JP6799818B2 - Fiber structure and its manufacturing method - Google Patents

Description

The present invention relates to a fiber structure having excellent heat settability, heat resistance, deodorant property, recoverability, and elongation, and a method for producing the same.

Fiber structures containing polyurethane elastic fibers are widely used for elastic clothing applications such as legwear, innerwear and sportswear, and elastic materials such as disposable diapers and sanitary products due to their excellent elastic properties (stretch function). There is.

The content of polyurethane elastic fibers in the fiber structure is increasing more and more in order to further improve the stretch function as the application is expanded. Against this background, fiber structures containing polyurethane elastic fibers have come to be required to have more advanced properties. Typical characteristics required are heat settability at low temperatures that can be processed at lower temperatures to save energy in the manufacturing process, and high temperatures to improve yield when repeated post-processing is applied. In addition to having heat resistance and improving the deodorant property required for most inner apparel products and sports apparel products today, it has higher strength, elongation and resilience.

On the other hand, regarding polyurethane elastic fibers, a technique for disclosing the structure and properties (see, for example, Patent Document 1) and a technique for disclosing the composition and properties have been proposed (see, for example, Patent Documents 2 and 3).

Patent Document 1 discloses in detail an example of fiber structure analysis based on small-angle X-ray scattering measurement of polyurethane elastic fiber and its long period, and has been observed in polyurethane elastic fiber including this document. It is known that the long period in small-angle X-ray scattering measurement is usually 7 to 16 nm.

Japanese Unexamined Patent Publication No. 8-003815 JP-A-2005-48306 International Publication 2015/056763 Pamphlet

However, when the above technique is applied to a fiber structure containing polyurethane elastic fibers, further improvement is required in terms of heat resistance and recoverability in Patent Document 1 and in terms of deodorant property in Patent Documents 2 and 3. It was. An object of the present invention is to further improve these properties and to provide a fiber structure suitable for stretchable clothing and stretchable materials and a method for producing the same.

The fiber structure of the present invention employs any of the following means in order to achieve the above object.
[1] A fiber structure containing a polyurethane elastic fiber and an alkyldiphenyl ether-based compound, wherein the first long period (J1) in the fiber direction in the small angle X-ray scattering measurement of the polyurethane elastic fiber is 20 to 100 nm. Stuff.
[2] There are two types of long periods in the fiber direction in the small-angle X-ray scattering measurement of the polyurethane elastic fiber, and the scattering intensity for detecting the long period is smaller than the first long period (J1). The fiber structure according to the above [1] in which J2) is present.
[3] The fiber structure according to the above [1] or [2], wherein the second long period (J2) is 7 to 19 nm.
[4] The ratio of the second long period (J2) to the first long period (J1) is 2 ± 0.2, 3 ± 0.2, 4 ± 0.2 or 5 ± 0.2. The fiber structure according to any one of [1] to [3].
[5] A fiber structure using the polyurethane elastic fiber according to any one of [1] to [4] above, wherein the long period in the equatorial line direction in the small-angle X-ray scattering measurement of the polyurethane elastic fiber is 10 to 20 nm. ..
[6] The fiber structure according to any one of [1] to [5] above, wherein the alkyl diphenyl ether compound contains an alkyl diphenyl ether sulfonic acid and / or an alkyl diphenyl ether sulfonate.
[7] The fiber structure according to any one of claims [1] to [6], wherein the alkyldiphenyl ether compound is contained in the polyurethane elastic fiber.
[8] Alkyldiphenyl ether-based compound at the same time as and / or after dyeing the fiber structure to be treated containing polyurethane elastic fibers having a first long period (J1) in the fiber direction of 20 to 100 nm in small angle X-ray scattering measurement. A method for producing a fiber structure to be treated in a bath using.
[9] A fiber structure in which a fiber structure to be treated containing polyurethane elastic fibers having a first long period (J1) in the fiber direction of 20 to 100 nm in small-angle X-ray scattering measurement is padded with an alkyldiphenyl ether-based compound. Manufacturing method.

The fiber structure of the present invention is excellent in heat setting property, heat resistance, deodorant property, recoverability, and elongation, and is also excellent in appearance, and is suitable for elastic clothing and elastic materials.

It is a small-angle X-ray scattering image of PU114 in the Example of this invention. It is a small-angle X-ray scattering image of PU3X0 in the comparative example.

In the present invention, the polyurethane elastic fiber shows a novel scattering image in an image obtained by small-angle X-ray scattering measurement (hereinafter, may be referred to as a scattering image), that is, the first length in the fiber direction (mediline direction). When the period (J1) is set to 20 to 100 nm, which is longer than the conventional one, and the fiber structure to be treated containing the polyurethane elastic fiber is further made into a fiber structure containing an alkyldiphenyl ether-based compound, the above-mentioned problems can be solved. I found that. This is because the fiber structure containing the polyurethane elastic fiber having the first long period (J1) of 20 to 100 nm and the alkyldiphenyl ether-based compound has higher deodorizing property as the fiber structure, particularly ammonia deodorizing property. .. From this point of view, it is more preferable that the first long period (J1) is 25 to 70 nm, and when such a range is taken, the adjustment range of deodorant property by changing the content of the alkyldiphenyl ether compound is a fiber having another structure. This is because it is significantly wider than the above.

From the scattering image obtained by small-angle X-ray scattering measurement of polyurethane elastic fibers and the calculated long period, crystals are arranged in layers in a cross section perpendicular to the fiber direction, and the interstices of the crystals arranged in layers are amorphous. It can be seen that there is an area of. In polyurethane elastic fibers, the amorphous region (hereinafter, may be referred to as a gap) is considered to be composed of a soft segment chain in a segmented polyurethane-urethane chain or a segmented polyurethane-urea chain. We have found that an alkyldiphenyl ether-based compound that functions as a deodorant can stably exist in a polyurethane elastic fiber having a fiber structure having a large gap volume, that is, a fiber structure having a long cycle, and led to the present invention. It is a thing.

In the polyurethane elastic fiber used in the present invention, there may be a plurality of long periods in the fiber direction in the small-angle X-ray scattering measurement, but in that case, the first in the small-angle X-ray scattering measurement of the polyurethane elastic fiber used in the present invention. The long period of is a long period having the maximum value of the X-ray scattering intensity (Intensity) for identifying the long period, and corresponds to the brightest peak in the small-angle X-ray scattering image. Further, it is preferable that a plurality of long periods in the present invention exist not only in the fiber direction but also in the equatorial axis direction, and it is also preferable to have two types of high strength and weak strength. Of these, if the first long period in the fiber direction calculated from the peak of maximum intensity is J1 and the second long period calculated from the second intensity peak is J2, J2 is preferably 7 to 19 nm. More preferably, it is 9 to 16 nm. Further, when the structure satisfies these conditions, the alkyldiphenyl ether-based compound can be stably retained in a larger amount. As a result, the elastic structure is also excellent, and the fiber structure such as the cloth containing the polyurethane elastic fiber exhibits good deodorizing property.

Further, the ratio of J2 to J1 is preferably in the vicinity of an integral multiple, and more preferably in the vicinity of 2 to 5 (that is, in the vicinity of 2, 3, 4 or 5). More preferably, it is in the vicinity of 2 or 3. Here, the neighborhood of an integral multiple means the range of ± 0.2. When it is in the vicinity of an integer of 2 or more, the stretch characteristics are further improved, and when it is made into a fabric, the stretch characteristics are better. When it is in the vicinity of an integer of 5 or less, the permanent strain is not excessive, and the fiber structure and the fiber structure. Even when it is used, the expansion and contraction characteristics will be better.

Regarding the long period in the equatorial line direction in the small-angle X-ray scattering measurement of polyurethane elastic fibers, it has been generally accepted that the long period observed in polyurethane elastic fibers so far is less than 15 nm, usually 5 to 10 nm. In the polyurethane elastic fiber having J1 of 20 to 100 nm, a long period in the equatorial line direction is preferably observed at 10 to 20 nm, and a fiber structure exhibiting even better heat setting property can be obtained.

In the present invention, the method of measuring the polyurethane elastic fiber with a small angle X-ray and calculating the long period can be performed by the method described in Patent Document 1, but is not limited thereto.

Specifically, the long period J can be obtained from the following Bragg's equation.
J = λ / 2 sin [{tan -1 (r / R)} / 2]
However, in the above formula, λ is the wavelength of the X-ray, R is the camera length (distance between the measurement sample and the scattering intensity detector), and r is calculated from the method described below according to a conventional method.

For example, in the scattered image shown in FIG. 1, the long period in the meridian direction may be obtained from the above Bragg's equation, where r is the distance from the equator line 2 to the maximum scattering intensity peak. (Similarly, the long period in the equatorial line direction can be obtained from the above Bragg's equation, where r is the distance from the meridian to the scattering intensity of the maximum scattering intensity peak.)
The scattering intensity detector may be a camera or an imaging plate, but the polyurethane elastic fiber used in the present invention shows a novel scattering image in a small-angle X-ray scattering image and shows a long period J of 20 to 100 nm. In order to measure the long period J more accurately, it is more preferable to use synchrotron radiation as a light source and to digitize the scattering intensity detection using an imaging plate. In particular, for synchrotron radiation, a high-energy light source on the order of several tens of keV to several keV, which was not possible with a conventional goniometer, can be constantly used, and the measurement time can be shortened. It is possible to minimize the time effect of deformation and alteration due to slight distortion and gravity. Preferable examples of synchrotron radiation include SPring-8 in Japan, which is a third-generation synchrotron radiation facility, APS in the United States, and ESRF in Europe. For example, SPring-8 can be used for general use research, and specifically, Hyogo Prefecture Beamline (BL08B2 and BL24XU) is suitable. The scattering angle (referred to as 2θ) in the Bragg's equation is approximated by {tan -1 (r / R)}, but 2θ can be detected with higher accuracy by using the above-mentioned synchrotron radiation or a detector. It is. For long-period calculation, r is usually from a continuous plot (scattering intensity profile) with the reciprocal space axis (4πλ / sinθ (nm-1)) along the meridian 1 and equator line 2 on the horizontal axis and the scattering intensity on the vertical axis. It is more preferable to obtain it.

A typical composition constituting polyurethane in the polyurethane elastic fiber used in the present invention will be described.

The polyurethane-based resin used in the present invention may be any polyurethane as long as the main constituents are a polymer diol and a diisocyanate, and is not particularly limited. Further, the synthesis method is not particularly limited. The main component refers to a component that constitutes 50% by mass or more of the components that form polyurethane.

That is, for example, it may be a polyurethane urea composed of a polymer diol, a diisocyanate and a diamino compound (low molecular weight diamine) as a chain extender, or a polyurethane composed of a polymer diol, a diisocyanate and a low molecular weight diol as a chain extender. May be good. Further, a polyurethane urea using a compound having a hydroxyl group and an amino group in the molecule as a chain extender may be used. It is also preferable to use a polyfunctional glycol or isocyanate having trifunctionality or higher as long as the effect of the present invention is not impaired.

Here, typical structural units constituting the polyurethane-based resin used in the present invention will be described.

As the polymer diol of the structural unit constituting the polyurethane resin, polyether glycol, polyester glycol, polycarbonate diol and the like are preferable. Further, it is preferable to use a polyether glycol from the viewpoint of deodorizing property, flexibility, and imparting high elongation when made into a fiber.

The polyether glycol preferably contains a copolymerized diol compound containing a unit represented by the following general formula (1).

(However, a and c are integers of 1 to 3, b is an integer of 0 to 3, R3 and R4 are H or alkyl groups having 1 to 3 carbon atoms)
Specific examples of the polyether glycol compound include polyethylene glycol, modified polyethylene glycol, polypropylene glycol, polytrimethylene ether glycol, polytetramethylene ether glycol (hereinafter abbreviated as PTMG), tetrahydrofuran and 3-methyl- tetrahydrofuran. Modified PTMG, which is a copolymer of, modified PTMG, which is a copolymer of tetrahydrofuran and 2,3-dimethyl- tetrahydrofuran, modified PTMG, which is a copolymer of tetrahydrofuran and neopentyl glycol, tetrahydrofuran and ethylene oxide and / or propylene oxide. Examples thereof include random copolymers in which are irregularly arranged. As the polyurethane resin used in the present invention, one of these polyether glycols may be used, or two or three or more of them may be mixed or copolymerized. Of these, it is preferable to use PTMG or modified PTMG.

From the viewpoint of enhancing the abrasion resistance and light resistance of the polyurethane resin, by decomposing a mixture of butylene adipate, polycaprolactone diol, 3-methyl-1,5-pentanediol and polypropylene polyol with adipic acid or the like. A dicarboxylic acid ester derived from a polyester glycol such as a polyester diol having a side chain obtained, or a dicarboxylic acid component consisting of 3,8-dimethyldecanedioic acid and / or 3,7-dimethyldecanedioic acid and a diol component. A polycarbonate diol containing a unit is preferably used.

Further, these polymer diols may be used alone, or may be used by mixing or copolymerizing two or more kinds.

Next, as the structural unit diisocyanate constituting the polyurethane-based resin used in the present invention, aromatic diisocyanates, alicyclic diisocyanates, aliphatic diisocyanates and the like are preferable. Examples of the aromatic diisocyanate include diphenylmethane diisocyanate (hereinafter abbreviated as MDI), tolylene diisocyanate, 1,4-diisocyanate benzene, xylylene diisocyanate, and 2,6-naphthalene diisocyanate, which are polyurethanes having particularly high heat resistance and strength. Suitable for synthesizing. Further, examples of the alicyclic diisocyanate include methylenebis (cyclohexylisocyanate) (hereinafter abbreviated as PICM), isophorone diisocyanate, methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate, cyclohexane-1,4-. Diisocyanates, hexahydroxylylene diisocyanates, hexahydrotolylene diisocyanates, octahydro-1,5-naphthalenedisocyanates and the like are preferable. Aliphatic diisocyanates can be effectively used especially when suppressing yellowing of polyurethane. Of these, 4,4'-MDI is preferable. Then, these diisocyanates may be used alone or in combination of two or more.

Next, as the chain extender for the structural unit constituting the polyurethane resin, it is also preferable to use at least one or more of the low molecular weight diamine and the low molecular weight diol. In addition, like ethanolamine, it may have both a hydroxyl group and an amino group in the molecule.

Preferred low molecular weight diamines include, for example, ethylenediamine (hereinafter abbreviated as EDA), 1,2-propanediamine, 1,3-propanediamine, hexamethylenediamine, p-phenylenediamine, p-xylylenediamine, m-xylyl. Examples thereof include rangeamine, p, p'-methylenedianiline, 1,3-cyclohexyldiamine, hexahydrometaphenylenediamine, 2-methylpentamethylenediamine, bis (4-aminophenyl) phosphine oxide and the like. EDA is particularly preferable. By using EDA, it is possible to obtain a resin having excellent elongation, elasticity recovery, and heat resistance. A triamine compound capable of forming a crosslinked structure, such as diethylenetriamine, may be added to these chain extenders to the extent that the effect is not lost.

Preferred low molecular weight diols include ethylene glycol (hereinafter abbreviated as EG), 1,3-propanediol, 1,4-butanediol, bishydroxyethoxybenzene, bishydroxyethylene terephthalate, 1-methyl-1,2. -Ethandiol is a typical example. Particularly preferred are EG, 1,3-propanediol and 1,4-butanediol. When these are used, the heat resistance of the diol-extended polyurethane is high, and the strength of the polyurethane fiber can be increased.

The most suitable chain extender in the polyurethane used in the present invention is a low molecular weight diol.

Further, it is also preferable that one or more end-sealing agents are used in the polyurethane in the present invention. As the terminal sequestering agent, monool such as ethanol, propanol, butanol, isopropanol, allyl alcohol and cyclopentanol, monoisocyanate such as phenylisocyanate and the like are preferable.

In synthesizing such polyurethane, it is also preferable to use one or a mixture of two or more catalysts such as an amine catalyst and an organometallic catalyst.

Examples of amine-based catalysts include N, N-dimethylcyclohexylamine, N, N-dimethylbenzylamine, triethylamine, N-methylmorpholin, N-ethylmorpholin, N, N, N', N'-tetramethylethylenediamine, and the like. N, N, N', N'-tetramethyl-1,3-propanediamine, N, N, N', N'-tetramethylhexanediamine, bis-2-dimethylaminoethyl ether, N, N, N' , N', N'-pentamethyldiethylenetriamine, tetramethylguanidine, triethylenediamine, N, N'-dimethylpiperazine, N-methyl-N'-dimethylaminoethyl-piperazine, N- (2-dimethylaminoethyl) morpholine, 1-Methylimidazole, 1,2-dimethylimidazole, N, N-dimethylaminoethanol, N, N, N'-trimethylaminoethylethanolamine, N-methyl-N'-(2-hydroxyethyl) piperazine, 2, Examples thereof include 4,6-tris (dimethylaminomethyl) phenol, N, N-dimethylaminohexanol, and triethanolamine.

Examples of the organometallic catalyst include tin octanate, dibutyltin dilaurate, and lead dibutyl octanate.

The method for synthesizing polyurethane as the polyurethane-based resin used in the present invention is not particularly limited, such as a melt polymerization method or a solution polymerization method.

In the case of the solution polymerization method, such polyurethane contains, for example, N, N-dimethylacetamide (hereinafter abbreviated as DMAc), dimethylformamide (hereinafter abbreviated as DMF), dimethyl sulfoxide, N-methylpyrrolidone and the like as main components. It is obtained by synthesizing using the above-mentioned raw materials in the solvent. For example, a method in which each of the above raw materials is added and dissolved in such a solvent and heated to an appropriate temperature to react to obtain polyurethane, or a polymer diol and diisocyanate are first melt-reacted, and then the reaction product is used as a solvent. A method of dissolving in a polyurethane and reacting with the above-mentioned chain extender to obtain polyurethane can be adopted as a particularly suitable method. In this case, the concentration of the obtained polyurethane solution is usually preferably in the range of 30% by mass or more and 80% by mass or less.

Further, in the solution polymerization method, it is preferable to apply so-called multi-stage polymerization in which diisocyanate is stepwise added to the polymer diol. As a specific step, the first step is performed without a solvent, and after obtaining the prepolymer at the theoretical end point, the prepolymer is dissolved in a solvent at least twice its mass and once sufficiently diluted. Is more preferable. The total amount of diisocyanate added in the second and subsequent stages may be smaller than the molar ratio of the terminal isocyanate group of the diisocyanate to the terminal hydroxyl group of the polymer diol in terms of the reaction equivalent ratio (molar ratio) of the first stage. More preferred.

The timing of adding the chain extender composed of a low molecular weight diol is preferably at or immediately after the addition of the diisocyanate to be added in the second stage, and all the reactions are preferably carried out at a low temperature of 100 ° C. or lower.

The fiber structure of the present invention contains an alkyldiphenyl ether-based compound. If the fibrous structure of the present invention does not contain an alkyldiphenyl ether compound, the fibrous structure does not have useful deodorant properties.

Conventionally, even if a certain amount of alkyl diphenyl ether compound is contained in order to obtain high deodorant property, the effect reaches a plateau relatively quickly, and it is difficult to obtain a sufficient effect. That is, the adjustment range of the deodorant property was narrow, and the level of the deodorant property that peaked out was also low. Specifically, the content of the alkyldiphenyl ether-based compound in the fiber structure peaked at about 0.5% by mass. Further, from the viewpoint of obtaining better basic physical properties as a fiber structure, it was preferable that the content of the alkyldiphenyl ether compound was not too large. However, when an alkyl diphenyl ether compound is contained in the fiber structure to be treated containing the polyurethane elastic fiber having the structure specified in the present invention, the deodorant property is adjusted by increasing or decreasing the content of the alkyl diphenyl ether compound. The width is wider, and the adjustment upper limit of the deodorant property adjusted thereby is also higher. Furthermore, even if a large amount of alkyldiphenyl ether-based compound is contained, it is possible to maintain better basic physical properties as a fiber structure, and the fiber structure exhibits a clear difference in expansion and contraction characteristics from the conventional one.

The mass ratio of the alkyldiphenyl ether compound contained in the fiber structure of the present invention is preferably in the range of 0.03 to 30% by mass with respect to the mass of the fiber structure. Here, the place where the alkyldiphenyl ether compound is contained may be adhered to the entire fiber structure, or may be localized and adhered to the elastic yarn made of polyurethane. It is more preferable that it is contained in an elastic yarn made of polyurethane. If it is less than 0.03% by mass, a sufficient deodorizing effect cannot be exhibited, and if it exceeds 30% by mass, the texture of the fiber structure is hindered, which is not preferable. From the viewpoint of satisfying both the deodorant effect and the texture, it is more preferably 1.0 to 20% by mass, further preferably 2.0 to 10% by mass, and 2.0 to 5.0% by mass. Is most preferable. The content may be tested in advance according to the intended use, and the optimum value may be appropriately determined.

The fiber structure of the present invention contains at least one alkyl diphenyl ether compound. As the alkyldiphenyl ether-based compound, those represented by the general formula (2) are preferably used.

(In the formula, R1 and R2 are independently alkyl groups having 1 to 20 carbon atoms. R3 and R4 each independently have M selected from H, Na, K, Mg and Ca-SO ₃ M. m and n are integers from 0 to 5, either n or m is greater than or equal to 1. p is an integer from 0 to (5-m) and q is 0 to (5-n). ) Is an integer.)

In the general formula (2), R1 and R2 are independently alkyl groups having 1 to 20 carbon atoms. Here, "independently" means that when m + n is 2 or more, the carbon numbers of the respective alkyl groups may all be different. When the number of carbon atoms of the alkyl group is 20 or less, the solubility in water is good, which is preferable.

Further, in the general formula (2), R3 and R4 are −SO ₃ M having M selected from H, Na, K, Mg and Ca, respectively. Here, −SO ₃ M refers to a combination of SO ₃ − and counterion M, sulfonic acid when M is H, and sulfonate when M is any of Na, K, Mg and Ca. Indicates that. Further, "independently" means that when p + q is 2 or more, all Ms selected from H, Na, K, Mg and Ca may be different for each -SO ₃ M.

In the general formula (2), the alkyl group R1 and the alkyl group R2 may be linear or branched, and the alkyl group R1 and the alkyl group R2 may satisfy the condition that hydrogen in the benzene ring can be substituted. It can be located anywhere.

As the alkyldiphenyl ether-based compound, it is preferable that a sulfonic acid or a sulfonate is substituted at an arbitrary position on the benzene ring (that is, p + q is 1 or more in the general formula (2)). The presence of the sulfonic acid group can be expected to obtain a higher deodorizing effect. R3 and R4 can be located at any position as long as the conditions under which hydrogen in the benzene ring can be substituted are satisfied, as described above for R1 and R2. Further, the total of p and q is more preferably 3 or less from the viewpoint of production efficiency.

The alkyl diphenyl ether compound of the present invention can be used at least one kind or a combination of two or more kinds.

In the present invention, when the alkyldiphenyl ether compound is contained in the elastic yarn made of polyurethane, it is preferable to dissolve or disperse it in any of the above-mentioned solvents in advance. In the case of dispersion, those having an average primary particle diameter of 3.0 μm or less are preferable from the viewpoint of suppressing clogging of the spinning stock solution into the spinning cap. More preferably, it is 1.5 μm or less. Further, when the average primary particle size is smaller than 0.05 μm from the viewpoint of dispersibility, the cohesive force increases and it becomes difficult to uniformly mix the particles in the spinning stock solution. Therefore, those having an average primary particle size of 0.05 μm or more are used. preferable. More preferably, it is 0.15 μm or more.

The fiber structure of the present invention simultaneously dyes and / or dyes a fiber structure to be treated containing a polyurethane elastic yarn having a first long period (J1) in the fiber direction of 20 to 100 nm in small-angle X-ray scattering measurement. It can also be obtained by treating in a bath with an alkyldiphenyl ether-based compound.

When treating in the bath at the same time as dyeing, an alkyl diphenyl ether compound is mixed with an auxiliary agent such as a dye and a leveling agent used in normal dyeing to prepare a dyeing solution, and the dyeing treatment is performed at a normal dyeing temperature and time. do it.

Further, when the dyeing solution is discharged once after dyeing to prepare an aqueous solution containing an alkyldiphenyl ether compound and treated in the bath, the temperature and time may be set separately for the treatment in the bath. The temperature of the treatment in the bath in such a case is preferably in the range of 50 to 130 ° C. If it is lower than 50 ° C., the washing durability becomes insufficient, and if it exceeds 130 ° C., the texture of the fiber structure may be impaired. The processing time is preferably in the range of 10 to 60 minutes.

When preparing a staining solution or an aqueous solution containing an alkyldiphenyl ether compound, the pH of the solution is preferably adjusted in the range of 2.0 to 5.0. The pH adjustment may be any acid usually used in dyeing / finishing, and examples thereof include acetic acid, formic acid, citric acid, and malic acid, but any of them may be used.

As the apparatus used for the treatment in the bath, any of a liquid flow dyeing machine, an air flow dyeing machine, a jigger dyeing machine, a beam dyeing machine, a wins and the like may be used.

As another production method, a fiber structure to be treated containing a polyurethane elastic yarn having a first long period (J1) in the fiber direction of 20 to 100 nm in small-angle X-ray scattering measurement is padded with an alkyldiphenyl ether-based compound. Can be obtained by That is, it can be treated by a pad dry cure method in which a fiber structure is impregnated with a treatment liquid containing an alkyldiphenyl ether compound, then squeezed with a mangle roll and heat-treated. As the heat treatment, the drying temperature is preferably in the range of 100 to 150 ° C., and the finishing set temperature is preferably in the range of 150 to 200 ° C. When preparing a treatment liquid containing an alkyldiphenyl ether-based compound, the pH of the liquid is preferably adjusted in the range of 2.0 to 5.0. The pH adjustment may be any acid usually used in dyeing / finishing, and examples thereof include acetic acid, formic acid, citric acid, and malic acid, but any of them may be used. As the apparatus used in the padding process, in addition to a general resin processing machine, a gravure roll, a knife coater, or the like may be used, or a dryer having a mangle roll, a heat setter, or the like may be used.

It is also possible to prepare a treatment liquid containing an alkyldiphenyl ether-based compound by mixing it with a printing paste and apply it to a fiber structure at the same time as printing.

As a manufacturing method at the yarn stage, it is also possible to add an alkyldiphenyl ether compound alone or in combination with an oil agent by using an oil agent applying roll or the like in applying an oil agent in dry spinning or melt spinning of polyurethane elastic fibers. In addition, when making composite processed yarns such as covering of synthetic fibers or natural fibers and elastic yarns made of polyurethane, air entanglement, twisting, false twisting, core spun yarn, etc., alkyl diphenyl ether compounds are used using oiling rolls and the like. Can be added alone or in combination with an oil agent.

It may be preferable to add various additives described below to the polyurethane resin used in the present invention. Any method can be adopted as the method for adding various additives. As a typical method, various means such as a static mixer method, a stirring method, a homomixer method, and a twin-screw extruder method can be adopted. Here, when the polyurethane is synthesized by solution polymerization, the various additives to be added are preferably added as a solution from the viewpoint of uniform addition to the polyurethane.

In addition, when various additives are added to the polyurethane solution, a phenomenon may occur in which the solution viscosity of the mixed solution after the addition becomes higher than expected as compared with the viscosity of the polyurethane solution before the addition. From the viewpoint of preventing this phenomenon, dimethylamine, diisopropylamine, ethylmethylamine, diethylamine, methylpropylamine, isopropylmethylamine, diisopropylamine, butylmethylamine, isobutylmethylamine, isopentylmethylamine, dibutylamine, diamylamine, etc. It is also preferable to use one or a mixture of two or more end-blocking agents such as monool such as monoamine, ethanol, propanol, butanol, isopropanol, allyl alcohol and cyclopentanol, and monoisocyanate such as phenylisocyanate.

Further, the polyurethane resin used in the present invention may contain various stabilizers, pigments and the like, if necessary, as long as the effects of the present invention are not impaired. For example, as stabilizers, an addition polymer of divinylbenzene and p-cresol (“Metachlor®” 2390 manufactured by DuPont), t-butyldiethanolamine and methylene-bis- (4-cyclohexyl isocyanate). Alternate copolymer polyurethane (Dupont's "Metachlor (registered trademark)" 2462), light-resistant agent, antioxidant, etc., so-called BHT and Sumitomo Chemical Co., Ltd.'s "Smilizer (registered trademark)" GA-80 Both hindered phenolic drugs such as, benzotriazole-based drugs such as "Chinubin (registered trademark)" manufactured by Ciba Geigy, benzophenone-based drugs, "Sumilyzer (registered trademark)" P-16 manufactured by Sumitomo Chemical Industries, Ltd. Phosphorus chemicals such as, various hindered amine chemicals, inorganic pigments such as titanium oxide and carbon black, fluororesin powder or silicone resin powder, metal soaps such as magnesium stearate, silver and zinc and theirs. Bactericides and deodorants containing compounds, lubricants such as silicones and mineral oils, barium sulfate, cerium oxide, various antistatic agents such as betaine and phosphoric acid, etc. may be added, or with polymers. It may be reacted and present. In order to further enhance the durability against light and various types of nitrogen oxides, for example, HN-150 manufactured by Nippon Hydrazine Co., Ltd. as a nitrogen oxide scavenger, and Sumitomo Chemical Co., Ltd. as a thermal oxidation stabilizer (for example, "Sumilyzer (registered trademark)" GA-80 manufactured by Sumitomo Chemical Co., Ltd. and, for example, "Sumisorb (registered trademark)" 300 # 622 manufactured by Sumitomo Chemical Co., Ltd. may be contained as a light stabilizer.

These additives may be added directly to the polyurethane solution when preparing the above-mentioned polyurethane spinning stock solution, or a dispersion of such additives may be prepared in advance and mixed with the polyurethane solution. You may. The content of these additives is appropriately determined according to the purpose and the like.

The polyurethane-based resin used in the present invention is particularly preferably selected from the polymer diol and diisocyanate from the viewpoint of obtaining a resin having no practical problems including process passability and excellent heat resistance. It is obtained by reacting, and the melting point on the low temperature side is in the range of −20 ° C. or higher and 20 ° C. or lower, and the melting point on the high temperature side is in the range of 150 ° C. or higher and 300 ° C. or lower. Here, the melting point on the low temperature side and the melting point on the high temperature side correspond to the melting point caused by the so-called soft segment of polyurethane or polyurethane urea as measured by a differential scanning calorimeter (DSC) and the melting point of a hard segment crystal.

Examples of the method for setting the melting point of polyurethane or polyurethane urea on the high temperature side within the range of 150 ° C. or higher and 300 ° C. or lower include a method of controlling the ratio of polymer diol and diisocyanate. For example, when the number average molecular weight of the polymer diol is 1000 or more, the melting point on the high temperature side becomes 150 ° C. by advancing the polymerization at a ratio of (number of moles of diisocyanate) / (number of moles of polymer diol) = 1.5 or more. The above polyurethane can be obtained.

Further, from the viewpoint of enhancing the deodorizing property, the urethane group concentration of the polyurethane constituting the polyurethane resin used in the present invention is preferably about 0.2 mol / kg or more and 3.5 mol / kg or less, more preferably about 0. It is 4 mol / kg or more and 1.0 mol / kg or less. The urethane group concentration is calculated as (polymer diol (mol) contained in polyurethane resin) x 2 / (polyurethane resin mass (kg)).

The most suitable composition of polyurethane in the present invention is to obtain polyurethane by polymerizing a chain extender composed of a polymer diol having a number average molecular weight of 500 or more and 5000 or less, an organic diisocyanate, and a low molecular weight diol to obtain the organic. The reaction equivalent ratio (molar ratio) of the terminal isocyanate group of the diisocyanate to the total terminal hydroxyl group of the high molecular weight diol and the low molecular weight diol is 2.5 to 4.0 or less, and the mass of the low molecular weight diol with respect to the high molecular weight diol. The ratio is in the range of 1/9 to 5/5.

When the reaction equal amount ratio exceeds 4.0, the elongation at break, recoverability, and heat settability of the obtained polyurethane elastic fiber are lowered, and the appearance quality and expansion / contraction of the fiber structure such as the fabric or knitted fabric using the same are lowered. The characteristics may deteriorate.

Further, the molecular weight of polyurethane in the present invention is preferably in the range of 40,000 or more and 150,000 or less as a number average molecular weight from the viewpoint of obtaining fibers having high durability and strength. In the present invention, the molecular weight is measured by GPC and converted into polystyrene.
In synthesizing such polyurethane, it is also preferable that one or a mixture of two or more catalysts such as an amine catalyst and an organometallic catalyst are used.

Examples of amine-based catalysts include N, N-dimethylcyclohexylamine, N, N-dimethylbenzylamine, triethylamine, N-methylmorpholin, N-ethylmorpholin, N, N, N', N'-tetramethylethylenediamine, and the like. N, N, N', N'-tetramethyl-1,3-propanediamine, N, N, N', N'-tetramethylhexanediamine, bis-2-dimethylaminoethyl ether, N, N, N' , N', N'-pentamethyldiethylenetriamine, tetramethylguanidine, triethylenediamine, N, N'-dimethylpiperazine, N-methyl-N'-dimethylaminoethyl-piperazine, N- (2-dimethylaminoethyl) morpholine, 1-Methylimidazole, 1,2-dimethylimidazole, N, N-dimethylaminoethanol, N, N, N'-trimethylaminoethylethanolamine, N-methyl-N'-(2-hydroxyethyl) piperazine, 2, Examples thereof include 4,6-tris (dimethylaminomethyl) phenol, N, N-dimethylaminohexanol, and triethanolamine.

Examples of the organometallic catalyst include tin octanate, dibutyltin dilaurate, and lead dibutyl octanate.

The concentration of the polyurethane thus obtained in the spinning stock solution is usually preferably in the range of 30% by mass or more and 80% by mass or less.

The polyurethane elastic fiber used in the present invention can be obtained by, for example, dry spinning, wet spinning, or melt spinning and winding the undiluted spinning solution constructed as described above. Of these, dry spinning is preferable from the viewpoint of stable spinning at all finenesses from thin to thick.

The fineness, number of single threads, cross-sectional shape, etc. of the polyurethane elastic fiber used in the present invention are not particularly limited. For example, the yarn may be a monofilament composed of one single yarn or a multifilament composed of a plurality of single yarns. The cross-sectional shape of the thread may be circular or flat.

The dry spinning method is also not particularly limited, and spinning may be performed by appropriately selecting spinning conditions and the like suitable for the desired characteristics and spinning equipment.

For example, the permanent strain rate and stress relaxation characteristics of the polyurethane elastic fiber used in the present invention are particularly susceptible to the speed ratio between the Gode roller and the winder, and thus are appropriately determined according to the purpose of use of the yarn. preferable. That is, from the viewpoint of obtaining a polyurethane elastic fiber having a desired permanent strain rate and stress relaxation, the speed ratio between the Gode roller and the winder is preferably in the range of 1.15 or more and 1.65 or less. Further, since the strength of the polyurethane elastic fiber can be improved by increasing the spinning speed, it is preferable to take a spinning speed of 450 m / min or more in order to obtain a practically suitable strength level. Further, considering the point of industrial production, about 450 to 1000 m / min is preferable.

The fiber structure of the present invention containing the polyurethane elastic fiber described above or the polyurethane elastic fiber obtained by the manufacturing method described above is excellent in deodorizing property, stretchability property, heat setting and other processability. Even when this is used to make a thin cloth, sufficient elasticity and aesthetics can be obtained, so that it is possible to obtain high-quality clothing with an excellent appearance. Such a feature can be remarkably obtained in the knitted fabric. In particular, the circular knitted fabric, which is a fiber structure of the present invention using the polyurethane elastic fiber described above or the polyurethane elastic fiber obtained by the manufacturing method described above, makes the best use of its body fit when used as clothing. It can also be preferably applied to applications pursuing aesthetics, such as underwear, hosiery, and tights.

Next, a preferable example of the material in the fiber structure of the present invention will be given.
The fiber structure refers to, but is not limited to, woven and knitted fabrics, non-woven fabrics, and cotton.

The fabric which is the fiber structure of the present invention is constructed by using the polyurethane elastic fibers as described above. Such a cloth can also exhibit the effect of the present invention even in a mixed elastic cloth in which polyester yarn, polyamide yarn (nylon yarn) and the like are mixed.

For example, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, or ethylene terephthalate unit is the main repeating component (preferably about 90 mol% or more of the repeating unit), and trimethylene terephthalate unit is the main repeating component. Fibers consisting of those (preferably those having about 90 mol% or more of the repeating unit), those having butylene terephthalate unit as the main repeating component (preferably those having about 90 mol% or more of the repeating unit) and the like can be preferably used. .. Among them, a fiber made of polyester having an ethylene terephthalate unit of about 90 mol% or more as a repeating component is preferable, and a fiber made of polyester having an ethylene terephthalate unit of about 95 mol% or more of a repeating component is more preferable. It is more preferable that the polyester has an ethylene terephthalate unit of about 100 mol% as a repeating component, that is, a fiber made of polyethylene terephthalate. This polyethylene terephthalate fiber has a good texture, gloss, and easy care properties such as being less likely to wrinkle, and is suitable as a fiber material constituting a stretchable fabric. Further, the polyethylene terephthalate fiber is suitable when used in combination with the polyurethane urea fiber preferably used in the present invention, and can be used as a good cloth. (CDPET requirements) Next, the cationic dyeable polyester fiber used in the present invention will be described.

Usually, cationic dyeable polyester fibers are obtained by copolymerizing a compound containing a metal sulfonate group in a polyester molecular structure. Various types of compounds containing a metal sulfonate group and different copolymerization rates have been developed in order to improve dyeability and texture, but the cation dyeable polyester fiber used in the present invention is a normal cation. It is not particularly limited as long as it exhibits dyeability to the dye.

Further, in the present invention, the cross-sectional shape of the polyester fiber may be round or irregular. Further, a water-absorbing quick-drying polyester fiber yarn or the like is preferably used. As water-absorbing and quick-drying polyester fibers, fibers having many smaller holes on the wall surface of hollow fibers and many grooves and holes on the fiber surface and the like are provided, and the water absorption of these fibers themselves is very small. Use various commercially available water-absorbing and quick-drying fibers by synthetic fiber manufacturers, such as fibers with irregular cross-sectional shapes that allow moisture to be absorbed into the pores, grooves on the fiber surface, gaps between fibers, and gaps between threads. Can be done. For example, examples of the water-absorbing and quick-drying polyester fiber include "Coolmax (registered trademark)" manufactured by INVISTA and "Theo α (registered trademark)" manufactured by Toray Industries, Inc. (Bimetal Requirement T-400) In particular, when polytrimethylene terephthalate is used, a side-by-side type composite fiber cross section is preferable. The fiber cross-sections are round, triangular, multi-lobular, flat, Dharma-shaped, C-shaped, M-shaped, H-shaped, X-shaped, W-shaped, I-shaped, and + -shaped. However, from the viewpoint of the balance between crimping and texture, semi-circular side-by-side with a round cross section, hollow side-by-side for light weight and heat retention, and side-by-side with a triangular cross section for dry texture. It is preferably used.

In order to impart water absorption and quick drying, as described above, a material having low hygroscopicity such as polyester fiber or acrylic fiber is used as the polymer itself, and the fiber is made into a hollow fiber and has many smaller holes on its wall surface. Many grooves and holes are provided in the shape or on the surface of the fiber, and the water absorption is absorbed by the minute holes of the fiber itself, the grooves on the surface of the fiber, the gaps between the fibers, and the gaps between the threads. Examples thereof include fibers having a deformed cross-sectional shape and the like, which are provided with minute holes or voids through which moisture can enter.

Further, if necessary, polyester conductive fiber or the like may be used as the antistatic synthetic fiber. As the conductive fiber, a composite polyester fiber using, for example, carbon black as a conductive substance (for example, "Bertron (registered trademark)" manufactured by Kanebo Synthetic Fiber Co., Ltd.), white copper iodide or a metal composite oxide (for example, TiO ₂₎ -Composite polyester fibers using SnO ₂ and Sb ₂ O ₂ ) and the like can be mentioned, but the present invention is not limited thereto.

The polyamide-based fiber referred to in the present invention refers to a fiber made of nylon 6, nylon 66, nylon 12, or the like.

For example, polyamide is a resin composed of a high molecular weight material in which so-called hydrocarbon groups are linked to the main chain via an amide bond, and the polyamide has excellent mechanical properties and is mainly composed of polycaproamide (nylon 6). ), Polyhexamethylene adipamide (nylon 66) is preferable, and polycaproamide (nylon 6) is more preferable because of its good dyeability. The term "mainly" as used herein means that the ε-caprolactam unit constituting the polycarbonate is 80 mol% or more, more preferably 90 mol% or more, based on the total monomer unit. The other components are not particularly limited, but are, for example, polydodecanoamide, polyhexamethylene adipamide, polyhexamethylene azelamide, polyhexamethylene sebacamide, polyhexamethylene dodecanoamide, polymethoxylylen adipa. Examples thereof include units such as aminocarboxylic acid, dicarboxylic acid, and diamine, which are monomers constituting mid, polyhexamethylene terephthalamide, polyhexamethylene isophthalamide, and the like.

As the synthetic fiber used in the present invention, for example, the fiber surface area per 1 g of the woven or knitted fabric is preferably about 0.02 m ² or more and 0.2 m ² or less, and is about 0.1 m ² or more and 0.2 m ² or less. are more preferred, even more preferably not more 0.2 m ² or less to about 0.12 m ² or more. Further, as the synthetic fiber in the present invention, for example, one having a single fiber fineness of about 3 decitex (dtex) or more and 300 decitex or less is preferable, and one having 10 decitex or more and 150 decitex or less is further preferable. Those having such a fiber surface area and / or a single fiber fineness can further improve the deodorizing property.

Further, the polyester fiber used in the present invention may contain various stabilizers, pigments and the like, if necessary, as long as the effect of the present invention is not impaired, as in the case of the above-mentioned polyurethane. For example, stabilizers such as addition polymers of divinylbenzene and p-cresol (“Metachlor (registered trademark)” 2390 manufactured by DuPont), lightfasteners; so-called BHT and Sumitomo Chemical Industries, Ltd. as antioxidants. Both hindered phenolic agents such as "Sumilyzer (registered trademark)" GA-80 manufactured by Ciba Geigy Co., Ltd .; benzotriazole-based and benzophenone-based agents such as "Chinubin (registered trademark)" manufactured by Ciba Geigy Co., Ltd .; Phosphorus chemicals such as "Smilizer (registered trademark)" P-16 manufactured by Japan; various hindered amine chemicals; inorganic pigments such as titanium oxide and carbon black; fluororesin powder or silicone resin powder; magnesium stearate, etc. Metal soaps; bactericides containing silver, zinc, compounds of these, etc .; deodorants; lubricants such as silicones and mineral oils; various antistatic agents such as barium sulfate, cerium oxide, betaine and phosphoric acid. May be added, or may be present by reacting with the polymer. In order to further enhance the durability against light and various types of nitric oxide, a nitrogen oxide scavenger such as HN-150 manufactured by Nippon Hydrazine Co., Ltd. and a thermal oxidation stabilizer such as Sumitomo Chemical Co., Ltd. ), Such as "Sumilyzer (registered trademark)" GA-80, and other light stabilizers, for example, "Sumisorb (registered trademark)" 300 # 622 manufactured by Sumitomo Chemical Co., Ltd. Good.

The fabric which is the fiber structure of the present invention may be obtained, for example, by producing a fabric from the polyurethane fiber and other synthetic fibers according to a conventional method, and particularly contains the polyurethane fiber 2 It is more preferable to contain more than one kind of synthetic fiber. The fabric which is the fiber structure of the present invention may be a woven fabric, a knitted fabric, or a non-woven fabric. For example, a synthetic fiber may be covered with a polyurethane elastic fiber to obtain a cloth as a covering fiber, or a polyurethane elastic fiber may be woven and knitted as a bare yarn (bare) into a synthetic fiber to obtain a cross-woven knitted fabric. Good.

The mixing ratio of the polyurethane elastic fibers in the mixed fabric depends on the mating yarn, the knitted structure, and the woven structure, but may be in the range of, for example, about 2% by mass to 40% by mass. With such a mixing ratio, it is possible to obtain a fabric that is excellent in tightening feeling and fit feeling, and is thinner and lighter than the conventional one.

Other materials include polyacrylic nitrile fibers, which are synthetic fibers, polyvinyl alcohol fibers, polyvinyl chloride fibers, polyurethane fibers, acetate fibers, which are semi-synthetic fibers, and biscous rayon, which is a recycled fiber. Cellulous fibers containing cupra, milk protein fibers, protein fibers including soybean protein fibers, polylactic acid fibers, or filament yarns and spun yarns, or blended yarns, or plants containing cotton and hemp. There are natural fibers, animal-based natural fibers including wool, cashmere, and silk, or blended yarns thereof.

When the fabric which is the fiber structure of the present invention is a woven fabric, it may be woven only with synthetic fibers, or other fibers may be interwoven. As the synthetic fiber, it is preferable that two or more kinds including the polyurethane fiber are contained. The structure of the polyurethane elastic fiber woven fabric is the three original structures such as plain weave, velvet weave, and satin weave, the change structure such as change plain weave, change diagonal weave, and change satin weave, and the special structure such as honeycomb weave, velvet weave, and satin weave. , Single double weave such as vertical double weave, horizontal double weave, double weave such as ventilation weave, bag weave, double velvet, multi-layered structure such as belt weave, vertical velvet, towel, seal, velor, etc. Vertical pile weave, beskin, horizontal velvet, velvet, horizontal pile weave such as corduroy, and entwined texture such as satin, gauze, and crest are preferable.

The weaving is not particularly limited as long as the effect of the present invention is not impaired, but the weaving is performed by a loom (fly shuttle loom, etc.) or a loomless loom (rapia loom, gripper loom, water jet loom, air jet loom, etc.). Is preferable.

Further, when the fabric which is the fiber structure of the present invention is a knitted fabric, it may be knitted only with synthetic fibers, or fibers other than these may be interwoven. As the synthetic fiber, it is preferable that two or more kinds including the polyurethane fiber are contained. The type of knitted fabric may be a horizontal (weft) knitted fabric, a vertical (warp) knitted fabric, or the like. As for the structure of the knitted fabric, the horizontal knitting is preferably flat knitting, rubber knitting, double-sided knitting, pearl knitting, tack knitting, floating knitting, single ridge knitting, lace knitting, hair addition, etc. Atlas knit, double cord knit, half tricot knit, fleece knit, jacquard knit and the like are preferable. The number of layers may be a single layer or two or more layers.

Knitting is not particularly limited as long as the effect of the present invention is not impaired, but by a circular knitting machine, a flat knitting machine, a flat knitting machine such as a cotton knitting machine, a tricot knitting machine, a Raschel knitting machine, a Milanese knitting machine, etc. It is preferred to be done.

The fiber structure of the present invention is also preferably dyed with an acid dye, a cationic dye, a disperse dye or the like. These dyes are not limited to specific ones, but those having high dyeing fastness are preferable.

Specifically, the acid dye may be any commercially available acid dye, and may be any of leveling type, half milling type, milling type, and metal-containing type. For example, "Nairosan (registered trademark)" E series, "Nairosan (registered trademark)" N series, "Nairosan (registered trademark)" S series, "Nairosan (registered trademark)" F series, "Lanacin (registered trademark)" F series , "Lanacin (registered trademark)" M series (above, manufactured by Arkroma), "Techtilon (registered trademark)", "Elionil (registered trademark)", "Pola (registered trademark)", "Lanacron S (registered trademark)" , "Irgalan (registered trademark)", "Lanaset (registered trademark)", "Lanaset (registered trademark)" PA (above, manufactured by Huntsman), "Kayanol (registered trademark)", "Kayanor Milling (registered trademark)" (The above is manufactured by Nippon Kayakusha). The cationic dye may be any commercially available cationic dye, and may be either a regular type (commonly known as a raw cation) or a dispersion type. For example, "Kayakuriru (registered trademark)", "Kayakuriru (registered trademark)" ED (above, manufactured by Nippon Kayaku Co., Ltd.), "Nichiron (registered trademark)" (manufactured by Nissei Kasei Co., Ltd.), "Astrazon (registered trademark)" ( (Made by Distar) and the like.

The disperse dye may be any commercially available disperse dye. For example, "Kayaron Polyester UT series (manufactured by Nippon Kayaku Co., Ltd.), (registered trademark)" "Kayaron polyester (registered trademark)" PUT series ( Examples include Kiwa Kagaku Co., Ltd.) and "Teracil (registered trademark)" W series (Huntsman Co., Ltd.).

The dyeing machine used for the dyeing treatment of the fiber structure of the present invention is not particularly limited and may be either dyeing or printing, but a normal liquid flow dyeing machine, a beam dyeing machine, a paddle dyeing machine or the like may be used for productivity. It is preferable from the viewpoint of uniform dyeing. The dyeing temperature is preferably 90 ° C. or higher and 140 ° C. or lower from the viewpoint of dyeing fastness and dyeing quality. Further, since the fiber structure of the present invention has excellent dimensional stability, a small dimensional change rate, and less wrinkles, it is possible to lower the temperature of a heat set such as a preset or a final set. Further, the heat setting temperature is preferably 120 ° C. or higher and 200 ° C. or lower from the viewpoint of fabric quality and dimensional stability.

The fiber structure of the present invention preferably has a washing fastness of 4th grade or higher according to the JIS L-0848: 2011 (revised) A-2 method. The fibrous structure of the present invention not only evaluates the dyeing rate, that is, the balance of the dye after several washings, but also practically, the resistance corresponding to home washing and industrial washing under repeated or high temperature. It shows that it can hold.

Further, the fabric which is the fiber structure of the present invention includes, for example, outerwear such as coats, kimonos, suits, uniforms, sweaters, skirts, slacks, cardigans, sportswear, dress shirts, casual wear, tights, stockings, pantyhose, etc. Socks such as socks, pajamas, shorts, lingerie, foundations, underwear such as hogery, sheets, duvet covers, duvet side areas, blankets, pillowcases and other bedding, sofa covers, table cloths and other interiors, and It is used for small items such as gloves, ties, scarves, and shawls, and is particularly preferably used for underwear, socks, bedding, etc. in terms of dissipating fragrance components.

The fabric which is the fiber structure of the present invention preferably contains, for example, about 2 to 100% by mass of the synthetic fiber, more preferably about 50 to 100% by mass, and further preferably about 80 to 100% by mass. What is more preferable. Further, it is also preferable that the fiber component is only synthetic fiber because the appearance quality is particularly excellent. Further, from the viewpoint of excellent appearance quality, the polyurethane elastic fiber is preferably contained in an amount of about 1 to 30% by mass, more preferably about 5 to 20% by mass, based on the total synthetic fiber.

Also, the fabric is a fiber structure of the present invention, from the viewpoint of deodorant is particularly excellent, it is preferable that the basis weight is 80~1000g / ^{m 2,} more preferably from 100 to 500 g / ^{m 2,} 100 It is more preferably ~ 280 g / m ² . Further, the elongation rate is preferably 5% or more in both the vertical direction and / or the horizontal direction.

Further, the fabric which is the fiber structure of the present invention preferably has a dimensional change rate of -5% or less due to home washing, and more preferably -3% or less.

The present invention will be described in more detail by way of examples.

[Permanent strain rate, breaking strength, breaking elongation of polyurethane elastic fiber]
The permanent strain rate, stress relaxation, breaking strength, and breaking elongation were measured by performing a tensile test on polyurethane elastic fibers using an Instron 4502 type tensile tester. The number of measurements was n = 3, and the average value thereof was adopted. A sample with a trial length of 5 cm (L1) was repeated 5 times at a tensile rate of 50 cm / min and 300% elongation was repeated, and the stress at the 5th 100, 200, 300% elongation was measured, and the stress at 300% elongation was measured (G1). ). Next, the length of the sample was kept at 300% elongation for 30 seconds. The stress after holding for 30 seconds was defined as (G2). Next, the elongation of the sample was restored, the stress at 200 and 100% elongation (recovery stress) was measured, and the length of the sample when the stress became 0 was defined as (L2). Further, it was stretched until the sample was cut for the sixth time. The stress at break was defined as (G3), and the sample length at break was defined as (L3). Hereinafter, the above characteristics are calculated by the following formula.
Breaking strength (cN) = (G3)
Permanent distortion factor (%) = 100 × ((L2)-(L1)) / (L1)
Elongation at break (%) = 100 × ((L3)-(L1)) / (L1).

[Heat setability of polyurethane elastic fiber]
The sample yarn (length = L5) was stretched 100% (length = 2 × (L5)). It was treated at 160 ° C. for 1 minute with this length. Further, it was left at room temperature for one day with the same length. Next, the stretched state of the sample yarn was removed, and the length (L6) thereof was measured.

Heat setability = 100 × ((L5)-(L6)) / (L5)
The higher the value, the better the heat settability.

[Heat resistance of polyurethane elastic fiber]
The heat resistance was measured by performing a tensile test on the sample yarn after heat setting as described above with an Instron 4502 type tensile tester.

These are defined below. A 5 cm sample was repeatedly stretched 300% 5 times at a tensile rate of 50 cm / min. The stress at break was defined as (G4). Hereinafter, the above characteristics are given by the following formula.

Heat resistance = (G4)
The higher the value of heat resistance, the better.

[Classic nitrogen content of polyurethane elastic fiber]
It was determined by a known method, that is, by dissolving the fiber in a solvent, neutralizing the primary amine and the secondary amine with a large excess of strong acid, and then neutralizing and titrating the tertiary amine.

[Melting point of polyurethane elastic fiber]
The melting point on the high temperature side, that is, the melting point of the hard segment crystal was measured as one of the indexes of the heat resistance of the polyurethane yarn. For the polyurethane yarn, a irreversible heat flow was measured at a heating rate of 5 ° C./min using a 2920 modulated DSC manufactured by TE Instruments, and the peak top was taken as the melting point.

[Small-angle X-ray scattering measurement and long period of polyurethane elastic fiber]
The method of measuring the polyurethane elastic fiber with a small angle X-ray and calculating the long period was carried out by the following method.

The long period J was obtained from, for example, the following Bragg's equation.

J = λ / 2 sin [{tan -1 (r / R)} / 2]
However, in the above formula, λ is the wavelength of the X-ray, R is the camera length (distance between the measurement sample and the scattering intensity detector), and r is calculated from the method described below according to a conventional method.

In the scattering image shown in FIG. 1, the distance from the equatorial line 2 to the maximum scattering intensity peak 3 is r for the long period in the meridian direction, and the scattering intensity from the meridian 1 to the maximum scattering intensity peak 4 for the long period in the equatorial line direction. It was calculated from the above Bragg's equation, where r was the distance to.

Then, an imaging plate was used as a scattering intensity detector, and synchrotron radiation was used as a light source in order to more accurately measure a long period J of 20 to 100 nm. The scattering angle 2θ in the Bragg's equation was approximated by {tan -1 (r / R)}. r was obtained from a continuous plot (scattering intensity profile) with 4πλ / sinθ (nm-1) along the meridian 1 and the equator line 2 on the horizontal axis and the scattering intensity on the vertical axis.
Sample preparation: The fibers were aligned and tensioned to remove slack, and the fibers were wound 50 times around a cardboard with a hole of 4 cm in length and the ends of both threads were tied to prepare a sample for measurement.
Equipment and conditions:
(1) Synchrotron radiation facility SPring-8 BL08B2
(2) Wavelength 0.10 nm
(3) Beam diameter 0.3 mm in length and 0.3 mm in width
(4) Camera length 2385 mm
(5) Exposure time 60 sec
(6) Detector R-AXIS-IV ++ (imaging plate) manufactured by Rigaku.

[Evaluation method of deodorant property]
SEK mark textile product certification standard (establisher: General Incorporated Association Textile Evaluation Technology Council Product Certification Department, revision date: April 1, 2015) conforms to the deodorant property test, and odor component by the detector tube method Deodorant property was evaluated. Ammonia, acetic acid, isovaleric acid, and nonenal were used as odor components.

The initial concentration of the odorous component is 100 ppm of ammonia, 30 ppm of acetic acid, 38 ppm of isovaleric acid, and 14 ppm of nonenal. As a blank test, a 5 L sample bag (made of film) is filled with only odorous components for each component, sealed, left for 2 hours, and then the residual gas concentration is measured using a gas detector tube corresponding to each component, and this is a blank test. Let it be the concentration. Next, a sample (10 cm x 10 cm) used for measurement is placed in a sample bag (made of film), filled with the above-mentioned odorous component having a predetermined concentration, sealed, and the residual gas concentration after 2 hours is measured by a gas detector tube corresponding to each component. Measure with, and use this as the measured concentration. The measurement is performed three times, and using the average value, the reduction rate of the residual gas concentration is calculated by the following formula and expressed as the deodorization rate.

Deodorant rate of each deodorant component (%) = ((blank test concentration-measured concentration of each sample) / blank test concentration)) x 100
The evaluation criteria for the deodorization rate were 70% or more for ammonia, 70% or more for acetic acid, 85% or more for isovaleric acid, and 75% or more for nonenal.

[Washing method]
In accordance with the standard washing method described in the washing method for SEK mark textile products (established by the Japan Textile Evaluation Technology Council Product Certification Department, revised date: April 1, 2014), JIS L 0217: 1995. Using a household electric washing machine specified in Washing Method 103 described in "Indication Symbols for Handling Textile Products and Their Labeling Methods", JAFET standard compound detergent (polyoxyethylene) at a ratio of 40 mL to 30 L of water at 40 ° C. Add alkyl ether and sodium alphaolefin sulfonate) to make a washing liquid, add a sample and a load cloth if necessary so that the bath ratio is 1:30, wash for 5 minutes, dehydrate, and rinse for 2 minutes. The steps of washing, dehydration, rinsing for 2 minutes, and dehydration were performed once, and this was repeated 10 times and 50 times, and then dried by hanging.

[Dimensional change rate]
JISL-1096: 2010 (revised) The pulsator type household electric washing machine method specified in the G method, according to the washing method of No. 103 of JISL-0217: 1995 (revised), liquid temperature 40 ° C., bath ratio 1: At 30, the detergent used was "Attack" (registered trademark, manufactured by Kao Co., Ltd.) at the manufacturer's standard concentration, and washing 5 minutes-dehydration-rinsing 2 minutes-dehydration-rinsing 2 minutes-dehydration was repeated 5 times as one washing. .. Then, the test piece was air-dried on a flat table. For the dimensional change rate, obtain the average value of the measurement sections at each of the three measurement sections in the vertical direction (wale direction) and the horizontal direction (course direction), and use the following equations for each of the vertical direction (wale direction) and the horizontal direction (course direction). The dimensional change rate of was calculated.
Dimensional change rate (%) = 100 x (L2-L1) / L1
L1: Average value (mm) of the length of the measurement section in the vertical direction (wale direction) or horizontal direction (course direction) before washing.
L2: The average value (mm) of the lengths of the measurement sections in the vertical direction (wale direction) or the horizontal direction (course direction) after washing.

[Appearance quality]
A light source was irradiated from the back surface of the processed knitted fabric, and the wrinkle / streak quality on the surface was visually evaluated with transmitted light based on the following five-step judgment.

5: No defects such as wrinkles and streaks 4: Almost no defects such as wrinkles and streaks 3: Some defects such as wrinkles and streaks 2: Many defects such as wrinkles and streaks 1: Defects such as wrinkles and streaks Is very large.

[Preparation of polyurethane elastic fiber PU112 used in Examples]
A container was charged with 4,4'-MDI to 1.55 mol with respect to 1 mol of PTMG having a number average molecular weight of 2000, reacted at 70 ° C., and the obtained reaction product was N, N-dimethylacetamide (DMAc). Was thoroughly stirred and dissolved to obtain a solution. Next, 1.15 mol of 4,4'-MDI was added to 1 mol of PTMG having the above-mentioned number average molecular weight of 2000, and the mixture was sufficiently stirred, and then a DMAc solution containing ethylene glycol (EG) as a chain extender was added. After stirring well, a DMAc solution containing butanol as a terminal sequestering agent was added to prepare a polyurethane solution pu1 having a polymer solid content of 35% by mass. The resulting solution had a viscosity of about 3000 poise at 40 ° C. The polymer had an intrinsic viscosity of 0.83 as measured in DMAc at a solution concentration of 0.5 g / 100 ml at 25 ° C.

Then, an addition polymer of divinylbenzene and p-cresol (“Metachlor (registered trademark)” 2390 manufactured by DuPont) as a stabilizer and butyldiphenyl ether represented by the general formula (3) as an alkyldiphenyl ether compound are added to this polyurethane solution pu1. Sulfonic acid was added in an amount of 2% by mass based on the solid content of pu1 to prepare pu112. This polyurethane solution is discharged from a spinneret into an inert gas (nitrogen gas) at a high temperature (350 ° C.) with 4 filaments, dried by passing through the high temperature gas, and an air jet so that the yarns in the process of drying are twisted together. Two filaments were coalesced through a type twisting machine and wound at a speed of 600 m / min to produce a 22 dtex polyurethane elastic fiber (PU112) by the two filaments fused.
Table 1 shows these characteristics such as long period.

[Preparation of polyurethane elastic fibers PU114 and PU118 used in Examples]
Only the amount of the alkyldiphenyl ether compound to be added to pu1 in PU112 was changed to the formulation shown in Table 1 to prepare the compound.

Table 1 shows these characteristics such as long period.

A small-angle X-ray scattering image of PU 114 is shown in FIG.

[Preparation of polyurethane elastic fiber PU212 used in Examples]
87.5 mol of dehydrated tetrahydrofuran and 12.5 mol of dehydrated 3-methyl-tetrahydrofuran were placed in a reactor with a stirrer, and the catalyst (70% by mass of perchloric acid and anhydrous) was charged at a temperature of 10 ° C. under a nitrogen seal. A copolymerized tetramethylene ether diol having a number average molecular weight of 2500, obtained by a polymerization method in which a polymerization reaction was carried out for 8 hours in the presence of a mixture of 30% by mass of acetic acid and the reaction completion solution was neutralized with an aqueous sodium hydroxide solution. A structural unit (a) derived from 3-methyl-tetrahydrofuran (containing 12.5 mol%) was used as the polyalkylene ether diol.

To 1 mol of this copolymerized tetramethylene ether diol, 1.2 mol of 4,4'-MDI was charged in a container and reacted at 80 ° C. until the NCO% by weight became 0.60. Add 4,4'-MDI to 0.5 mol of the initial copolymerized tetramethylene ether diol to 0.5 mol of the reaction product, react at 80 ° C, and N, N-dimethyl. Acetamide (DMAc) was added, and the mixture was thoroughly stirred and dissolved to obtain a solution. Next, 0.4 mol of 4,4'-MDI and a DMAc solution containing ethylenediamine (EDA) as a chain extender are simultaneously added to 1 mol of the above-mentioned copolymerized tetramethylene ether diol, and the mixture is sufficiently stirred. Next, a DMAc solution containing diethylamine (DEA) as an end-blocking agent was added to prepare a polyurethane solution pu2 having a polymer solid content of 35% by mass. The resulting solution had a viscosity of about 2900 poise at 40 ° C. The polymer had an intrinsic viscosity of 0.90 as measured in DMAc at a solution concentration of 0.5 g / 100 ml at 25 ° C.

Then, in this polyurethane solution pu2, an addition polymer of divinylbenzene and p-cresol as a stabilizer (“Metachlor (registered trademark)” 2390 manufactured by DuPont) and an alkyldiphenyl ether compound are represented by the general formula (3). Butyl diphenyl ether sulfonic acid was added in an amount of 2% by mass based on pu2 solid content to prepare pu212. This polyurethane solution is discharged from a spinneret into an inert gas (nitrogen gas) at a high temperature (350 ° C.) with 4 filaments, dried by passing through the high temperature gas, and an air jet so that the yarns in the process of drying are twisted together. Two filaments were coalesced through a type twisting machine and wound at a speed of 600 m / min to produce a 22 dtex polyurethane elastic fiber (PU212) by the two filaments fused.
Table 1 shows these characteristics such as long period.

[Preparation of polyurethane elastic fibers PU214 and PU218 used in Examples]
Only the amount of the alkyldiphenyl ether compound to be added to pu2 in PU212 was changed to the formulation shown in Table 1 to prepare the compound.

Table 1 shows these characteristics such as long period.

[Preparation of polyurethane elastic fibers PU122, PU124 and PU128 used in Examples]
The alkyldiphenyl ether compound to be blended with pu1 in PU112 was changed to sodium dodecyldiphenyl ether sulfonate represented by the general formula (4), and the addition amount was prepared according to the formulation shown in Table 1.

Table 1 shows these characteristics such as long period.

[Preparation of polyurethane elastic fiber PU10 used in Examples]
Only the amount of the alkyldiphenyl ether compound to be added to pu1 in PU112 was changed to the formulation shown in Table 1 to prepare the compound.

That is, it was prepared by changing to a formulation in which only the alkyldiphenyl ether-based compound in the preparation of PU112 was not added.

Table 1 shows these characteristics such as long period.

PU10 is the same as PU1X0 described later.

[Preparation of polyurethane elastic fiber PU3X14 used in comparative example]
4,4'-MDI was charged into a container so as to be 2.01 mol with respect to 1 mol of PTMG having a number average molecular weight of 2000, reacted at 70 ° C., and the obtained reaction product was N, N-dimethylacetamide (DMAc). Was thoroughly stirred and dissolved to obtain a solution. Next, a DMAc solution containing ethylene glycol (EG) as a chain extender was added, and the mixture was sufficiently stirred. Further, a DMAc solution containing butanol as a terminal sequestering agent was added to provide a polyurethane solution having a polymer solid content of 35% by mass. Pu3x was prepared. The resulting solution had a viscosity of about 3100 poise at 40 ° C. The polymer had an intrinsic viscosity of 0.90 as measured in DMAc at a solution concentration of 0.5 g / 100 ml at 25 ° C.

Thereafter, the polyurethane solution Pu3x, addition polymer of divinylbenzene and p- cresol as a stabilizer (manufactured by DuPont "meta crawling (registered trademark)" 2390), as a diphenyl ether compound Bed chill diphenyl ether sulfonic acid, Pu3x solid 4% by mass of each compound was added, and this polyurethane solution was discharged from the spinneret into a high-temperature (350 ° C.) inert gas (nitrogen gas) with 4 filaments, dried by passing through this high-temperature gas, and during drying. Two filaments were coalesced through an air jet twisting machine so that the yarns were twisted, and wound at a speed of 600 m / min to produce a 22 dtex polyurethane elastic fiber (PU3 × 14) by the two filaments fused.
Table 1 shows these characteristics such as long period.

[Preparation of polyurethane elastic fiber PU4X14 used in Comparative Example]
87.5 mol of dehydrated tetrahydrofuran and 12.5 mol of dehydrated 3-methyl-tetrahydrofuran were placed in a reactor with a stirrer, and the catalyst (70% by mass of perchloric acid and anhydrous) was charged at a temperature of 10 ° C. under a nitrogen seal. A copolymerized tetramethylene ether diol having a number average molecular weight of 2500, obtained by a polymerization method in which a polymerization reaction was carried out for 8 hours in the presence of a mixture of 30% by mass of acetic acid and the reaction completion solution was neutralized with an aqueous sodium hydroxide solution. A structural unit (a) derived from 3-methyl-tetrahydrofuran (containing 12.5 mol%) was used as the polyalkylene ether diol.

To 1 mol of this copolymerized tetramethylene ether diol, 4,4'-MDI was charged in a container so as to be 2.1 mol, reacted at 80 ° C., and reacted until NCO% became ~, and N, N- Dimethylacetamide (DMAc) was added, and the mixture was thoroughly stirred and dissolved to obtain a solution. Next, a DMAc solution containing ethylenediamine (EDA) as a chain extender is added, and the mixture is sufficiently stirred. Next, a DMAc solution containing diethylamine (DEA) as a terminal blocker was added to prepare a polyurethane solution pu4 having a polymer solid content of 35% by mass. The resulting solution had a viscosity of about 2500 poise at 40 ° C. The polymer had an ultimate viscosity of 0.86 as measured in DMAc at a solution concentration of 0.5 g / 100 ml at 25 ° C.

Thereafter, the polyurethane solution PU4, addition polymer of divinylbenzene and p- cresol as a stabilizer (manufactured by DuPont "meta crawling (registered trademark)" 2390), as an alkyl diphenyl ether compound Bed chill diphenyl ether sulfonate PU4 2% by mass of each solid content was added to adjust pu4 × 14. This polyurethane solution is discharged from a spinneret into an inert gas (nitrogen gas) at a high temperature (350 ° C.) with 4 filaments, dried by passing through the high temperature gas, and an air jet so that the yarns in the process of drying are twisted together. Two filaments were coalesced through a type twisting machine and wound at a speed of 600 m / min to produce a 22 dtex polyurethane elastic fiber (PU4 × 14) by the two-filament coupling.
Table 1 shows these characteristics such as long period.

[Preparation of polyurethane elastic fiber PU3X24 used in Comparative Example]
The alkyldiphenyl ether compound to be blended with pu3x in PU3X14 was changed to sodium dodecyldiphenyl ether sulfonate, and the amount added was prepared according to the formulation shown in Table 1.

Table 1 shows these characteristics such as long period.

[Preparation of polyurethane elastic fiber PU1X0 used in comparative example]
Only the amount of the alkyldiphenyl ether compound to be added to pu1 in PU112 was changed to the formulation shown in Table 1 to prepare the compound.

That is, it was prepared by changing to a formulation in which only the alkyldiphenyl ether-based compound in the preparation of PU112 was not added.

Table 1 shows these characteristics such as long period.

[Preparation of polyurethane elastic fiber PU2X0 used in comparative example]
Only the amount of the alkyldiphenyl ether compound to be added to pu2 in PU212 was changed to the formulation shown in Table 1 to prepare the compound.

That is, it was prepared by changing to a formulation in which only the alkyldiphenyl ether compound in the preparation of PU212 was not added.

Table 1 shows these characteristics such as long period.

[Preparation of polyurethane elastic fiber PU3X0 used in comparative example]
Only the amount of the alkyldiphenyl ether compound to be added to pu3x in PU3X14 was changed to the formulation shown in Table 1 to prepare the compound.

That is, it was prepared by changing to a formulation in which only the alkyldiphenyl ether-based compound in the preparation of PU3X14 was not added.

Table 1 shows these characteristics such as long period.

A small-angle X-ray scattering image of PU3X0 is shown in FIG.

[Preparation of polyurethane elastic fiber PU4X0 used in comparative example]
Only the amount of the alkyldiphenyl ether compound to be added to pu4x in PU4X14 was changed to the formulation shown in Table 1 to prepare the compound.

That is, it was prepared by changing to a formulation in which only the alkyldiphenyl ether compound in the preparation of PU4X14 was not added.

Table 1 shows these characteristics such as long period.

[Examples 1 to 18]
Polyurethane fibers PU112, PU114, PU118, PU122, PU124, PU128, PU10, PU212, PU214, and PU218 were used, and fiber structures were produced by combining the fiber contents shown in Table 2.

The fiber structure 1 was manufactured by the processing step-L in Table 3, and the fiber structure 2 was manufactured by the processing step-M in Table 3.

The fiber structures 3 to 5 were prepared by the processing step-LA2, the processing step-LA4, and the processing step LA8 in Table 3, respectively.

Table 2 shows the deodorant rate%, the dimensional change rate, and the appearance quality of each deodorant component of Examples 1 to 18.

[Comparative Examples 1 to 10]
Polyurethane fibers PU3X14, PU3x24, PU4X14 and PU1X0 to PU4x0 were used, and a fiber structure was produced by combining the fiber contents shown in Table 2.
The fiber structure 1X was manufactured by the processing step-L in Table 3, the fiber structure 2X was manufactured by the processing step-M in Table 3, and the fiber structure 4x was manufactured by the processing step-LA4 in Table 3.

Table 2 shows the deodorant rate%, the dimensional change rate, and the appearance quality of each deodorant component of Comparative Examples 1 to 10.

The fiber structure of the present invention has heat-setting property, heat resistance, deodorant property, recoverability, and elongation. Therefore, clothes, non-woven fabrics, and the like using this fiber structure are excellent in detachability, fit, wearing feeling, heat retention, appearance quality, and the like.

Due to these excellent properties, the polyurethane yarn used in the present invention can be used alone or in combination with various fibers to obtain an excellent stretch fabric, which can be knitted, woven, and stringed. Is suitable for. Specific uses that can be used include socks, stockings, tights, circular knitting, tricots, ski trousers, work clothes, fire clothes, golf trousers, wet suits, brassieres, girdles, gloves and other various textile products, tightening materials, Further, there are examples of tightening materials for preventing leakage of sanitary products such as paper socks, tightening materials for waterproof materials, imitation bait, artificial flowers, electrical insulating materials, wiping cloths, copy cleaners, gaskets and the like.

2 Equatorial line r Distance from the equatorial line to the maximum scattering intensity peak

Claims (9)

A fiber structure containing a polyurethane elastic fiber and an alkyldiphenyl ether-based compound, wherein the first long period (J1) in the fiber direction in the small angle X-ray scattering measurement of the polyurethane elastic fiber is 20 to 100 nm. There are two types of long cycles in the fiber direction in the small-angle X-ray scattering measurement of the polyurethane elastic fiber, and the second long cycle (J2) whose scattering intensity for detecting the long cycle is smaller than the first long cycle (J1) The fibrous structure according to claim 1 that exists. The fiber structure according to claim 1 or 2, wherein the second long period (J2) is 7 to 19 nm. Claim 1 in which the ratio of the second long period (J2) to the first long period (J1) is 2 ± 0.2, 3 ± 0.2, 4 ± 0.2 or 5 ± 0.2. The fiber structure according to any one of ~ 3. The fiber structure using the polyurethane elastic fiber according to any one of claims 1 to 4, wherein the long period in the equatorial line direction in the small-angle X-ray scattering measurement of the polyurethane elastic fiber is 10 to 20 nm. The fiber structure according to any one of claims 1 to 5, wherein the alkyl diphenyl ether compound contains an alkyl diphenyl ether sulfonic acid and / or an alkyl diphenyl ether sulfonate. The fiber structure according to any one of claims 1 to 6, wherein the alkyldiphenyl ether-based compound is contained in the polyurethane elastic fiber. Using an alkyldiphenyl ether-based compound at the same time and / or after dyeing the fiber structure to be treated containing polyurethane elastic fibers having a first long period (J1) in the fiber direction of 20 to 100 nm in small angle X-ray scattering measurement. A method for producing a fiber structure to be treated in a bath. A method for producing a fiber structure in which a fiber structure to be treated containing polyurethane elastic fibers having a first long period (J1) in the fiber direction of 20 to 100 nm in small-angle X-ray scattering measurement is padded with an alkyldiphenyl ether-based compound. ..