10) was dispersed in DMAc using a homomixer. CAB was then dissolved as a resin component, and a horizontal mill was used for mechanical grinding to obtain dispersion (C1) (35% by mass of zirconium phosphate, median diameter 0.56 μm, 17.5% by mass of CAB).

[0184] (Dispersion (C2)) As the zirconium component (Zr source), zirconium phosphate (Toagosei Co., Ltd., "Kesmon" (registered trademark), grade: NS-10) was dispersed in DMAc using a homomixer, then a polymer solution (A3) was added, and a horizontal mill was used for mechanical grinding to obtain dispersion (C2) (35% by mass of zirconium phosphate, median diameter 0.56 μm, 17.5% by mass of polyurethane urea polymer).

[0185] Spinning solutions D1 to D11 were prepared by mixing A1 to A3 and B1 to B4 in the combinations and ratios shown in Table 1 below.

[0186] [Table 1]

[0187] Furthermore, spinning solutions E1 to E7 were prepared by mixing A1, C1, and C2 in the combinations and ratios shown in Table 2 below.

[0188] [Table 2]

[0189] [Example 1] Liquid was supplied to a distribution plate so that D1 was placed in the sheath portion of the polyurethane fiber and E1 in the core portion. The liquid was measured in a ratio of 2 parts by mass of D1 and 98 parts by mass of E1 and discharged from the die hole. This was dry-spun at a spinning speed of 600 m / min with a speed ratio of 1.25 between the Gode roller and the winding machine, and wound up to obtain a wound yarn of polyurethane fiber (elastic fiber) having a core-sheath structure (a structure in which the fibrous portion (B) is the core and the fibrous portion (A) is the sheath) with 44 dtex and 4 filaments. Tables 3 and 4 show a list of the composition and properties of the obtained polyurethane fibers.

[0190] In Table 3, Ag refers to silver (element), Ag source refers to the silver component (silver source), Zr refers to zirconium (element), Zr source refers to the zirconium component (zirconium source), and M refers to a metal (element) selected from Zn (zinc), Mg (magnesium), Ca (calcium), Al (aluminum), Ti (titanium), Cu (copper), and Ag (silver).

[0191] [Example 2] Liquid was supplied to a distribution plate so that D5 was placed in the sheath portion of the polyurethane fiber and E2 in the core portion. D5 was measured in a ratio of 10 parts by mass and E2 in a ratio of 90 parts by mass and discharged from the die hole. This was dry-spun at a spinning speed of 600 m / min with a speed ratio of 1.25 between the Gode roller and the winding machine, and wound up to obtain a wound polyurethane fiber with a core-sheath structure (a structure in which the fibrous portion (B) is the core and the fibrous portion (A) is the sheath) of 44 dtex and 4 filaments. Tables 3 and 4 show a list of the composition and properties of the obtained polyurethane fibers.

[0192] [Example 3] Liquid was supplied to a distribution plate so that D5 was placed in the sheath portion of the polyurethane fiber and E1 in the core portion. D5 was measured in a ratio of 2 parts by mass and E1 in a ratio of 98 parts by mass and extruded from the die hole. This was dry-spun at a spinning speed of 600 m / min with a speed ratio of 1.25 between the Gode roller and the winding machine, and then wound up to obtain a wound polyurethane fiber with a core-sheath structure (a structure in which the fibrous portion (B) is the core and the fibrous portion (A) is the sheath) of 44 dtex and 4 filaments. Tables 3 and 4 show a list of the composition and properties of the obtained polyurethane fibers.

[0193] [Example 4] Liquid was supplied to a distribution plate so that D1 was placed in the sheath portion of the polyurethane fiber and E5 in the core portion. The liquid was measured in a ratio of 2 parts by mass of D1 and 98 parts by mass of E5 and discharged from the die hole. This was dry-spun at a spinning speed of 600 m / min with a speed ratio of 1.25 between the Gode roller and the winding machine, and then wound up to obtain a wound polyurethane fiber with a core-sheath structure (a structure in which the fibrous portion (B) is the core and the fibrous portion (A) is the sheath) of 44 dtex and 4 filaments. Tables 3 and 4 show a list of the composition and properties of the obtained polyurethane fibers.

[0194] [Example 5] Liquid was supplied to a distribution plate so that D3 was placed in the sheath portion of the polyurethane fiber and E3 in the core portion. D3 was measured in a ratio of 10 parts by mass to E3 in a ratio of 90 parts by mass and discharged from the die hole. This was dry-spun at a spinning speed of 600 m / min with a speed ratio of 1.25 between the Gode roller and the winding machine, and then wound up to obtain a wound polyurethane fiber with a core-sheath structure (a structure in which the fibrous portion (B) is the core and the fibrous portion (A) is the sheath) of 44 dtex and 4 filaments. Tables 3 and 4 show a list of the composition and properties of the obtained polyurethane fibers.

[0195] [Example 6] A liquid was supplied to a distribution plate so that D3 was placed in the sheath portion of the polyurethane fiber and E5 in the core portion. D3 and E5 were measured in a ratio of 10 parts by mass and 90 parts by mass, and discharged from the die hole. This was dry-spun at a spinning speed of 600 m / min with a speed ratio of 1.25 between the Gode roller and the winding machine, and wound up to obtain a wound body of polyurethane fiber having a core-sheath structure with 44 dtex and 4 filaments. The composition and properties of the obtained polyurethane fiber are shown in Tables 3 and 4.

[0196] [Example 7] Liquid was supplied to a distribution plate so that D3 was placed in the sheath portion of the polyurethane fiber and E1 in the core portion. D3 was measured in a ratio of 10 parts by mass and E1 in a ratio of 90 parts by mass and extruded from the die hole. This was dry-spun at a spinning speed of 600 m / min with a speed ratio of 1.25 between the Gode roller and the winding machine, and then wound up to obtain a wound polyurethane fiber with a core-sheath structure (a structure in which the fibrous portion (B) is the core and the fibrous portion (A) is the sheath) of 44 dtex and 4 filaments. Tables 3 and 4 show a list of the composition and properties of the obtained polyurethane fibers.

[0197] [Example 8] Liquid was supplied to a distribution plate so that D5 was placed in the sheath portion of the polyurethane fiber and E1 in the core portion. D5 was measured in a ratio of 10 parts by mass and E1 in a ratio of 90 parts by mass and discharged from the die hole. This was dry-spun at a spinning speed of 600 m / min with a speed ratio of 1.25 between the Gode roller and the winding machine, and wound up to obtain a wound polyurethane fiber with a core-sheath structure (a structure in which the fibrous portion (B) is the core and the fibrous portion (A) is the sheath) of 44 dtex and 4 filaments. Tables 3 and 4 show a list of the composition and properties of the obtained polyurethane fibers.

[0198] [Example 9] A liquid was supplied to a distribution plate so that D6 was placed in the sheath portion of the polyurethane fiber and E3 in the core portion. D6 was measured in a ratio of 10 parts by mass to E3 in a ratio of 90 parts by mass and extruded from the die hole. This was dry-spun at a spinning speed of 600 m / min with a speed ratio of 1.25 between the Gode roller and the winding machine, and wound up to obtain a wound body of polyurethane fiber having a core-sheath structure with 44 dtex and 4 filaments. The composition and properties of the obtained polyurethane fibers are shown in Tables 3 and 4.

[0199] [Example 10] Liquid was supplied to a distribution plate so that D5 was placed in the sheath portion of the polyurethane fiber and E5 in the core portion. D5 was measured in a ratio of 10 parts by mass to E5 in a ratio of 90 parts by mass and discharged from the die hole. This was dry-spun at a spinning speed of 600 m / min with a speed ratio of 1.25 between the Gode roller and the winding machine, and wound up to obtain a wound polyurethane fiber with a core-sheath structure (a structure in which the fibrous portion (B) is the core and the fibrous portion (A) is the sheath) of 44 dtex and 4 filaments. Tables 3 and 4 show a list of the composition and properties of the obtained polyurethane fibers.

[0200] [Example 11] Liquid was supplied to a distribution plate so that D4 was placed in the sheath portion of the polyurethane fiber and E2 in the core portion. D4 was measured in a ratio of 20 parts by mass and E2 in a ratio of 80 parts by mass and discharged from the die hole. This was dry-spun at a spinning speed of 600 m / min with a speed ratio of 1.25 between the Gode roller and the winding machine, and wound up to obtain a wound polyurethane fiber with a core-sheath structure (a structure in which the fibrous portion (B) is the core and the fibrous portion (A) is the sheath) of 44 dtex and 4 filaments. Tables 3 and 4 show a list of the composition and properties of the obtained polyurethane fibers.

[0201] [Example 12] Liquid was supplied to a distribution plate so that D1 was placed in the sheath portion of the polyurethane fiber and E1 in the core portion. D1 was measured in a ratio of 20 parts by mass and E1 in a ratio of 80 parts by mass and discharged from the die hole. This was dry-spun at a spinning speed of 600 m / min with a speed ratio of 1.25 between the Gode roller and the winding machine, and then wound up to obtain a wound polyurethane fiber with a core-sheath structure (a structure in which the fibrous portion (B) is the core and the fibrous portion (A) is the sheath) of 44 dtex and 4 filaments. Tables 3 and 4 show a list of the composition and properties of the obtained polyurethane fibers.

[0202] [Example 13] Liquid was supplied to a distribution plate so that D5 was placed in the sheath portion of the polyurethane fiber and E2 in the core portion. D5 was measured in a ratio of 20 parts by mass and E2 in a ratio of 80 parts by mass and discharged from the die hole. This was dry-spun at a spinning speed of 600 m / min with a speed ratio of 1.25 between the Godet roller and the winding machine, and wound up to obtain a wound polyurethane fiber with a core-sheath structure of 44 dtex and 4 filaments. Tables 3 and 4 show a list of the composition and properties of the obtained polyurethane fibers.

[0203] [Example 14] Liquid was supplied to a distribution plate so that D4 was placed in the sheath portion of the polyurethane fiber and E5 in the core portion. D4 was measured in a ratio of 20 parts by mass and E5 in a ratio of 80 parts by mass and discharged from the die hole. This was dry-spun at a spinning speed of 600 m / min with a speed ratio of 1.25 between the Gode roller and the winding machine, and then wound up to obtain a wound polyurethane fiber with a core-sheath structure (a structure in which the fibrous portion (B) is the core and the fibrous portion (A) is the sheath) of 44 dtex and 4 filaments. Tables 3 and 4 show a list of the composition and properties of the obtained polyurethane fibers.

[0204] [Example 15] Liquid was supplied to a distribution plate so that D1 was placed in the sheath portion of the polyurethane fiber and E3 in the core portion. D1 was measured in a ratio of 20 parts by mass and E3 in a ratio of 80 parts by mass and discharged from the die hole. This was dry-spun at a spinning speed of 600 m / min with a speed ratio of 1.25 between the Gode roller and the winding machine, and then wound up to obtain a wound polyurethane fiber with a core-sheath structure (a structure in which the fibrous portion (B) is the core and the fibrous portion (A) is the sheath) of 44 dtex and 4 filaments. Tables 3 and 4 show a list of the composition and properties of the obtained polyurethane fibers.

[0205] [Example 16] Liquid was supplied to a distribution plate so that D5 was placed in the sheath portion of the polyurethane fiber and E3 in the core portion. D5 was measured in a ratio of 20 parts by mass and E3 in a ratio of 80 parts by mass and discharged from the die hole. This was dry-spun at a spinning speed of 600 m / min with a speed ratio of 1.25 between the Gode roller and the winding machine, and wound up to obtain a wound polyurethane fiber with a core-sheath structure (a structure in which the fibrous portion (B) is the core and the fibrous portion (A) is the sheath) of 44 dtex and 4 filaments. Tables 3 and 4 show a list of the composition and properties of the obtained polyurethane elastic fibers.

[0206] [Example 17] D1 was weighed out in a ratio of 25 parts by mass to E5 in a ratio of 75 parts by mass. The mixture was then distributed so that D1 was 11 dtex and 1 filament, and E5 was 33 dtex and 3 filaments. After being extruded from the die hole and converged, the mixture was dry-spun at a spinning speed of 600 m / min with a speed ratio of 1.25 between the Gode roller and the winding machine, and then wound up to obtain a wound polyurethane fiber with a side-by-side (SBS) structure of 44 dtex and 4 filaments, with D1 and E5 arranged in the longitudinal direction of the fiber. Tables 3 and 4 show a list of the composition and properties of the obtained polyurethane fibers.

[0207] [Example 18] D1 and E5 were weighed out in a ratio of 50 parts by mass and 50 parts by mass, and the mixture was distributed so that D1 was 22 dtex and 2 filaments, and E5 was 22 dtex and 2 filaments. After being extruded from the die hole and converged, the mixture was dry-spun at a spinning speed of 600 m / min with a speed ratio of 1.25 between the Gode roller and the winding machine, and then wound up to obtain a wound polyurethane fiber having a side-by-side (SBS) structure with D1 and E5 arranged in the longitudinal direction of the fiber, resulting in 44 dtex and 4 filaments. Tables 3 and 4 show a list of the composition and properties of the obtained polyurethane fibers.

[0208] [Example 19] D1 was weighed out in a ratio of 75 parts by mass to E5 in a ratio of 25 parts by mass. The mixture was then distributed so that D1 was 33 dtex and 3 filaments, and E5 was 11 dtex and 1 filament. After being extruded from the die hole and converged, the mixture was dry-spun at a spinning speed of 600 m / min with a speed ratio of 1.25 between the Gode roller and the winding machine, and then wound up to obtain a wound polyurethane fiber with a side-by-side (SBS) structure of 44 dtex and 4 filaments, with D1 and E5 arranged in the longitudinal direction of the fiber. Tables 3 and 4 show a list of the composition and properties of the obtained polyurethane fibers.

[0209] [Example 20] Liquid was supplied to a distribution plate so that D7 was placed in the sheath portion of the polyurethane fiber and E3 in the core portion. D7 was measured in a ratio of 10 parts by mass and E3 in a ratio of 90 parts by mass and discharged from the die hole. This was dry-spun at a spinning speed of 600 m / min with a speed ratio of 1.25 between the Gode roller and the winding machine, and then wound up to obtain a wound polyurethane fiber with a core-sheath structure (a structure in which the fibrous portion (B) is the core and the fibrous portion (A) is the sheath) of 44 dtex and 4 filaments. Tables 3 and 4 show a list of the composition and properties of the obtained polyurethane elastic fibers.

[0210] [Example 21] Liquid was supplied to a distribution plate so that D8 was placed in the sheath portion of the polyurethane fiber and E3 in the core portion. D8 was measured in a ratio of 10 parts by mass and E3 in a ratio of 90 parts by mass and extruded from the die hole. This was dry-spun at a spinning speed of 600 m / min with a speed ratio of 1.25 between the Gode roller and the winding machine, and then wound up to obtain a wound polyurethane fiber with a core-sheath structure (a structure in which the fibrous portion (B) is the core and the fibrous portion (A) is the sheath) of 44 dtex and 4 filaments. Tables 3 and 4 show a list of the composition and properties of the obtained polyurethane elastic fibers.

[0211] [Example 22] D9 and E3 were weighed out in a ratio of 50 parts by mass and 50 parts by mass, and the mixture was distributed so that D9 was 22 dtex and 2 filaments, and E3 was 22 dtex and 2 filaments. After being extruded from the die hole and converged, the mixture was dry-spun at a spinning speed of 600 m / min with a speed ratio of 1.25 between the Gode roller and the winding machine, and then wound up to obtain a wound polyurethane fiber having a side-by-side (SBS) structure with D9 and E3 arranged in the longitudinal direction of the fiber, resulting in 44 dtex and 4 filaments. Tables 3 and 4 show a list of the composition and properties of the obtained polyurethane fibers.

[0212] [Example 23] D3 was weighed out in a ratio of 25 parts by mass and E7 in a ratio of 75 parts by mass. The mixture was then distributed so that D3 was 11 dtex and 1 filament, and E7 was 33 dtex and 3 filaments. After being extruded from the die hole and converged, the mixture was dry-spun at a spinning speed of 600 m / min with a speed ratio of 1.25 between the Gode roller and the winding machine, and then wound up to obtain a wound polyurethane fiber with a side-by-side (SBS) structure of 44 dtex and 4 filaments, with D3 and E7 arranged in the longitudinal direction of the fiber. Tables 3 and 4 show a list of the composition and properties of the obtained polyurethane fibers.

[0213] [Example 24] Liquid was supplied to a distribution plate so that D9 was placed in the sheath portion of the polyurethane fiber and E7 in the core portion. The liquid was measured in a ratio of 20 parts by mass of D9 and 80 parts by mass of E7 and discharged from the die hole. This was dry-spun at a spinning speed of 600 m / min with a speed ratio of 1.25 between the Gode roller and the winding machine, and then wound up to obtain a wound polyurethane fiber with a core-sheath structure (a structure in which the fibrous portion (B) is the core and the fibrous portion (A) is the sheath) of 44 dtex and 4 filaments. Tables 3 and 4 show a list of the composition and properties of the obtained polyurethane elastic fibers.

[0214] [Example 25] Liquid was supplied to a distribution plate so that D10 was placed in the sheath portion of the polyurethane fiber and E1 in the core portion. D10 was measured in a ratio of 10 parts by mass and E1 in a ratio of 90 parts by mass and discharged from the die hole. This was dry-spun at a spinning speed of 600 m / min with a speed ratio of 1.25 between the Gode roller and the winding machine, and then wound up to obtain a wound polyurethane fiber yarn with a core-sheath structure (a structure in which the fibrous portion (B) is the core and the fibrous portion (A) is the sheath) of 44 dtex and 4 filaments. Tables 3 and 4 show a list of the composition and properties of the obtained polyurethane elastic fibers.

[0215] [Example 26] Liquid was supplied to a distribution plate so that D11 was placed in the sheath portion of the polyurethane fiber and E1 in the core portion. D11 was measured in a ratio of 10 parts by mass and E1 in a ratio of 90 parts by mass and discharged from the die hole. This was dry-spun at a spinning speed of 600 m / min with a speed ratio of 1.25 between the Gode roller and the winding machine, and then wound up to obtain a wound polyurethane fiber with a core-sheath structure (a structure in which the fibrous portion (B) is the core and the fibrous portion (A) is the sheath) of 44 dtex and 4 filaments. Tables 3 and 4 show a list of the composition and properties of the obtained polyurethane elastic fibers.

[0216] [Comparative Example 1] A1 was extruded from the die hole, and dry-spun at a spinning speed of 600 m / min with a speed ratio of 1.25 between the Gode roller and the winding machine, and then wound up to obtain a wound yarn of 44 dtex, 4 filaments of polyurethane fiber. Tables 3 and 4 show a list of the composition and properties of the obtained polyurethane fibers.

[0217] [Comparative Example 2] D2 was extruded from the die hole, and dry-spun at a spinning speed of 600 m / min with a speed ratio of 1.25 between the Gode roller and the winding machine, and then wound up to obtain a wound body of 44 dtex, 4 filament polyurethane fiber. Tables 3 and 4 show a list of the composition and properties of the obtained polyurethane fibers.

[0218] [Comparative Example 3] E4 was extruded from the die hole, and dry-spun at a spinning speed of 600 m / min with a speed ratio of 1.25 between the Gode roller and the winding machine, and then wound up to obtain a wound body of 44 dtex, 4 filament polyurethane fiber. Tables 3 and 4 show a list of the composition and properties of the obtained polyurethane fibers.

[0219] [Comparative Example 4] D2 and E6 were uniformly mixed in a ratio of 50 parts by mass to 50 parts by mass to form a spinning stock, which was then extruded through the die hole. This stock was dry-spun at a spinning speed of 600 m / min with a Gode roller-to-winding machine speed ratio of 1.25, and wound up to obtain a 44 dtex, 4-filament polyurethane fiber winding. The composition and properties of the obtained polyurethane fibers are shown in Tables 3 and 4.

[0220] [Comparative Example 5] D2 and E2 were uniformly mixed in a ratio of 50 parts by mass to 50 parts by mass to form a spinning stock, which was then extruded through the die hole. This stock was dry-spun at a spinning speed of 600 m / min with a Gode roller-to-winding machine speed ratio of 1.25, and wound up to obtain a 44 dtex, 4-filament polyurethane fiber winding. The composition and properties of the obtained polyurethane fibers are shown in Tables 3 and 4.

[0221] [Comparative Example 6] D2 and E1 were uniformly mixed in a ratio of 50 parts by mass to 50 parts by mass to form a spinning stock, which was then extruded through the die hole. This stock was dry-spun at a spinning speed of 600 m / min with a Gode roller-to-winding machine speed ratio of 1.25, and wound up to obtain a 44 dtex, 4-filament polyurethane fiber winding. The composition and properties of the obtained polyurethane fibers are shown in Tables 3 and 4.

[0222] [Table 3]

[0223] [Table 4] [Industrial applicability]

[0224] According to the present invention, polyurethane fibers and the like can be provided.

Claims

1. A polyurethane fiber comprising a portion (A) containing silver and polyurethane, and a portion (B) containing zirconium and polyurethane.

2. The polyurethane fiber according to claim 1, wherein the silver component contains a silver compound.

3. The polyurethane fiber according to claim 1, wherein the median diameter of the silver component is 0.01 to 10 μm.

4. The polyurethane fiber according to claim 1, wherein the proportion of silver in part (A) is 0.0001 to 5% by mass.

5. The polyurethane fiber according to claim 1, wherein in portion (A), the ratio of zirconium to 1 part by mass of silver is less than 25 parts by mass.

6. The polyurethane fiber according to claim 1, wherein the zirconium component contains zirconium phosphate.

7. The polyurethane fiber according to claim 1, wherein the median diameter of the zirconium component is 0.01 to 10 μm.

8. The polyurethane fiber according to claim 1, wherein the proportion of zirconium in portion (B) is 0.01 to 15% by mass.

9. The polyurethane fiber according to claim 1, wherein in portion (B), the ratio of silver to 1 part by mass of zirconium is less than 0.01 parts by mass.

10. The polyurethane fiber according to claim 1, wherein in portion (B), the ratio of at least one metal M selected from Zn, Mg, Ca, Al, Ti, Cu, and Ag to 1 part by mass of zirconium is less than 0.01 parts by mass.

11. The polyurethane fiber according to claim 1, wherein part (A) and part (B) are fibrous.

12. The polyurethane fiber according to claim 1, which is a composite fiber comprising a fibrous portion (A) and a fibrous portion (B).

13. The polyurethane fiber according to claim 1, wherein at least a portion of portion (A) is exposed to at least a portion of the fiber surface.

14. The polyurethane fiber according to claim 1, wherein at least a portion of portion (B) is located inside the fiber more than at least a portion of portion (A).

15. A polyurethane fiber according to claim 1, comprising a fibrous portion (A) and a fibrous portion (B), wherein at least a portion of the fibrous portion (A) is exposed to at least a portion of the fiber surface, and at least a portion of the fibrous portion (B) is located inside the fiber more than at least a portion of the fibrous portion (A).

16. The polyurethane fiber according to claim 1, wherein the ratio of part (A) to the total amount of part (A) and part (B) is 0.1 to 99.5% by mass.

17. The polyurethane fiber according to claim 1, wherein the proportion of silver is 0.00001 to 3% by mass.

18. The polyurethane fiber according to claim 1, wherein the proportion of zirconium is 0.01 to 15% by mass.

19. A fabric containing polyurethane fibers according to any one of claims 1 to 18.

20. A molded article containing polyurethane fibers according to any one of claims 1 to 18.

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