CN116607229A

CN116607229A - Polyurethane elastic fiber and fabric containing same

Info

Publication number: CN116607229A
Application number: CN202310110316.5A
Authority: CN
Inventors: 河原慎太朗; 森孝正; 山本太郎
Original assignee: Asahi Kasei Corp
Current assignee: Asahi Kasei Corp
Priority date: 2022-02-15
Filing date: 2023-02-14
Publication date: 2023-08-18
Also published as: JP2023118668A

Abstract

Polyurethane elastic fiber and fabric containing the same. Disclosed is a polyurethane elastic fiber which has excellent antibacterial and deodorizing properties and which is maintained even after dyeing or washing. [ solution ] to provide a polyurethane elastic fiber, which is characterized by comprising an Ag-containing compound, a zirconium phosphate-containing compound that is different from the Ag-containing compound, and a polyurethane polymer, wherein the mass ratio of Zr element to Ag element is 25-100.

Description

Polyurethane elastic fiber and fabric containing same

Technical Field

The present application relates to a polyurethane elastic fiber and a fabric containing the same.

Background

Polyurethane elastic fibers have high elongation and high stretchability, and are widely used for such excellent physical properties as underwear, masks, pantyhose, swimwear, jeans, sportswear, diapers, and the like.

Among these uses, the consumer's intention to clean is increasing, and there are increasing demands for antibacterial performance and deodorizing performance, and many products having antibacterial performance and deodorizing performance are on the market among masks, clothes, bedclothes, daily necessities, and the like.

Patent document 1 below proposes a method of imparting antibacterial performance by post-processing of an antibacterial agent. Specifically, there has been proposed a method of fixing an antibacterial/antibacterial agent and a chemical agent exhibiting a morphological stabilizing effect to a sewn product by performing a heat treatment step after using, adhering or impregnating the sewn product in combination with the antibacterial agent and the chemical agent exhibiting a morphological stabilizing effect.

Patent document 2 below reports polyurethane elastomers and elastic fibers containing an antibacterial agent and 2 kinds of deodorant agents. The polyurethane elastic fiber is excellent in antibacterial property and deodorizing property, and by using the polyurethane elastic fiber, post-processing is not required, so that the number of working steps is reduced, and a cloth excellent in hand feeling can be obtained.

Patent document 3 below reports polyurethane elastic yarns spun from a spinning dope containing a metal phosphate and a quaternary ammonium salt compound. The polyurethane elastic yarn in this patent document exhibits antibacterial properties by releasing a monoamine compound having a molecular weight of 120 or less, and is excellent in antibacterial properties and deodorizing properties.

Prior art literature

Patent literature

Patent document 1: japanese patent laid-open No. 2001-248058

Patent document 2: japanese patent laid-open No. 2006-28453

Patent document 3: international publication No. 2012/053401

Disclosure of Invention

Problems to be solved by the application

However, the application described in patent document 1 imparts performance by post-processing, and the antibacterial agent adhering to the cloth surface due to washing falls off, causing a problem of performance degradation.

The application described in patent document 2 achieves performance by adding a plurality of inorganic compounds to a polyurethane solution, and even in the application described in patent document 2, it has been found that the antibacterial property after washing is greatly reduced.

The application described in patent document 3 exhibits antibacterial performance by releasing a low-molecular organic compound such as a monoamine compound having a molecular weight of 120 or less, but the low-molecular organic compound such as an amine is liable to volatilize, and there is a problem in maintaining antibacterial performance from the viewpoint of maintaining the antibacterial performance as compared with an inorganic compound that does not volatilize.

In view of the above problems of the prior art, an object of the present application is to provide a polyurethane elastic fiber which is excellent in antibacterial performance and deodorizing performance and which is maintained even after dyeing and washing.

Solution for solving the problem

The present inventors have conducted intensive studies and repeated experiments to solve the above problems, and as a result, have unexpectedly found that the above problems can be solved by the ratio of Ag to Zr in a polyurethane elastic fiber containing an Ag-containing compound and a zirconium phosphate-containing compound different from the Ag-containing compound being within a specific range, and have completed the present application.

Namely, the present application is as follows.

[1] A polyurethane elastic fiber characterized by comprising an Ag-containing compound, a zirconium phosphate-containing compound different from the Ag-containing compound, and a polyurethane polymer, wherein the mass ratio of Zr element to Ag element is 25-100.

[2] The polyurethane elastic fiber according to the above [1], wherein the mass ratio of the Zr element to the Ag element is 25 or more and 55 or less.

[3] The polyurethane elastic fiber according to the above [1] or [2], wherein the Ag-containing compound contains Ag element and at least one or more elements selected from the group consisting of Na, zr, cu, zn, al, mg, ti, P, sc, pt and Si.

[4] The polyurethane elastic fiber according to any one of the above [1] to [3], wherein the content of Ag element is 0.015 mass% or more and 0.200 mass% or less with respect to the polyurethane elastic fiber.

[5] The polyurethane elastic fiber according to any one of the above [1] to [4], wherein the content of Ag element is 0.030 mass% or more and 0.090 mass% or less relative to the polyurethane elastic fiber.

[6] The polyurethane elastic fiber according to any one of the above [1] to [5], wherein the Ag-containing compound contains Ag element, na element and Zr element at the same time.

[7] The polyurethane elastic fiber according to any one of the above [1] to [6], further comprising 0.1% by mass or more and less than 1% by mass of a chlorine-resistant agent.

[8] The polyurethane elastic fiber according to the above [7], wherein the chlorine-resistant agent is hydrotalcite and/or huntite.

[9] The polyurethane elastic fiber according to any one of the above [1] to [8], wherein the content of Zr element is 1.00 mass% or more with respect to the polyurethane elastic fiber.

[10] The polyurethane elastic fiber according to any one of the above [1] to [9], wherein the concentration of dimethylacetamide (DMAc) contained in the polyurethane elastic fiber is 2.00 mass% or less.

[11] The polyurethane elastic fiber according to any one of the above [1] to [10], wherein the total amount of the antibacterial agent containing an Ag-containing compound and the deodorant agent containing a zirconium phosphate-containing compound different from the Ag-containing compound is 5.00 mass% or more and 9.00 mass% or less.

[12] A fabric comprising the polyurethane elastic fiber according to any one of the above [1] to [11 ].

ADVANTAGEOUS EFFECTS OF INVENTION

The polyurethane elastic fiber of the present application exhibits high antibacterial and deodorizing properties, and further, the antibacterial properties are sustained even after dyeing and washing.

Detailed Description

An embodiment of the present application is a polyurethane elastic fiber, which contains an Ag-containing compound and a zirconium phosphate-containing compound different from the Ag-containing compound, and has a mass ratio of Zr element to Ag element of 25 to 100.

< Ag-containing Compound >)

The polyurethane elastic fiber of the present embodiment contains an Ag-containing compound. The Ag-containing compound is an inorganic compound having an Ag element, and the form of the Ag-containing compound is not particularly limited, and may be an inorganic compound in which an Ag simple substance or an Ag ion is incorporated into a structural formula, an inorganic compound carrying Ag, or both of them.

The Ag-containing compound preferably contains an Ag element and at least one element selected from the group consisting of Na, zr, cu, zn, al, mg, ti, P, sc, pt and Si. More specifically, it is preferable that the catalyst further contains zeolite, a composite oxide containing zinc oxide and zirconium oxide, a composite oxide containing silicon dioxide and zirconium oxide, zirconium phosphate, copper-supported zirconium phosphate, platinum-supported zirconium phosphate, sodium hydride, copper oxide, titanium oxide, magnesium oxide, and the like, and a compound composed of a combination thereof, in addition to Ag element. The Ag-containing compound may include a compound containing Ag element in the compound itself, such as silver-loaded zirconium phosphate or silver-loaded zeolite. From the viewpoint of further improving the antibacterial performance, the Ag-containing compound particularly preferably contains silver-loaded zirconium phosphate.

The Ag-containing compound is preferably a composite metal oxide containing Ag, na, and Zr at the same time. The polyurethane elastic fiber of the present embodiment exhibits excellent antibacterial performance by containing an Ag-containing compound containing both of these three elements, and maintains antibacterial performance even after dyeing and washing. The reason for this is examined as follows:

the Ag ions eluted from the Ag-containing compound become the main component of the antibacterial action, and the zirconium phosphate traps the Ag ions generated in the fiber system. By capturing Ag ions, elution of Ag ions out of the fiber system, that is, elution of antibacterial components during dyeing and washing treatment can be suppressed;

in addition, na ions eluted from the Ag-containing compound affect the increase in osmotic pressure outside the cell membrane of the bacterium, and Ag ions are efficiently transported from outside the cell membrane to inside the cell, and as a result, the antibacterial performance is higher even after dyeing and washing than in the prior art. In order to effectively dissolve Na ions, the Ag-containing compound is preferably in the form of a Na salt.

Zirconium phosphate-containing compound different from Ag-containing compound

The polyurethane elastic fiber of the present embodiment contains a zirconium phosphate-containing compound (hereinafter also simply referred to as "zirconium phosphate-containing compound") different from the Ag-containing compound. The form of the zirconium phosphate-containing compound is not particularly limited, and may be zirconium phosphate alone, zirconium phosphate loaded with other chemical species, or both. Zirconium phosphate may have an alpha, gamma, or other crystal structure.

< mass ratio of Zr element to Ag element >

The weight ratio of Zr to Ag specified by fluorescence X-ray analysis (XRF) of the polyurethane elastic fiber of the present embodiment is 25 or more, preferably 26 or more, more preferably 27 or more, further preferably 28 or more, and further 100 or less, preferably 80 or less, more preferably 60 or less, further preferably 55 or less, and particularly preferably 50 or less. When the mass ratio of Ag to Zr is within the above range, zirconium phosphate captures Ag ions released from the Ag-containing compound, and thus the Ag ions are not eluted out of the fiber, and therefore the antibacterial performance of the Ag ions can be effectively and continuously utilized even in a small amount, and the antibacterial performance can be maintained high even after washing.

< polyurethane Polymer >)

The polyurethane elastic fiber of the present embodiment contains a polyurethane polymer. The polyurethane polymer is obtained by a known urethanization reaction technique in which a prepolymer is obtained by a reaction between a high molecular diol and a diisocyanate, and the prepolymer is chain-extended with a polyfunctional active hydrogen-containing compound as a chain extender.

Examples of the polymer diol include polyether diol, polyester diol, polycarbonate diol, polyacrylic diol, and polythioester diol, and polyether diol is preferable, and polyalkylene ether diol is more preferable.

In the polyalkylene ether glycol, a linear or branched hydrocarbon chain having 2 to 10 carbon atoms is bonded by an ether bond, and in order to exhibit excellent stretch properties of the polyurethane elastic fiber, the number average molecular weight calculated from the hydroxyl value of the polyalkylene ether glycol is preferably 500 or more, more preferably 1000 or more, and still more preferably 1500 or more. On the other hand, from the viewpoint of heat resistance and abrasion resistance of the product yarn, it is preferably 5000 or less, more preferably 3000 or less, and further preferably 2500 or less.

Examples of the diisocyanate include aliphatic, alicyclic and aromatic diisocyanates having 2 isocyanate groups in the molecule. Examples thereof include 4,4 '-diphenylmethane diisocyanate, 2, 4-or 2, 6-toluene diisocyanate, m-or p-phenylene diisocyanate, 1, 5-or 2, 6-naphthalene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4' -dicyclohexylmethane diisocyanate, a mixture thereof, and a copolymer thereof. In addition, a compound having a blocked isocyanate group converted into a diisocyanate group may also be used.

In the synthetic polyurethane polymer, the molar ratio of the polymeric diol to the diisocyanate (diisocyanate/polymeric diol) is preferably 1.20 or more and 1.80 or less, more preferably 1.30 or more and 1.70 or less, and still more preferably 1.40 or more and 1.60 or less, from the viewpoint of obtaining a uniform polymer with little gel.

Examples of the polyfunctional active hydrogen-containing compound include low molecular diamines such as ethylenediamine, propylenediamine, tolylenediamine, m-xylylenediamine, 1, 3-diaminocyclohexane, isophoronediamine, hydrazine, 4' -diaminodiphenylmethane, dihydrazide, piperazine, and low molecular diols such as ethylene glycol, 1, 2-propanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, diethylene glycol, and dipropylene glycol. These chain extenders may be used alone or in the form of mixtures.

In the synthesis of polyurethane polymers, it is also possible to use chain terminators having monofunctional active hydrogen atoms. Examples of the chain terminator include primary amines such as dimethylamine, diethylamine, di-n-butylamine, di-t-butylamine, diisobutylamine, diisopropylamine, and 2-ethylhexyl amine, and primary alcohols such as methanol, ethanol, isopropanol, 2-methyl-2-propanol, and 1-butanol. These chain terminators may be used singly or in the form of mixtures.

In the synthesis of the polyurethane polymer, in the synthesis of the prepolymer containing the high-molecular diol and the diisocyanate, or in the reaction of the prepolymer with the active hydrogen-containing compound, an organic solvent such as Dimethylformamide (DMF), dimethylacetamide (DMAc), dimethylsulfoxide (DMSO) or the like may be used, and dimethylacetamide (DMAc) is preferable.

The polyurethane polymer may contain various stabilizers, pigments, and the like. For example, antioxidants such as hindered phenols, benzotriazoles, benzophenones, phosphoric acids, and hindered amines, various chemical agents, inorganic substances such as zinc oxide, iron oxide, titanium oxide, and magnesium oxide, carbon black, various pigments, light stabilizers, nitrogen oxide capturing materials, heat stabilizers, and various resins can be contained.

Polyurethane elastic fiber >, and process for producing the same

The polyurethane elastic fiber of the present embodiment can be produced by forming the polyurethane polymer into a fiber shape by known dry spinning, wet spinning, melt spinning, or the like. Dry spinning is preferable because physical crosslinks formed by hydrogen bonds between hard segments can be formed more firmly than wet spinning and melt spinning. In the case of dry spinning, an amide-based polar solvent may be used.

The polyurethane elastic fiber may contain any lubricant for reducing the friction in use. The lubricant may be kneaded into the polyurethane polymer in advance, or may be applied to the filaments during spinning. Specific examples of the lubricant include mineral fine particles such as polydimethylsiloxane, polyester-modified silicone, polyether-modified silicone, amino-modified silicone, mineral oil, silica, colloidal alumina, and talc, higher fatty acid metal salt powders such as magnesium stearate, and calcium stearate, higher aliphatic carboxylic acid, higher aliphatic alcohol, paraffin, polyethylene, and the like, which may be added singly or in any combination.

The content of the Ag element specified by ICP emission spectrometry (ICP-AES) in the polyurethane elastic fiber according to the present embodiment is preferably 0.015 mass% or more, more preferably 0.030 mass% or more, still more preferably 0.040 mass% or more, and further preferably 0.200 mass% or less, more preferably 0.150 mass% or less, still more preferably 0.100 mass% or less, and particularly preferably 0.090 mass% or less, relative to the polyurethane elastic fiber. When the content of the Ag element is 0.015 mass% or more, the antibacterial property derived from the Ag element is sufficient. When the content of Ag element is 0.200 mass% or less, a large amount of zirconium phosphate is not required for effective capture of Ag ions, and thus the addition of inorganic matters in the production process is reduced, and the spinning stability such as filter clogging and breakage is improved.

The polyurethane elastic fiber of the present embodiment preferably contains 0.1 mass% or more and less than 1 mass% of the chlorine-resistant agent from the viewpoint of exhibiting sufficient chlorine discoloration resistance.

The chlorine-resistant agent is preferably hydrotalcite and/or huntite. Hydrotalcite and huntite are uniformly dispersed in the polyurethane polymerization solution, so that chloride ions can be effectively trapped, and high chlorine discoloration resistance is exhibited.

The content of Zr element specified by ICP emission spectrometry (ICP-AES) in the polyurethane elastic fiber according to the present embodiment is preferably 1.00 mass% or more, more preferably 1.50 mass% or more, further preferably 2.00 mass% or more, and further preferably 4.00 mass% or less, further preferably 3.00 mass% or less, relative to the polyurethane elastic fiber. When the content of Zr element relative to the polyurethane elastic fiber is 1.00 mass% or more, effective capturing of Ag element by a zirconium phosphate-containing compound different from the Ag-containing compound can be achieved, and when it is 4.00 mass% or less, a large amount of zirconium phosphate is not required for effective capturing of Ag ions, so that the addition of inorganic matters in the production process is reduced, and problems such as clogging of the filter and breakage of the yarn can be avoided, and thus the spinning stability is improved.

The concentration of dimethylacetamide (DMAc) contained in the polyurethane elastic fiber of the present embodiment is preferably 2.00 mass% or less, more preferably 1.00 mass% or less, and still more preferably 0.500 mass% or less. When the concentration of dimethylacetamide (DMAc) contained in the polyurethane elastic fiber is 2.00 mass% or less, deterioration of the physical properties of the yarn during long-term storage can be suppressed, and the stability of the product during storage is excellent.

The total amount of the antibacterial agent containing an Ag-containing compound and the deodorant containing a zirconium phosphate-containing compound different from the Ag-containing compound in the polyurethane elastic fiber of the present embodiment is preferably 5.00 mass% or more, more preferably 5.50 mass% or more, further preferably 6.00 mass% or more, and further preferably 9.00 mass% or less, more preferably 8.00 mass% or less, further preferably 7.00 mass% or less. The total amount of the antibacterial agent containing the Ag-containing compound and the deodorant containing the zirconium phosphate-containing compound different from the Ag-containing compound falls within the above range, and thus the antibacterial and deodorant properties are provided, and the amount of the inorganic substance added in the production process is reduced, and problems such as clogging of the filter and breakage of the yarn can be avoided, and the spinning stability is improved.

The polyurethane elastic fiber can be used as a processed yarn obtained by, for example, interweaving with a material other than the polyurethane elastic fiber (hereinafter, also referred to as "other material"), covering with another material, or interlacing with or twisting with another material. The types of the other raw materials are not particularly limited as long as they are appropriately selected, and specific examples thereof include natural fibers such as cotton, silk, wool, and hemp, polyamide fibers such as polyester fibers, nylon 6 fibers, and nylon 66 fibers, and chemical fibers such as polyimide fibers, polyacrylic fibers, cuprammonium rayon, viscose fibers, and acetate rayon.

< fabric >

Another embodiment of the present application is a fabric containing the polyurethane elastic fiber. The fabric may be a woven fabric, a knitted fabric, or a nonwoven fabric. The fabric may contain the other raw materials in accordance with the purpose.

The fabric may be used as a diaper, swimwear, panty hose (panty), a substrate (foundation), a sock, a rib cuff, a corset, a diaper, a bandage, an undergarment, a coat, a sock system, a sportswear, jeans, or other sanitary materials.

Examples (example)

The present application will be specifically described below with reference to examples and comparative examples, but the present application is not limited to these examples. The present application also includes polyurethane elastic fibers separated from products such as clothing and sanitary materials.

First, measurement methods, various evaluation methods, and the like used in examples and comparative examples will be described.

(1) Evaluation method of antibacterial performance

The fabric sample prepared in the example and the sample obtained by washing the fabric sample were subjected to an antibacterial property test procedure (bacterial liquid absorption method defined in JIS L1902 (ISO 20743)) specified by the general society act fiber evaluation technical protocol, and a (antibacterial activity value) was obtained from the result of measuring the number of viable bacteria of staphylococcus aureus (staphylococcus aureus).

A (antimicrobial activity value) is an index of the strength of antimicrobial property, and the effect is greater as the value is greater. In this example, considering the deviation of antibacterial performance between products, it was defined that antibacterial performance was sufficient for the case that A (antibacterial activity value) was not less than 4.5 before and after washing.

(2) Method for evaluating deodorizing performance

According to the JEC301 SEK MARK fiber product authentication standard, the method is implemented according to the following steps.

For the fabric sample prepared in the example, the sample was subjected to humidity control at 20℃under an RH atmosphere of 65% relative humidity for 24 hours or more, and then cut out to 100cm ² Cloth, and put into a Tesla bag (200 cm in case of sample weight less than 1 g) ² The sample weight was adjusted to 1g in the following range). Ammonia gas 3L having a concentration of 100ppm was injected into a Tesla bag, and the residual gas concentration after 2 hours of storage at 20℃was measured by a detection tube (manufactured by Ming's chemical Co., ltd.). Ammonia gas at a concentration of 100ppm was adjusted by dilution with dry air. The same evaluation was performed as a null test without using a sample according to the following formula:

ammonia deodorization rate [% ] =100× (residual ammonia concentration in air test-gas residual gas concentration of sample)/(residual ammonia concentration in air test)

The reduction rate of the residual gas concentration was calculated as ammonia deodorization rate [% ]. In this example, the deodorizing ability was judged to be sufficient for the case where the deodorizing rate of ammonia [% ] was not less than 70[% ].

(3) Method for washing during evaluation of antibacterial property and deodorizing property

Washing method according to JEC326 "washing method of SEK MARK fiber product", as a detergent, "JAFET standard compounding detergent" was used.

(4) Determination method of mass ratio of Zr element to Ag element

For polyurethane elastic fiber, a fluorescent X-ray analysis device was used: EDX-8000 (manufactured by Shimadzu corporation) was measured, and the weight ratio of Zr to Ag was determined as the mass ratio of each element in the polyurethane elastic fiber based on the quantitative ratio calculated from the fluorescent X-ray intensity ratio of each element.

(measurement conditions)

The using device comprises: EDX-8000 (Shimadzu manufacturing Co., ltd.)

Voltage: 50kV, 15kV

Analytical diameter: 10mm of

Measuring atmosphere: vacuum

(5) Method for measuring content of Ag element

The content of Ag element in the polyurethane elastic fiber was determined by measuring the solution in which the polyurethane elastic fiber was dissolved by ICP emission spectrometry (ICP-AES). In addition, the solubilization of polyurethane elastic fiber uses microwave decomposition.

(6) Determination method of Zr element content

The content of Zr element in the polyurethane elastic fiber was determined by measuring the solution in which the polyurethane elastic fiber was dissolved by ICP emission spectrometry (ICP-AES). In addition, the solubilization of polyurethane elastic fiber uses microwave decomposition.

(7) Method for measuring chlorine resistance agent content

For polyurethane elastic fibers, analysis was performed using X-ray diffraction measurement (XRD), and compared with the spectrum of chlorine resistance, thereby performing identification. Next, the respective quantitative ratios of the metal elements constituting the chlorine-resistant agent were measured by fluorescent X-ray analysis of the polyurethane elastic fiber, and the chlorine-resistant agent content was specified by a standard curve prepared separately from the result of measuring the polyurethane elastic fiber to which the prescribed amount of the chlorine-resistant agent was added.

(8) Na element detection method

For polyurethane elastic fibers or Ag-containing compounds, scanning electron microscopy was used: the JSM-IT500 (JEOL) can determine the presence or absence of Na element by performing elemental analysis.

(9) Method for measuring concentration of dimethylacetamide (DMAc)

Dimethylacetamide (DMAc) concentration [% ] in the polyurethane elastic fiber was measured as described below using gas chromatography (manufactured by Shimadzu corporation: GC-2014).

As a column, stabilwax (length: 30mm, inner diameter: 0.53 mm) manufactured by RESTEK was used.

The polyurethane elastic fiber was cut out to 0.20g, immersed in 7.0g of acetone, and subjected to shaking extraction at room temperature for 2 hours. Then, the extracted solution was subjected to gas chromatography to determine the peak area of dimethylacetamide (DMAc) and acetone. Further, 4 standards (DMAc concentration: 50ppm, 250ppm, 500ppm, 1000 ppm) obtained by diluting dimethylacetamide (DMAc) with acetone were subjected to gas chromatography measurement, and a standard curve was prepared using the obtained peak areas. The amount of dimethylacetamide (DMAc) in the extracted solution [ ppm ] was calculated using the obtained standard curve, using the following formula:

dimethylacetamide (DMAc) concentration [% ] = [ (acetone weight [ g ]. Times.dimethylacetamide (DMAc) amount calculated by standard curve [ ppm ])/. Degree.

The concentration [% ] of dimethylacetamide (DMAc) was determined.

The lower the concentration [% ] of dimethylacetamide (DMAc) in the polyurethane elastic fiber, the more preferable is that the lower the concentration [% ] is, and in consideration of the influence on the reduction of the physical properties of the filaments at the time of long-term storage, the case where the concentration of dimethylacetamide (DMAc) is 0.5 mass% or less is defined as an a-evaluation, the case where it exceeds 0.5 mass% and 1.0 mass% or less is defined as a-evaluation, the case where it exceeds 1.0 mass% and 2.0 mass% or less is defined as a C-evaluation, the case where it exceeds 2.0 mass% is defined as a-evaluation, and the samples of the a-evaluation or the B-evaluation are qualified.

(10) Evaluation of spinning stability

Spinning was performed for 24 hours using a single-end spinning machine under the conditions described in the following examples and comparative examples, and the spinning pressure was varied to 1kg/cm without causing breakage ² In the following cases, "good" was determined as having good spinning stability.

Example 1

2000g of polytetramethylene ether glycol having a number average molecular weight of 1800, 2800g of N, N-dimethylacetamide and 445g of 4,4' -diphenylmethane diisocyanate were reacted while stirring for 90 minutes under a nitrogen gas stream at 60℃to obtain a polyurethane prepolymer having isocyanate groups at both ends. To this was added 32g of ethylenediamine and 6g of diethylamine dissolved in 2000g of dimethylacetamide (DMAc) to give a polyurethane urethane polymer solution having a viscosity of 4200 poise (30 ℃ C.).

Hydrotalcite 0.7 mass%, 4 '-butylidenebis (3-methyl-6-t-butylphenol) 1.0 mass%, 2- (2' -hydroxy-3 '-t-butyl-5' -methylphenyl) -5-chlorobenzotriazole 0.5 mass%, silver-loaded zirconium phosphate (chemicalThe formula: ag, naH, zr (H) ₃ PO ₄ ) "NOVARON" (registered trademark), grade, manufactured by Toyama Synthesis Co., ltd.): AG 300) 2.0 mass%, zirconium phosphate (formula: zr (HPO) ₄ ) ₂ ·nH ₂ O (formula, n is 0 to 2), kesmon (registered trademark) manufactured by Toyama Synthesis Co., ltd., grade: NS-10) 5.0 mass% and magnesium stearate 0.1 mass%, and dimethylacetamide (DMAc) was added thereto, dispersed by a homomixer to prepare a 20 mass% dispersion, and then mixed with a polyurethane solution to form a uniform solution, which was defoamed at room temperature under reduced pressure to prepare a spinning dope.

The dope was dry-spun at a winding speed of 800 m/min and a hot air temperature of 300 ℃ using a spinneret having 2 round holes, and after bundling by a false twisting device using compressed air, a surface treatment agent of 4.0 mass% was applied to the polyurethane elastic fiber, and the resultant was wound around a paper tube, to obtain a wound package of polyurethane elastic fiber of 22dtex/2 filaments. As the surface treatment agent, an oil solution containing 67 mass% of polydimethylsiloxane, 30 mass% of mineral oil, and 3.0 mass% of amino-modified silicone was used.

Using the polyurethane elastic fiber, a plain jersey knit fabric knitted with polyester 84dtex/36 filaments was produced using a 3.5 inch 18 gauge 200 gauge single circular knitting machine. The content of the polyurethane elastic fiber in the knitted fabric was 10%. Then, the knitted fabric is dyed to obtain an elastic fabric.

The results of various evaluation analyses of the obtained polyurethane elastic fiber and the results of the antibacterial property evaluation and the deodorizing property evaluation of the elastic fabric are shown in table 1 below.

Example 2, 8

Polyurethane elastic fiber and elastic fabric were obtained in the same manner as in example 1, except that the addition amounts of the silver-loaded zirconium phosphate and hydrotalcite were changed.

Example 3

Polyurethane elastic fiber and stretch fabric were obtained in the same manner as in example 2, except that hydrotalcite was not used.

Example 4

Polyurethane elastic fiber and stretch fabric were obtained in the same manner as in example 2, except that silver-loaded zirconium phosphate containing no Na element was used as the silver-loaded zirconium phosphate.

Example 5

Polyurethane elastic fiber and elastic fabric were obtained in the same manner as in example 2, except that hydrotalcite was replaced with calcium magnesium carbonate Dan Laiti.

Example 6

Polyurethane elastic fiber and elastic fabric were obtained in the same manner as in example 2, except that the addition amount of hydrotalcite was changed and further, huntite was added.

Example 7

Polyurethane elastic fiber and stretch fabric were obtained in the same manner as in example 2, except that the amount of zirconium phosphate added was changed.

Examples 9 and 10

Polyurethane elastic fiber and elastic fabric were obtained in the same manner as in example 2, except that the addition amounts of silver-loaded zirconium phosphate and zirconium phosphate were changed.

Comparative example 1

Polyurethane elastic fiber and elastic fabric were obtained in the same manner as in example 1, except that the addition amounts of zirconium phosphate and hydrotalcite on which silver was supported were changed without using zirconium phosphate.

Comparative example 2

A polyurethane elastic fiber and an elastic fabric were obtained in the same manner as in example 8, except that a silver-loaded zirconium phosphate containing no Na element was used as the silver-loaded zirconium phosphate, and that the amount of added zirconium phosphate was changed without using hydrotalcite, and that zinc oxide was added so as to be 0.5 mass% relative to the polyurethane polymer.

Comparative example 3

Polyurethane elastic fiber and elastic fabric were obtained in the same manner as in example 2, except that the amounts of silver-loaded zirconium phosphate and zirconium phosphate added were changed.

Comparative example 4

Polyurethane elastic fiber and elastic fabric were obtained in the same manner as in example 2, except that zirconium phosphate loaded with silver was not used.

The mass ratio of Zr element to Ag element cannot be calculated without detecting Ag element from the polyurethane elastic fiber.

TABLE 1

As is clear from table 1, the polyurethane elastic fibers and the fabrics of examples 1 to 10 were excellent in antibacterial performance and deodorizing performance, and the antibacterial performance was maintained even after washing.

Industrial applicability

The polyurethane elastic fiber and the fabric containing the same of the present application are excellent in antibacterial performance and deodorizing performance and maintain antibacterial performance even after dyeing and washing, and therefore can be suitably used as a paper diaper, swimwear, panty liner, panty hose, backing, sock belt, rib cuff, corset, paper diaper, bandage, underwear, outer garment, sock system, sportswear, jeans, or other sanitary material.

Claims

1. A polyurethane elastic fiber characterized by comprising an Ag-containing compound, a zirconium phosphate-containing compound different from the Ag-containing compound, and a polyurethane polymer, wherein the mass ratio of Zr element to Ag element is 25-100.

2. The polyurethane elastic fiber according to claim 1, wherein a mass ratio of Zr element to Ag element is 25 or more and 55 or less.

3. The polyurethane elastic fiber according to claim 1 or 2, wherein the Ag-containing compound contains Ag element and at least one or more elements selected from the group consisting of Na, zr, cu, zn, al, mg, ti, P, sc, pt and Si.

4. The polyurethane elastic fiber according to claim 1 or 2, wherein the content of Ag element is 0.015 mass% or more and 0.200 mass% or less with respect to the polyurethane elastic fiber.

5. The polyurethane elastic fiber according to claim 1 or 2, wherein the content of Ag element is 0.030 mass% or more and 0.090 mass% or less with respect to the polyurethane elastic fiber.

6. The polyurethane elastic fiber according to claim 1 or 2, wherein the Ag-containing compound contains Ag element, na element and Zr element at the same time.

7. The polyurethane elastic fiber according to claim 1 or 2, further comprising 0.1 mass% or more and less than 1 mass% of a chlorine-resistant agent.

8. The polyurethane elastic fiber according to claim 7, wherein the chlorine-resistant agent is hydrotalcite and/or huntite.

9. The polyurethane elastic fiber according to claim 1 or 2, wherein the content of Zr element is 1.00 mass% or more with respect to the polyurethane elastic fiber.

10. The polyurethane elastic fiber according to claim 1 or 2, wherein the polyurethane elastic fiber contains dimethylacetamide (DMAc) at a concentration of 2.00 mass% or less.

11. The polyurethane elastic fiber according to claim 1 or 2, wherein the total amount of the antibacterial agent containing an Ag-containing compound and the deodorant agent containing a zirconium phosphate-containing compound different from the Ag-containing compound is 5.00 mass% or more and 9.00 mass% or less.

12. A fabric comprising the polyurethane elastic fiber according to claim 1 or 2.