JP2017119938A - Fiber structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fiber structure excellent in heat setting, heat resistance, dyeability, recoverability and elongation, and a manufacturing method thereof.SOLUTION: A fiber structure comprises polyurethane elastic fiber, the polyurethane elastic fiber having a first long cycle (J1) of 20 to 100 nm in the fiber direction in the measurement of small angle X-ray scattering, containing a tertiary nitrogen compound.SELECTED DRAWING: None

Description

  The present invention relates to a fiber structure excellent in heat setability, heat resistance, dyeability, recoverability, and elongation.

  Fiber structures containing polyurethane elastic fibers are widely used for stretchable clothing such as legwear, innerwear, sportswear, and stretchable materials such as paper diapers and sanitary products because of their excellent stretch properties (stretch function). Yes.

  In addition, with the expansion of its use, the content of polyurethane elastic fibers in the fiber structure is becoming higher in order to further improve the stretch function. From such a background, fiber structures including polyurethane elastic fibers have been required to have higher characteristics. Typical required properties include heat setting at low temperatures that can be processed at lower temperatures to save energy in the manufacturing process, and higher temperatures to improve yield when applying post-processing repeatedly. It has heat resistance, the improvement of the dyeability supposing the case where it contains the polyurethane elastic fiber of a high mixing rate, and also having higher strength, elongation, and recoverability.

  On the other hand, techniques (for example, see Patent Document 1) that disclose the structure and characteristics of polyurethane elastic fibers and techniques that disclose the composition and characteristics have been proposed (for example, see Patent Documents 2 and 3).

  Patent Document 1 discloses in detail an example of fiber structure analysis based on the long period of small-angle X-ray scattering measurement of polyurethane elastic fibers. It is known that the long period in the small-angle X-ray scattering measurement is usually 7 to 16 nm.

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

  However, when the above technique is applied to a fiber structure containing polyurethane elastic fibers, Patent Document 1 requires further improvement in terms of heat resistance and recoverability, and Patent Documents 2 and 3 in terms of dyeability. .

  An object of the present invention is to further improve these characteristics and provide a fiber structure suitable for stretchable clothing and stretchable materials, and a method for producing the same.

In order to achieve the above object, the fiber structure of the present invention employs any one of the following means.
[1] A fiber structure containing polyurethane elastic fibers, wherein the first long period (J1) in the fiber direction in small-angle X-ray scattering measurement of the polyurethane elastic fibers is 20 to 100 nm and contains a tertiary nitrogen compound. Fiber structure.
[2] There are two types of long periods in the fiber direction in small-angle X-ray scattering measurement of polyurethane elastic fibers, and the second long period (J2) in which the scattering intensity for detecting the long period is smaller than the first long period (J1) [1] The fiber structure according to [1].
[3] The fiber structure according to any one of [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], wherein the long period in the equator 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], wherein the content of the tertiary nitrogen compound is 0.05 to 7 meq / kg as a tertiary amine nitrogen atom.
[7] Any of the above [1] to [6], wherein the tertiary nitrogen compound is a polyurethane having a structure starting from a tertiary nitrogen-containing diol, a tertiary nitrogen-containing diamine and an organic diisocyanate, or polyurethane urea. The fiber structure according to 1.
[8] The above-mentioned tertiary nitrogen compound is a polyurethane or polyurethane urea having a structure starting from a tertiary nitrogen-containing diol, a tertiary nitrogen-containing diamine and an organic diisocyanate, and the terminal group is a dialkyl semicarbazide. ] The fiber structure in any one of [7].
[9] The fiber structure according to any one of [1] to [8], including synthetic fibers other than polyurethane elastic fibers.
[10] The fiber structure according to any one of [1] to [9], including a polyurethane elastic fiber as a bare thread (bare).
[11] The fiber structure according to any one of [1] to [10], wherein the fastness to washing according to JIS L 0848: 2011 A-2 method is 4 or more.

  The fiber structure of the present invention is excellent in heat setability, heat resistance, dyeability, recoverability, and elongation, and has an excellent appearance and is suitable for stretchable clothing and stretchable materials.

It is a small angle X-ray-scattering image of PU12 in the Example of this invention. It is a small angle X-ray-scattering image of PU3X0 in a comparative example.

  In the present invention, an image obtained by small-angle X-ray scattering measurement of a polyurethane elastic fiber (hereinafter sometimes referred to as a scattered image) shows a new scattered image, that is, the first length in the fiber direction (meridian direction). It has been found that when the period (J1) is 20 to 100 nm longer than the conventional one and further contains a tertiary nitrogen compound, the above-described problems can be solved. This is because when the first long period (J1) is 20 to 100 nm, the dyeing property as the polyurethane elastic fiber, in particular, the dyeing property is further enhanced. From this point of view, the first long period (J1) is more preferably 25 to 70 nm. If such a range is adopted, the range of adjustment of the dyeing property by changing the content of the tertiary nitrogen compound is different from that of other structures. It is because it becomes remarkably wider than the fiber.

  From the scattered image obtained when small-angle X-ray scattering measurement of polyurethane elastic fiber and the calculated long period, crystals are arranged in a layered manner in a cross section perpendicular to the fiber direction, and amorphous in the gaps between the crystals arranged in a layered manner It can be seen that there is a sex area. In the polyurethane elastic fiber, the amorphous region (hereinafter sometimes referred to as a gap) is considered to be composed of a segmented polyurethane-urethane chain or a soft segment chain in the segmented polyurethane-urea chain. In the present invention, it has been found that a tertiary nitrogen compound that functions as a dyeing locus can be stably present in a polyurethane elastic fiber having a fiber structure having a large volume of the gap, that is, a fiber structure having a large long period. It has come.

  In the polyurethane elastic fiber used in the present invention, a plurality of long periods in the fiber direction in the small-angle X-ray scattering measurement may exist. 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 is a long period in which the X-ray scattering intensity (Intensity) for identifying the long period has the maximum value, and corresponds to the brightest peak in the small-angle X-ray scattering image. And it is also preferable that there exist a plurality of long periods in the equator axis direction in addition to the fiber direction, and it is also preferable to have two types of high strength and weak strength. Among them, if the first long period in the fiber direction calculated from the peak of the 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. Moreover, when it has the structure which satisfy | fills these, the tertiary nitrogen compound which is a dyeing locus can be stably hold | maintained still more. By these, it is excellent also in a stretching property, and fiber structures, such as a fabric containing this polyurethane elastic fiber, show favorable dyeability.

  Further, the ratio of J2 to J1 is preferably in the vicinity of an integral multiple, from the viewpoint of stretch characteristics, 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 vicinity of the integral multiple means a range of ± 0.2. When it is in the vicinity of an integer of 2 or more, the stretchability is further improved, and the stretchability when it is made into a fabric is better, and when it is in the vicinity of an integer of 5 or less, the permanent set is not excessive, and the fiber structure When it is applied, the stretchability will be better.

  As for the long period in the equator line direction in the small-angle X-ray scattering measurement of polyurethane elastic fibers, it has been customary that the long period observed in conventional polyurethane elastic fibers is less than 15 nm, usually 5 to 10 nm. In the polyurethane elastic fiber having J1 of 20 to 100 nm, the long period in the equator direction is preferably observed at 10 to 20 nm, and a fiber structure exhibiting better heat setting properties can be obtained.

  In the present invention, the method of measuring polyurethane elastic fibers with small-angle X-rays 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 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 Bragg equation, where r is the distance from the equator line 2 to the maximum scattering intensity peak. (Similarly, the long period in the equator direction can be obtained from the above Bragg equation, where r is the distance from the meridian to the scattering intensity maximum scattering intensity peak.)
And although a scattering intensity detector may be a camera or an imaging plate, since the polyurethane elastic fiber used for the present invention shows a new scattering image in a small angle X-ray scattering image, and shows a long period J of 20-100 nm, In order to measure the long period J more accurately, it is more preferable to use radiated light as a light source and digitize the scattered intensity detection using an imaging plate. In particular, synchrotron radiation, which is impossible with a conventional goniometer, can be constantly used as a high-energy light source of the order of several tens of keV to several GeV, and the measurement time can be shortened. It is possible to minimize the time effect of deformation and alteration due to micro distortion and gravity. Suitable examples of synchrotron radiation include Japan's SPring-8, which is a third generation synchrotron radiation facility, APS in the United States, and ESRF in Europe. For example, SPring-8 allows general use research, and specifically, the Hyogo Prefecture beam line (BL08B2 or BL24XU) is suitable. The scattering angle (referred to as 2θ) in the Bragg equation is approximated by {tan −1 (r / R)}, but 2θ can be detected with higher accuracy by using the emitted light or the detector. It is. For long-period calculation, r is usually from a continuous plot (scattering intensity profile) with the abscissa representing the inverse spatial axis (4πλ / sin θ (nm-1)) along the meridian 1 and the equator 2 and the ordinate representing the scattering intensity. It is more preferable to obtain it.

  The typical composition which comprises the polyurethane in the polyurethane elastic fiber used for this invention is described.

  The polyurethane-based resin used in the present invention may be any polyurethane as long as the main components are a polymer diol and a diisocyanate, and is not particularly limited. Also, the synthesis method is not particularly limited. In addition, a main component means the component which comprises 50 mass% or more among the components which form a polyurethane.

  That is, for example, it may be a polyurethane urea composed of a polymer diol, a diisocyanate and a chain extender and a diamino compound (low molecular weight diamine), or a polyurethane composed of a polymer diol, a diisocyanate and a low molecular weight diol as a chain extender. Also good. Moreover, the polyurethane urea which uses the compound which has a hydroxyl group and an amino group in a molecule | numerator as a chain extender may be used. In addition, it is also preferable to use trifunctional or higher polyfunctional glycols, isocyanates and the like as long as the effects of the present invention are not hindered.

  Here, typical structural units constituting the polyurethane 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. In particular, polyether glycols are preferably used from the viewpoint of imparting high elongation when deodorizing, flexibility, and fibers.

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

(Where a and c are integers of 1 to 3, b is an integer of 0 to 3, R3 and R4 are H or an alkyl group 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 PTFE, 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 Random copolymers in which are randomly arranged. As the polyurethane resin used in the present invention, one kind of these polyether glycols may be used, or two or more kinds may be used by mixing or copolymerizing. Among them, it is preferable to use PTMG or modified PTMG.

  Also, from the viewpoint of enhancing the wear resistance and light resistance in polyurethane resins, it is obtained by polycondensing a mixture of butylene adipate, polycaprolactone diol, 3-methyl-1,5-pentanediol and polypropylene polyol with adipic acid or the like. Dicarboxylic acid derived from a diol component and a polyester glycol such as a polyester diol having a side chain having a structure such as 3,8-dimethyldecanedioic acid and / or 3,7-dimethyldecanedioic acid A polycarbonate diol containing an acid ester unit is preferably used. Note that “having a structure obtained by condensation polymerization of...” Is indicated by a raw material and a reaction in order to specify a chemical structure. That is, as long as it has the structure specified by them, a raw material and reaction are not restrict | limited.

Moreover, these polymer diols may be used alone, or may be used by mixing or copolymerizing two or more thereof.
Next, as the diisocyanate of the structural unit constituting the polyurethane resin used in the present invention, aromatic diisocyanate, alicyclic diisocyanate, aliphatic diisocyanate and the like are preferable. As the aromatic diisocyanate, for example, diphenylmethane diisocyanate (hereinafter abbreviated as MDI), tolylene diisocyanate, 1,4-diisocyanate benzene, xylylene diisocyanate, 2,6-naphthalene diisocyanate, etc., particularly polyurethane having high heat resistance and strength. Suitable for synthesis. Examples of the alicyclic diisocyanate include methylene bis (cyclohexyl isocyanate) (hereinafter abbreviated as PICM), isophorone diisocyanate, methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate, cyclohexane-1,4- Diisocyanate, hexahydroxylylene diisocyanate, hexahydrotolylene diisocyanate, octahydro-1,5-naphthalene diisocyanate and the like are preferable. Aliphatic diisocyanates can be used effectively particularly in suppressing polyurethane yellowing. Among these, 4,4′-MDI is preferable. And these diisocyanates may be used independently and may use 2 or more types together.

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

  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-xylylene. Examples include range amine, p, p′-methylenedianiline, 1,3-cyclohexyldiamine, hexahydrometaphenylenediamine, 2-methylpentamethylenediamine, and bis (4-aminophenyl) phosphine oxide. Particularly preferred is EDA. By using EDA, it is possible to obtain a resin excellent in elongation, elastic recovery, and heat resistance. You may add to these chain extenders the triamine compound which can form a crosslinked structure, for example, diethylenetriamine, etc. to such an extent that an 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 -Ethanediol and the like are typical ones. Particularly preferred are EG, 1,3-propanediol, and 1,4-butanediol. When these are used, the diol-extended polyurethane has high heat resistance, and the strength can be increased when a polyurethane fiber is used.

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

  Furthermore, it is also preferable for the polyurethane in the present invention to use one or more end blockers. As end-capping agents, monools such as ethanol, propanol, butanol, isopropanol, allyl alcohol, cyclopentanol, and monoisocyanates such as phenyl isocyanate are preferred.

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

  Examples of the amine catalyst include N, N-dimethylcyclohexylamine, N, N-dimethylbenzylamine, triethylamine, N-methylmorpholine, N-ethylmorpholine, N, N, N ′, N′-tetramethylethylenediamine, 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-dimethyla Noethanol, N, N, N′-trimethylaminoethylethanolamine, N-methyl-N ′-(2-hydroxyethyl) piperazine, 2,4,6-tris (dimethylaminomethyl) phenol, N, N-dimethyl Examples include aminohexanol and triethanolamine.

  Examples of organometallic catalysts include tin octoate, dibutyltin dilaurate, and lead dibutyl octoate.

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

  In the solution polymerization method, it is preferable to apply so-called multistage polymerization in which diisocyanate is added stepwise to the polymer diol. As a specific process, the first stage should be carried out in the absence of a solvent, and after obtaining the theoretical end-point prepolymer, the prepolymer should be sufficiently diluted once by dissolving it in a solvent more than twice its mass. Is more preferable. The total amount of diisocyanate added after the second stage is smaller than the molar ratio of the first stage in terms of the reaction equivalent ratio (molar ratio) of the terminal isocyanate group of the diisocyanate to the terminal hydroxyl group of the polymer diol. Further preferred.

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

  The polyurethane elastic fiber constituting the fiber structure of the present invention contains a tertiary nitrogen compound. When a tertiary nitrogen compound is not contained in the polyurethane elastic fiber, useful dyeability cannot be obtained for the fiber structure.

  Conventionally, even if a large amount of a tertiary nitrogen compound is contained in order to increase the dyeing seat and obtain a high dyeing property, the effect has reached a relatively early level and it has been difficult to sufficiently dye. . That is, the adjustment range of the dyeing property was narrow, and the level of the dyeing property that reached its peak was low. Specifically, the content of the tertiary nitrogen compound in the polyurethane elastic fiber reached a peak at about 3 meq / kg as a tertiary amine nitrogen atom. Further, from the viewpoint of obtaining better basic physical properties as a polyurethane elastic fiber, it is preferable that the content of the tertiary nitrogen compound is not too much. However, when a tertiary nitrogen compound is contained in the polyurethane having the structure specified in the present invention, the range of adjustment of the dyeing property by increasing or decreasing the content of the tertiary nitrogen compound is wider. The upper limit value of the dyeing property adjusted by this also becomes higher. Furthermore, even if a large amount of a tertiary nitrogen compound is contained, it becomes possible to maintain better basic physical properties as a polyurethane elastic fiber, and the fiber structure shows a clear difference in stretch properties from the conventional one. The content of the tertiary nitrogen compound is preferably 0.05 to 7 meq / kg as a tertiary amine nitrogen atom, and is 0.1% by mass or more and 20% by mass or less, more preferably 1% by mass or more on a mass basis. 15 mass% or less, More preferably, the range of 3 mass% or more and 8 mass% or less is good. In addition, what is necessary is just to test this content beforehand according to a use and to determine an optimal value suitably.

  The tertiary nitrogen compound is not particularly limited except that it is a compound having tertiary nitrogen in the molecule. For example, a relatively low molecular weight monomeric material having a molecular weight of about 1000 or less may be used. It may be a relatively high molecular weight oligomer or polymer having a molecular weight of about 1000 or more (hereinafter referred to as a polymer having tertiary nitrogen). A polymer having N, N-dialkyl semicarbazide at the terminal is also preferred. In particular, from the viewpoint of dyeing fastness, a polymer having tertiary nitrogen is preferable.

  Preferable specific examples of the polymer having tertiary nitrogen include, for example, a tertiary nitrogen-containing diol, a tertiary nitrogen-containing diamine, and an organic diisocyanate known as antioxidants for polyurethane elastic fibers. A polyurethane or polyurethane urea having the structure In addition, “having a structure having a tertiary nitrogen-containing diol and a tertiary nitrogen-containing diamine and an organic diisocyanate as starting materials” is indicated by a starting material in order to specify the chemical structure. That is, any starting material may be used as long as it has a structure specified by these starting materials. Moreover, the polymer etc. which gave the N, N-dialkyl semicarbazide terminal group to such a polyurethane or polyurethane urea are mentioned. A compound having a tertiary nitrogen in the main chain and having an N, N-dialkyl semicarbazide at the terminal can exhibit high heat resistance during dyeing even at a low concentration of N, N-dialkyl semicarbazide. It can be made to have higher elastic recovery and higher strength than when it is not blended.

  Preferable specific examples of the tertiary nitrogen-containing diol include, for example, N-methyl-N, N-diethanolamine, N-methyl-N, N-dipropanolamine, N-methyl-N, N-diisopropanolamine, N-butyl-N, N-diethanolamine, Nt-butyl-N, N-diethanolamine (hereinafter abbreviated as TBDEA), N-octadecane-N, N-diethanolamine, N-benzyl-N, N-diethanolamine ( (Hereinafter abbreviated as BDEA), Nt-butyl-N, N-diisopropanolamine, and piperazine derivatives such as bishydroxyethylpiperazine and bishydroxyisopropylpiperazine can also be used. Of these, TBDEA or BDEA is particularly preferred.

  Preferable specific examples of the tertiary nitrogen-containing diamine include, for example, N-methyl-3,3′-iminobis (propylamine) (hereinafter abbreviated as MIBPA), N-butyl-aminobis-propylamine, and N-methyl. -Aminobis-ethylamine, Nt-butyl-aminobis-propylamine, piperazine-N, N'-bis (3-aminopropyl) (hereinafter abbreviated as BAPP), piperazine-N, N'-bis (2- Aminoethyl) and the like can be used. Among these, MIBPA or BAPP is particularly preferable.

  Preferable specific examples of the organic diisocyanate include, for example, aliphatic diisocyanates such as PICM, isophorone diisocyanate (hereinafter abbreviated as IPDI), lysine diisocyanate, and DDI derived from dimer acid. Of these, PICM or IPDI is particularly preferable.

  And when reacting with organic diisocyanate and forming a terminal semicarbazide group, it is preferable to use a substituted hydrazine. Preferable specific examples of the substituted hydrazine include, for example, N, N-dimethylhydrazine (hereinafter abbreviated as UDMH), N, N-diethylhydrazine, N, N-dipropylhydrazine, N, N-diisopropylhydrazine, N, N-dibutylhydrazine, N, N-diisobutylhydrazine, N, N-dihydroxyethylhydrazine (hereinafter abbreviated as UDHEH), N, N-dihydroxyisopropylhydrazine and the like can be used. Of these, UDMH or UDHEH is particularly preferable. Polymers with N, N-dialkylsemicarbazide end groups on polyurethane or polyurethaneurea contain isocyanate-terminated prepolymers and N, N-dialkylhydrazines, and stoichiometric amounts of hydrazine before adding other chain terminators. It is preferable to prepare it by adding it to complete reaction.

  The average molecular weight of the polymer having tertiary nitrogen is preferably 1000 or more and 20000 or less, and the semicarbazide group in 1 kg of the polymer having N, N-dialkyl semicarbazide at the terminal is 0.1 to 100 meq / kg (meq / kg). It is preferable to contain in the range of.

  In order to obtain a particularly high dyeing property, as a tertiary nitrogen compound, TBDEA and PICM are polymerized with an addition polymerization product in a ratio of 2 to 3 to 20 to 21, or UDMH is reacted at the terminal. A compound in which dimethyl semicarbazide is formed, a mixture of MIBPA and PICM and polyurethane urea in which PICM is 2 to 3 to 20:21, or a compound in which dimethyl semicarbazide is formed by reacting UDMH at the terminal thereof. Can be mentioned. The semicarbazide group is preferably contained in a range of 1 to 200 milliequivalents (meq / kg) in 1 kg of the yarn. Specific examples of TBDEA and PICM polyurethane include “METACROL (registered trademark)” 2462 manufactured by DuPont.

  Furthermore, it may be preferable to add various additives described later to the polyurethane resin used in the present invention. As a method for adding various additives, any method can be adopted. As typical methods, various means such as a method using a static mixer, a method using stirring, a method using a homomixer, a method using a biaxial extruder, and the like can be adopted. Here, the various additives to be added are preferably added in the form of a solution from the viewpoint of uniform addition to the polyurethane when the polyurethane is synthesized by solution polymerization.

  In addition, by adding various additives to the polyurethane solution, a phenomenon may occur in which the solution viscosity of the mixed solution after the addition becomes higher than expected compared to the polyurethane solution viscosity 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 more end-capping agents such as monoamines, ethanol, propanol, butanol, isopropanol, allyl alcohol, cyclopentanol and the like, and monoisocyanates such as phenyl isocyanate.

  Furthermore, the polyurethane-based resin used in the present invention may contain various stabilizers, pigments and the like as long as the effects of the present invention are not impaired. For example, as a stabilizer, an addition polymer of divinylbenzene and p-cresol (“Methacryl (registered trademark)” 2390 manufactured by DuPont), t-butyldiethanolamine and methylene-bis- (4-cyclohexyl isocyanate) As a starting material, polyurethane (DuPont "Metacral (registered trademark)" 2462), a light-proofing agent, an antioxidant, etc., so-called BHT and Sumitomo Chemical Co., Ltd. "Smilizer (registered trademark)" "Hindered phenolic drugs such as GA-80", benzotriazoles such as "Tinubin (registered trademark)" manufactured by Ciba Geigy, and "Sumilyzer (registered trademark)" manufactured by Sumitomo Chemical Co., Ltd. "P-16 and other phosphorus drugs, various hindered amine drugs, titanium oxide, carbon black Inorganic pigments such as lacquer, fluorine resin powder or silicone resin powder, metal soaps such as magnesium stearate, and bactericides, deodorants, silicones and minerals containing silver, zinc and their compounds Lubricants such as oil, various antistatic agents such as barium sulfate, cerium oxide, betaine and phosphoric acid may be added, or they may be allowed to react with the polymer. In particular, in order to further enhance the durability to light and various types of nitric oxide, for example, HN-150 manufactured by Nippon Hydrazine Co., Ltd. as a nitric oxide scavenger, and as a thermal oxidation stabilizer, for example, Sumitomo Chemical ( For example, “Sumisorb (registered trademark)” 300 # 622 manufactured by Sumitomo Chemical Co., Ltd. may be included as a light stabilizer.

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

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

  Further, from the viewpoint of enhancing dyeability, 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 0.00. 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) × 2 / (polyurethane resin mass (kg)).

  The most preferred composition of the polyurethane in the present invention is to obtain a polyurethane by polymerizing a polymer diol having a number average molecular weight of 500 or more and 5000 or less, an organic diisocyanate, and a chain extender comprising a low molecular diol, and 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 diol and the low molecular diol is 2.5 to 4.0 or less, and the mass of the low molecular diol to the high molecular diol The ratio is in the range of 1/9 to 5/5.

  When the reaction equivalence ratio exceeds 4.0, the elongation at break, recoverability, and heat setability of the resulting polyurethane elastic fiber are lowered, and the dyeability and stretch of fiber structures such as fabrics and knitted fabrics using the same are reduced. The characteristics may deteriorate.

Moreover, it is preferable that the molecular weight of the polyurethane in this invention is the range of 40,000 or more and 150,000 or less as a number average molecular weight from a viewpoint of obtaining fiber with durability and high intensity | strength. In the present invention, the molecular weight is a value measured by GPC and converted by polystyrene.
In the synthesis of such polyurethane, it is also preferable to use one or a mixture of two or more catalysts such as amine catalysts and organometallic catalysts.

  Examples of the amine catalyst include N, N-dimethylcyclohexylamine, N, N-dimethylbenzylamine, triethylamine, N-methylmorpholine, N-ethylmorpholine, N, N, N ′, N′-tetramethylethylenediamine, 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-dimethyla Noethanol, N, N, N′-trimethylaminoethylethanolamine, N-methyl-N ′-(2-hydroxyethyl) piperazine, 2,4,6-tris (dimethylaminomethyl) phenol, N, N-dimethyl Examples include aminohexanol and triethanolamine.

  Examples of organometallic catalysts include tin octoate, dibutyltin dilaurate, and lead dibutyl octoate.

  The concentration of the polyurethane solution thus obtained in the spinning dope is usually preferably in the range of 30% by mass to 80% by mass.

  Further, in the present invention, additives such as various stabilizers and pigments may be contained in the polyurethane elastic fiber and the later-described polyurethane spinning dope for spinning it. For example, hindered materials such as 2,6-di-t-butyl-p-cresol (BHT) and “Sumilyzer (registered trademark)” GA-80 (product name) manufactured by Sumitomo Chemical Co. Phenolic drugs, various benzotriazoles such as “Chinubin (registered trademark)” manufactured by Ciba Geigy, benzophenone drugs, phosphorus such as “Sumilyzer (registered trademark)” P-16 (product name) manufactured by Sumitomo Chemical Co., Ltd. Agents, various hindered amine agents, various inorganic pigments such as iron oxide, titanium oxide, and carbon black, fluorine or silicone resin powder, metal soaps such as magnesium stearate, calcium stearate, lithium stearate, and silver Bactericides, deodorants, silicones, amino-modified silicones containing zinc and zinc and their compounds , Carboxy modified silicone, lubricants such as mineral oil, are preferred and various antistatic agents such as cerium oxide, betaine and phosphoric acid and also the reaction of these with polymers preferred. And it is also preferable to use a nitric oxide scavenger in order to further enhance the durability to light and various nitric oxides.

In addition, from the viewpoint of improving heat resistance and functionality, inorganic materials and inorganic porous materials (for example, bamboo charcoal, charcoal, porous mud, clay minerals, diatomaceous earth, coconut husk activated carbon, coal-based activated carbon, zeolite, hadrotalcite, hydro (Magsite, huntite, pearlite, etc.) may be added within a range that does not impair the effects of the present invention.
From the viewpoint of the aesthetics of the fiber structure of the present invention, it is particularly preferable that the inorganic material contains a fine particle inorganic material.
Conventionally, even if a large amount of fine particle inorganic material is included to obtain high aesthetics, even if a certain amount of fine particle inorganic material is contained to some extent, the effect has reached a relatively early level and it has been difficult to sufficiently function. That is, the adjustment range for color development was narrow, and the level of aesthetics that reached its peak was also low. Specifically, curing has reached its peak before the aesthetics are sufficiently improved even if the content of the particulate inorganic substance in the polyurethane elastic fiber is increased. Further, from the viewpoint of obtaining better basic physical properties as a polyurethane elastic fiber, it was preferable that the content of the particulate inorganic material is not too much. However, when the particulate inorganic material is contained in the polyurethane having the structure specified in the present invention, the adjustment range of the aesthetics due to the increase or decrease in the content of the particulate inorganic material is wider, and the aesthetics adjusted thereby. The adjustment upper limit of the sex is also increased. Further, even if a large amount of fine inorganic particles are added, it is possible to maintain better basic physical properties as polyurethane elastic fibers, and the fiber structure shows a clear difference in stretch characteristics from the conventional one. The content of the fine inorganic particles is preferably 1 to 20% by mass, more preferably 1% to 15% by mass, and still more preferably 3% to 8% by mass. In addition, what is necessary is just to test this content beforehand according to a use and to determine an optimal value suitably.

A preferred example of the fine inorganic particles is a pigment.
The pigment suitable for the present invention is a pigment and / or dye, and is not particularly limited in hue and composition. For example, carbon fine particles (sometimes referred to as carbon black), phthalocyanine pigment, azo pigment, titanium oxide, zinc oxide, barium sulfate, iron oxide, cerium oxide, magnesium oxide, azo dye, indigoid dye, phthalocyanine dye Of these, carbon black and phthalocyanine compounds are preferred, and carbon black and copper phthalocyanine are more preferred. Furthermore, the pigment | dye used for this invention should just become a black hue as a polyurethane thread | yarn by the combination, About each pigment | dye, you may use what kind of hue. For example, it is also preferable to use a complementary color. Depending on the particle size of the dye, especially the average primary particle size and specific surface area of the carbon black, the hue of the polyurethane yarn may shift in the red direction. Add phthalocyanine compounds, especially pigment blue and pigment green of copper phthalocyanine pigments. Thus, the polyurethane yarn can be made achromatic black. Furthermore, from the viewpoint of compensating for the hue, pigments other than carbon black can be used in combination of two or more. In the polyurethane yarn of the present invention, when carbon black is contained, the effect of high aesthetics is remarkable, and when it is combined with other fibers to form a fiber structure such as a knitted fabric or a woven fabric, a remarkable dark color sharpness is obtained. This is preferable. As the carbon black used in the present invention, a hydrocarbon or a crystallite aggregate formed by burning or thermally decomposing a hydrocarbon-containing compound shown in JIS K6200 in a state where the supply of air is insufficient is applied. The oil furnace method, the gas furnace method, the channel method, or the thermal method can be used, and is not particularly limited. Examples thereof include acetylene black, ketjen black, oil furnace black, gas furnace black, channel black, roller black, fine thermal black, medium thermal black, lamp black, pine smoke, oil smoke, vegetable black and the like.

  The content of carbon black is preferably in the range of 0.1% by mass to 20% by mass from the viewpoint of obtaining good black uniformity and spinnability, and from the viewpoint of obtaining good aesthetics, 0.5% by mass or more. 10 mass% or less is more preferable. In addition, it is also preferable that these contents are suitably determined by testing in advance according to the use.

  Furthermore, carbon black has an average primary particle diameter of carbon black measured by an electron microscope of 20 nm to 100 nm from the viewpoint of speeding up dispersion in polyurethane and making the characteristics of the polyurethane yarn to be produced a target characteristic. Is preferred. Further, from the viewpoint of obtaining good aesthetics, 30 nm to 80 nm is more preferable.

Furthermore, carbon black preferably has a specific surface area (BET adsorption method) of 20 m ² / g or more from the viewpoint of increasing the darkness of the polyurethane yarn. Furthermore, it is preferably 30 m ² / g or more.

  Carbon black has a reduced weight (volatile content) when heated at 950 ° C. for 7 minutes as defined in Japanese Industrial Standard K6221 from the viewpoint of preventing impurities from being mixed into the polyurethane yarn to be produced and achieving the target characteristics. What is the range of 0.5-5 mass% is preferable.

  Furthermore, from the viewpoint of imparting deodorant properties to the fiber structure of the present invention, it is preferable to contain a metal phosphate.

Conventionally, even if a large amount of a metal phosphate is contained in order to increase the deodorizer and obtain a high deodorant property, it has been difficult to obtain a sufficient effect because the effect has reached its peak relatively quickly. That is, the deodorant adjustment range was narrow, and the level of deodorant that reached its peak was also low. Specifically, the content of the metal phosphate in the polyurethane elastic fiber reached a peak at about 3% by mass. Further, from the viewpoint of obtaining better basic physical properties as a polyurethane elastic fiber, it was preferable that the content of metal phosphate is not too much. However, when the metal phosphate is contained in the polyurethane having the structure specified in the present invention, the range of adjustment of the deodorizing property by the increase or decrease in the content of the metal phosphate is wider, and the adjustment is made thereby. The upper limit of the deodorant adjustment is also increased. Furthermore, even if a large amount of metal phosphate is contained, it becomes possible to maintain better basic physical properties as polyurethane elastic fibers, and as a fiber structure, a clear difference in stretch characteristics from the conventional one is exhibited. The content of the metal phosphate is preferably 0.5% by mass or more and 50% by mass or less, more preferably 1% by mass or more and 20% by mass or less, and further preferably 3% by mass or more and 8% by mass or less. Good. In addition, what is necessary is just to test this content beforehand according to a use and to determine an optimal value suitably.
From the viewpoint of deodorization, the metal phosphate is preferably an acidic phosphate of a tetravalent metal such as zirconium phosphate or titanium phosphate having a layered structure, aluminum dihydrogen phosphate dihydrate, or the like. More preferably, it is zirconium phosphate. These may be used alone or in combination of two or more.

  The metal phosphate preferably has an average primary particle diameter of 3.0 μm or less from the viewpoint of suppressing clogging of the spinning dope into the spinneret. More preferably, it is 1.5 μm or less. Also, from the viewpoint of dispersibility, when the average primary particle size is smaller than 0.05 μm, the cohesive force increases and it becomes difficult to mix uniformly into the spinning dope, so that the average primary particle size is 0.05 μm or more. preferable. More preferably, it is 0.15 μm or more.

  Furthermore, from the viewpoint of imparting cationic dyeability to the fiber structure of the present invention, it is preferable to contain a polymer of a compound having an anionic functional group.

Conventionally, even if a large amount of a polymer of a compound having an anionic functional group is included in order to increase dyeing seats and obtain high dyeing properties, the effect will reach its head relatively quickly and be sufficiently dyed. Was difficult. That is, the adjustment range of the dyeing property was narrow, and the level of the dyeing property that reached its peak was low. Specifically, the content of the polymer of the compound having an anionic functional group in the polyurethane elastic fiber reached a peak at about 2% by mass. Further, from the viewpoint of obtaining better basic physical properties as a polyurethane elastic fiber, it was preferable that the content of the polymer of the compound having an anionic functional group is not too much. However, when a polymer having a compound having an anionic functional group is contained in the polyurethane having the structure specified in the present invention, the dyeing is performed by increasing or decreasing the content of the polymer having a compound having an anionic functional group. The adjustment range of the property is wider, and the adjustment upper limit value of the dyeing property adjusted thereby becomes higher. Furthermore, even if a large amount of a polymer of a compound having an anionic functional group is contained, it becomes possible to maintain better basic physical properties as a polyurethane elastic fiber. It shows. As the content of the polymer of the compound having an anionic functional group, the amount of the functional group capable of sufficiently obtaining dye coloring is preferably 10 mmol / kg to 200 mmol / kg, and 20 mmol / kg in the polyurethane elastic yarn. More preferred is 100 mmol / kg or less. If the amount is too small, a sufficient amount of dye cannot be adsorbed. If the amount is excessive, dye coloration can be obtained, but the spinnability of polyurethane-based elastic yarn is deteriorated and the elasticity is lowered. On a mass basis, the range is from 0.1% by weight to 50% by weight, more preferably from 2% by weight to 10% by weight, and even more preferably from 3% by weight to 8% by weight. In addition, what is necessary is just to test this content beforehand according to a use and to determine an optimal value suitably.
Examples of the anionic functional group herein include sulfonic acid groups, nitro groups, carboxyl groups, phosphoric acid groups, and those whose ends are blocked with a metal salt as a counter cation. By introducing sulfonic acid groups and their salts into the polymer structure, it is possible to approximate the adsorption behavior of the dye species with cationic dye-dyeable polyester fibers and acrylic fibers that are used in combination with fabrics. , Dyeability can be enhanced. Among them, the anionic functional group is preferably a sulfonic acid group having high reactivity with the cationic dye. By containing a polymer of a compound having a sulfonic acid group in the polyurethane elastic yarn, the elastic yarn is likely to exhibit a lower L * when dyed with a black cationic dye.
The polymer of the compound having an anionic functional group used in the present invention is not particularly limited as long as it is a compound obtained by polymerizing a compound having an anionic functional group as a constituent monomer. A copolymer having both of the constituent monomers may be used. In the case of a copolymer, there is no particular limitation on the molar ratio of other constituent monomers and monomers having an anionic functional group.
In a particularly preferred polymer containing a sulfonic acid group, the molar concentration of the monomer having a sulfonic acid group is 5 mol% or more.
The monomer having a sulfonic acid group is preferably an aromatic sulfonic acid, the monomer having a sulfonic acid group is also preferably benzenesulfonic acid or phenolsulfonic acid, and the polymer containing the sulfonic acid group is formaldehyde degenerate. It is also preferable that it is a coalescence.
The most preferred example is that a copolymer of a monomer having a sulfonic acid group and a monomer having a sulfonyl group (excluding sulfonic acid) is a formaldehyde-condensed benzenesulfonic acid or phenolsulfonic acid and 4,4′-dihydroxydiphenylsulfone. It is a polymer.

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

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

  The fineness, the number of single yarns, the 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 yarn may be circular or flat.

  Also, the dry spinning method is not particularly limited, and spinning may be performed by appropriately selecting a spinning condition or the like suitable for 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 godet roller and the winder, and therefore are appropriately determined according to the intended use of the yarn. preferable. That is, from the viewpoint of obtaining a polyurethane elastic fiber having a desired permanent set rate and stress relaxation, it is preferable that the speed ratio between the godet roller and the winder is 1.15 to 1.65. 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 dyeability, stretchability, processability such as heat set, etc. Even when a thin fabric is used, sufficient stretch properties and aesthetics can be obtained, so that a high-quality clothing with excellent appearance can be obtained. Such a feature can be remarkably obtained in a knitted fabric. In particular, the circular knitted fabric, which is the 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, takes advantage of its body fit when used as clothing. Therefore, it can be preferably applied to uses for pursuing aesthetics, such as underwear, stockings and tights.

  Next, a preferable example is given about the raw material in the fiber structure of this invention.

  The fiber structure means a woven or knitted fabric, a non-woven fabric, a cotton or the like, but is not limited thereto.

  The fabric which is the fiber structure of the present invention is constituted by using the polyurethane elastic fiber as described above. Such a fabric can also exhibit the effects of the present invention in a mixed elastic fabric in which, for example, polyester yarn, polyamide yarn (nylon yarn) or the like is mixed.

  Examples of fibers to be combined with polyurethane elastic fibers in constituting a fiber structure include polyester yarn, polyamide yarn (nylon yarn), acrylic synthetic fiber, polypropylene synthetic fiber, semi-synthetic fiber represented by acetate fiber, cotton and hemp The effect of the present invention can be expressed in an elastic fabric using a single natural fiber typified by wool or wool, or a mixture of two or more of natural fibers.

  Further, the mixing ratio, the raw material fibers to be combined, and the mixing method may be appropriately selected and made into a fabric by a known manufacturing means. The elastic fiber may be used as bare thread as it is, or freely with one or more kinds of conventionally known fibers such as polyamide fibers, polyester fibers and synthetic fibers such as acrylic fibers, and natural fibers such as cotton and wool. You may use what was coat | covered in combination.

  For example, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, or ethylene terephthalate unit as the main repeating component (preferably about 90 mol% or more of the repeating unit), trimethylene terephthalate unit as the main repeating component Fibers (preferably those having a repeating unit of about 90 mol% or more), those having a butylene terephthalate unit as a main repeating component (preferably those having a repeating unit of about 90 mol% or more), etc. can be preferably used. . Among these, a fiber made of a polyester having an ethylene terephthalate unit as a repeating component of about 90 mol% or more is preferable, and a fiber made of a polyester having an ethylene terephthalate unit of about 95 mol% or more as a repeating component is more preferable. It is more preferable that the polyester is composed of about 100 mol% of ethylene terephthalate units, 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. The polyethylene terephthalate fiber is suitable for use in combination with the polyurethane urea fiber preferably used in the present invention, and can be a good fabric. (CDPET Requirements) Next, the cationic dyeable polyester fiber used in the present invention will be described.

  Usually, the cationic dyeable polyester fiber is obtained by copolymerizing a compound containing a metal sulfonate group into a polyester molecular structure. Various types of compounds containing different metal sulfonate groups and different copolymerization rates have been developed for improving dyeability and texture, but the cationic dyeable polyester fiber used in the present invention is an ordinary cation. There is no particular limitation as long as it exhibits dyeing properties with respect to the dye.

  Furthermore, in the present invention, the cross-sectional form of the polyester fiber may be round or irregular. Further, a water-absorbing quick-drying polyester fiber yarn is preferably used. The water-absorbing and quick-drying polyester fiber includes a fiber in which many hollows are provided on the wall surface of the hollow fiber, and a number of grooves and holes are provided on the fiber surface, etc. Use fibers with irregular cross-sections that absorb moisture in the pores, grooves on the fiber surface, between fibers, and spaces between yarns, and various types of water-absorbing quick-drying fibers sold by synthetic fiber manufacturers. Can do. Examples of the water-absorbing quick-drying polyester fiber include “COOLMAX (registered trademark)” manufactured by INVISTA, “Theo α (registered trademark)” manufactured by Toray Industries, Inc., and the like. (Bimetal requirement T-400) In particular, when polytrimethylene terephthalate is used, a side-by-side type composite fiber cross section is preferable. The cross-sectional shape of the fiber is round, triangular, multi-lobe, flat, dharma, C, M, H, X, W, I, +. However, in terms of the balance between crimp development and texture, a semicircular side-by-side with a round cross-section, a hollow side-by-side when aiming for light weight and heat retention, and a triangle-side side-by-side when aiming for a dry texture. Preferably used.

  In order to impart water-absorbing and quick-drying properties, as described above, a low-hygroscopic material such as a polyester fiber or an acrylic fiber is used as a polymer, and a hollow fiber is formed into a fiber having many smaller holes on its wall surface. Many grooves and holes are provided in the shape and on the fiber surface, etc., and the water absorption is absorbed by minute holes in the fiber itself, grooves on the fiber surface, spaces between fibers, and spaces between yarns. Examples thereof include a fiber having a modified cross-sectional shape and the like, and those provided with minute holes and voids into which moisture enters.

  If necessary, polyester conductive fibers or the like may be used as antistatic synthetic fibers. Examples of the conductive fibers include composite polyester fibers using carbon black as a conductive substance (for example, “Bertron (registered trademark)” manufactured by Kanebo Gosei Co., Ltd.), white copper iodide and metal composite oxides (for example, TiO 2. Composite polyester fibers using SnO 2 · Sb 2 O 2) can be mentioned, but the invention is not limited to these.

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

  For example, a polyamide is a resin composed of a high molecular weight substance in which a so-called hydrocarbon group is connected to a main chain through an amide bond, and such a polyamide has excellent mechanical properties and is mainly composed of polycaproamide (nylon 6 ), Polyhexamethylene adipamide (nylon 66) is preferred, and polycaproamide (nylon 6) is more preferred because of good dyeability. The term “mainly” as used herein means that ε-caprolactam units constituting polycaproamide are 80 mol% or more in all monomer units, and more preferably 90 mol% or more. Examples of other components include, but are not limited to, polydodecanoamide, polyhexamethylene adipamide, polyhexamethylene azelamide, polyhexamethylene sebamide, polyhexamethylene dodecanoamide, polymetaxylylene adipa Examples thereof include units such as aminocarboxylic acid, dicarboxylic acid, and diamine, which are monomers constituting imide, polyhexamethylene terephthalamide, polyhexamethylene isophthalamide and the like.

The synthetic fiber used in the present invention preferably has a fiber surface area per gram of woven or knitted fabric of about 0.02 m ² or more and 0.2 m ² or less, and 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. Moreover, as a synthetic fiber in this invention, for example, the single fiber fineness is preferably about 3 dtex or more and 300 dtex or less, more preferably 10 dtex or more and 150 dtex or less. What has such a fiber surface area and / or single fiber fineness can improve dyeability more.

  Furthermore, the polyester fiber used in the present invention may contain various stabilizers, pigments, and the like, as necessary, within a range not impairing the effects of the present invention, as in the case of the polyurethane. For example, stabilizers such as an addition polymer of divinylbenzene and p-cresol (“METACROL (registered trademark)” 2390 manufactured by DuPont), a light-resistant agent, an antioxidant, etc., so-called BHT and Sumitomo Chemical Co., Ltd. Both hindered phenolic drugs such as “Sumilyzer (registered trademark)” GA-80 manufactured by Chiba Geigy, Inc .; Benzotriazole and benzophenone drugs such as “Tinubin (registered trademark)” manufactured by Ciba Geigy; Sumitomo Chemical Co., Ltd. Phosphoric agents such as “Sumilyzer (registered trademark)” P-16 manufactured by the company; various hindered amine agents; inorganic pigments such as titanium oxide and carbon black; fluorine resin powder or silicone resin powder; magnesium stearate, etc. Metal soaps; bactericides containing silver, zinc and their compounds; deodorants; lubricants such as silicone and mineral oil; Barium, cerium oxide, may be added betaine and various antistatic agents phosphoric acid, etc., etc., also may be present to react with the polymer. In order to further enhance the durability to light and various types of nitric oxide, in particular, a nitric oxide scavenger such as HN-150 manufactured by Nippon Hydrazine Co., Ltd., a thermal oxidation stabilizer such as Sumitomo Chemical Co., Ltd. ) “Sumilyzer (registered trademark)” GA-80 and the like, and light stabilizers such as “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 includes the polyurethane fiber 2 More preferably, it contains more than one type of synthetic fiber. The fabric that is the fiber structure of the present invention may be a woven fabric, a knitted fabric, or a non-woven fabric. For example, a polyurethane elastic fiber may be covered with a synthetic fiber to obtain a fabric as a covering fiber, or a polyurethane elastic fiber may be woven and knitted with a bare fiber (bare) in a synthetic fiber to form an interwoven fabric. Good.

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

  Other materials include: synthetic acrylic polyacrylonitrile fiber, polyvinyl alcohol fiber, polyvinyl chloride fiber, polyurethane fiber or semi-synthetic acetate fiber or regenerated fiber viscose rayon, Cellulosic fibers including cupra, milk protein fibers, protein fibers including soy protein fibers, polylactic acid fibers, or the use of these filament yarns, spun yarns, blended yarns, or plants containing cotton and hemp There are natural fibers, or animal-based natural fibers including wool, cashmere, silk, and their blended yarns.

  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 woven. As the synthetic fiber, it is preferable that two or more kinds including the polyurethane fiber are contained. Polyurethane elastic fiber woven fabrics include plain fabrics, oblique weaves, satin weaves, etc., modified plain weaves, altered weaving fabrics, altered satin weaves, etc. special structures such as honeycomb, satin weaving, satin weaving, etc. Double weave, vertical double weave, double weave double weave, double weave, double velvet, double woven, belt woven, etc., velvet, towel, seal, velor, etc. Pile pile weaves, bevels, weave velvets, velvet, weep pile weaves, etc., and entangled structures such as coral, coral, crest, etc. are preferred.

  Weaving is not particularly limited as long as the effects of the present invention are not hindered, but weaving is carried out by a loom loom (fly shuttle loom, etc.) or a non-weaving loom (rapier loom, gripper loom, water jet loom, air jet loom, etc.). Is preferred.

  Moreover, 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 knitted. As the synthetic fiber, it is preferable that two or more kinds including the polyurethane fiber are contained. The type of the knitted fabric may be a weft (weft) knitted fabric or a warp (warp) knitted fabric. The knitting structure is preferably a flat knitting, rubber knitting, double-sided knitting, pearl knitting, tuck knitting, floating knitting, one-sided knitting, lace knitting, or splicing. Atlas knitting, double cord knitting, half tricot knitting, back hair knitting, jacquard knitting and the like are preferable. The number of layers may be a single layer or a multilayer of two or more layers.

  The knitting is not particularly limited as long as the effect of the present invention is not hindered, but by a flat knitting machine such as a circular knitting machine, a flat knitting machine, a cotton knitting machine, a tricot knitting machine, a Raschel knitting machine, a Miranese knitting machine, etc. Preferably it is done.

  The fiber structure of the present invention is dyed using 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 preferred.

  Specifically, the acid dye may be any commercially available acid dye, and may be any of a leveling type, a half milling type, a milling type, and a 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 "Lanasin (registered trademark)" M series (manufactured by Arkroma, Inc.), "Tectilon (registered trademark)", "Elionil (registered trademark)", "Pola (registered trademark)", "Lanacron S (registered trademark)" "Irgalan (registered trademark)", "Lanaset (registered trademark)", "Lanaset (registered trademark)" PA (manufactured by Huntsman), "Kayanol (registered trademark)", "Kayanol Milling (registered trademark)" (Nippon Kayaku Co., Ltd.). The cationic dye may be any commercially available cationic dye, and may be either a regular type (common name: raw cation) or a dispersion type. For example, “Kayacrill (registered trademark)”, “Kayacrill (registered trademark)” ED (manufactured by Nippon Kayaku Co., Ltd.), “Nichiron (registered trademark)” (manufactured by Nissei Kasei Co., Ltd.), “Astrazon (registered trademark)” ( Dystar Co., Ltd.).

  As the disperse dye, any commercially available disperse dye may be used. For example, “Kayalon Polyester UT series (manufactured by Nippon Kayaku Co., Ltd.)” (registered trademark) “Kayaron Polyester (registered trademark)” PUT series (Kiwa Chemical), “Terracil (registered trademark)” W series (manufactured by Huntsman), and the like.

  The dyeing machine used for the dyeing treatment of the fiber structure of the present invention is not particularly limited and may be either dip dyeing or printing. However, a normal liquid dyeing machine, a beam dyeing machine, a paddle dyeing machine, etc. It is preferable from the viewpoint of uniform dyeing. The dyeing temperature is preferably 90 ° C. or more and 140 ° C. or less from the viewpoint of fastness to dyeing and dyeing quality. Further, the fiber structure of the present invention has excellent dimensional stability, a small dimensional change rate, and less wrinkle generation, so that it is possible to lower the temperature of the heat set such as a preset or final set. In addition, the heat setting temperature is preferably 120 ° C. or more and 200 ° C. or less from the viewpoint of fabric quality and dimensional stability.

  The fiber structure of the present invention preferably has a wash fastness of 4 or more according to JIS L-0848: 2011A-2 method. The fiber structure of the present invention not only simply evaluates the dyeing rate, that is, the balance of the dye after several washings, but also practically resists equivalent to household washing and industrial washing under repeated and high temperatures. It is expressed that can be held.

  Furthermore, the fabric that is the fiber structure of the present invention includes, for example, a coat, a kimono, a suit, a uniform, a sweater, a skirt, a slack, a cardigan, a sportswear, a dress shirt, a casual wear, an outer garment, tights, stockings, pantyhose, Socks such as socks, underwear such as pajamas, shorts, lingerie, foundation, and foyer, bedclothes such as sheets, duvet covers, duvets, blankets, pillow covers, interiors such as sofa covers, tablecloths, and the like It is used for accessories such as gloves, ties, scarves, shawls, etc., and is particularly preferably used for underwear, socks, bedding, etc. in terms of the release of perfume ingredients.

  The fabric that 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 about 80 to 100% by mass. More preferred are: Moreover, the thing whose fiber component is only a synthetic fiber from the point which is excellent in dyeability is also preferable. Moreover, from the point which is excellent in dyeability, what contains about 1-30 mass% of polyurethane elastic fibers with respect to the whole synthetic fiber is preferable, and what contains about 5-20 mass% is further more preferable.

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

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

The invention is explained in more detail by means of examples.

[Permanent distortion rate, breaking strength, breaking elongation of polyurethane elastic fiber]
A permanent elastic modulus, stress relaxation, breaking strength, and breaking elongation were measured by tensile testing polyurethane elastic fibers using an Instron 4502 type tensile testing machine. The number of measurements was measured at n = 3, and the average value thereof was adopted.
A sample having a test length of 5 cm (L1) was repeatedly stretched 300% at a tensile rate of 50 cm / min five times, and the stress at the time of 100, 200, and 300% elongation at the fifth time was measured. ). Next, the length of the sample was maintained for 30 seconds with 300% elongation. The stress after holding for 30 seconds was defined as (G2). Next, the elongation of the sample was recovered, the stress at 200% and 100% elongation (recovery stress) was measured, and the length of the sample when the stress became zero was defined as (L2). Furthermore, it extended until the sample cut | disconnected 6th time. The stress at the time of rupture was defined as (G3), and the sample length at the time of rupture was defined as (L3). Hereinafter, the above characteristics are calculated by the following formula.
Breaking strength (cN) = (G3)
Permanent distortion rate (%) = 100 × ((L2) − (L1)) / (L1)
Elongation at break (%) = 100 × ((L3) − (L1)) / (L1).

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

Heat setting property = 100 × ((L5) − (L6)) / (L5)
A higher value indicates better heat setability.

[Heat resistance of polyurethane elastic fiber, return characteristics after heat setting]
The return characteristics after heat setting were measured by subjecting the sample yarn after heat setting as described above to a tensile test using an Instron 4502 type tensile tester.

  These are defined by: 300% elongation of a 5 cm (L7) sample was repeated 5 times at a tensile speed of 50 cm / min. Next, the length of the sample yarn when the elongation was recovered and the stress became zero was defined as (L8). Furthermore, it extended | stretched until the sample yarn cut | disconnected 6th time. The stress at the time of this break was defined as (G4). Hereinafter, the characteristic is given by the following equation.

Heat resistance = (G4)
Return characteristics after heat setting = 100 × ((L8) − (L7)) / (L7)
The heat resistance indicates that the higher the value, the better. The return characteristic after heat setting indicates that the lower the value, the better the stretchability.

[Tertiary 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 secondary amine with a large excess of strong acid, and then neutralizing and titrating the tertiary amine.

[Melting point of polyurethane elastic fiber]
As one of the heat resistance indexes of the polyurethane yarn, the high temperature side melting point, that is, the melting point of the hard segment crystal was measured. For the polyurethane yarn, an irreversible heat flow was measured at a rate of temperature increase of 3 ° C./minute using a 2920 modulated DSC manufactured by EE 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 small-angle X-rays and calculating the long period was performed by the following method.

  The long period J was obtained from, for example, the following Bragg 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 scattered image shown in FIG. 1, for the long period in the meridian direction, r is the distance from the equator line 2 to the scattering intensity maximum peak 3, and for the long period in the equator line direction, the scattering intensity from the meridian 1 to the scattering intensity maximum peak 4 is. The distance up to r was determined from the above Bragg equation.

Then, using an imaging plate as a scattering intensity detector, emitted light 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 equation was approximated by {tan −1 (r / R)}. r was determined from a continuous plot (scattering intensity profile) along the meridian 1 and the equator line 2 with 4πλ / sin θ (nm−1) as the horizontal axis and the scattering intensity as the vertical axis.
Sample preparation: Fibers were wound 50 times on cardboard with a 4 cm long hole in a state where the fibers were aligned and tensioned to remove slack, and the ends of both yarns were tied to obtain a measurement sample.
Equipment and conditions:
(1) Synchrotron radiation facility SPring-8 BL08B2
(2) Wavelength 0.10 nm
(3) Beam diameter 0.3mm length, 0.3mm width
(4) Camera length 2385mm
(5) Exposure time 60 sec
(6) Detector R-AXIS-IV ++ (imaging plate) manufactured by Rigaku Corporation.

[Dyeability evaluation]
A tubular knitted fabric made of 100% by mass of polyurethane fibers was prepared using a 29 gauge single neck knitting machine. Next, dry heat heat setting was performed on the tubular knitted fabric at 190 ° C. for 60 seconds, and a scouring agent (“Sanmor (registered trademark)” WX-HC, manufactured by Nikka Chemical Co., Ltd., at 80 ° C. for 20 minutes. ) Was refined using 0.1% by mass.
Using the produced tubular knitted fabric, the dyeability was evaluated by the following two methods.

(1) Measurement of dyeing rate A cylindrical knitted fabric after scouring was used with acid dye ("Lanacin Black (registered trademark)" M-DL, manufactured by Huntsman) 1% owf, bath ratio 1:30, 95 ° C. The tube knitted fabric for evaluation was obtained by dyeing using a mini color dyeing machine manufactured by Tecsum Giken Co., Ltd. under the conditions of 30 minutes. The absorbance (A1) and peak wavelength of the dye solution concentration before staining are measured in advance with a spectrophotometer (Spectrophotometer manufactured by JASCO Corporation, Model V-650), and an average value of three times is obtained. The subsequent residual liquid was collected, the absorbance (A2) at the peak wavelength was measured, the average value was obtained three times, and the dyeing rate of the dyed tubular knitted fabric was obtained from the following formula.

Dyeing rate (%) = 100 × (1-absorbance (A2) / absorbance (A1))
(2) Measurement of lightness L value The cylindrical knitted fabric after scouring is using an acid dye (Lanasin Black M-DL, manufactured by Huntsman) 1% owf, at a bath ratio of 1:30, 95 ° C., 30 minutes. Dyeing was performed using a mini color dyeing machine manufactured by Tecsum Giken Co., Ltd. to obtain a cylindrical knitted fabric for evaluation. This cylindrical knitted fabric is folded into a flat shape, and the color is measured using a spectrocolorimeter (Konica Minolta Co., Ltd., model CM-3700d) in a two-ply state, and the CIE 1976 L * a * b * color system The L * value was measured, and the average value of three measurements was taken as the measurement result. L * values indicate that the lower one is more intensely stained.

[Washing fastness]
JISL-0844: The method specified in the 2011 A-2 method, using nylon as the attached white cloth, discoloration of the test piece using the discoloration gray scale, and contamination of the attached white cloth using the contamination gray scale, respectively. did.

[Sweat fastness]
Using the method specified in JISL-0848: 2004, nylon is used as the attached white cloth, and for each of the artificial artificial sweat and alkaline artificial sweat, the fade color of the test piece is a gray scale for the fade color, and the attached white cloth is contaminated. Each was determined using a gray scale.

[Water fastness]
Nylon was used as the attached white cloth, the fading color of the test piece was judged using the gray scale for fading color, and the contamination of the attached white cloth was judged using the gray scale for contamination by the method prescribed in JISL-0846: 2004.

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

5: There are no defects such as wrinkles and lines 4: There are almost no defects such as wrinkles and lines 3: There are some defects such as wrinkles and lines 2: Many defects such as wrinkles and lines 1: Defects such as wrinkles and lines There are very many.

[Production of polyurethane elastic fiber PU12 used in Examples]
87.5 mol of dehydrated tetrahydrofuran and 12.5 mol of dehydrated 3-methyl-tetrahydrofuran were charged into a reactor equipped with a stirrer, and a catalyst (70% by mass of perchloric acid and anhydrous) was added at a temperature of 10 ° C. under a nitrogen seal. A copolymerized tetramethylene ether diol having a number average molecular weight of 2500 (by a copolymerization method in which a polymerization reaction is carried out in the presence of 30% by mass of acetic acid) for 8 hours and neutralized with an aqueous sodium hydroxide solution. The structural unit derived from 3-methyl-tetrahydrofuran (containing 12.5 mol%) was used as the polyalkylene ether diol.

  4,4′-MDI was charged to 1.7 mol per 1 mol of the copolymerized tetramethylene ether diol and reacted at 80 ° C., and the resulting reaction product was mixed with N, N-dimethylacetamide ( DMAc) was added, stirred well and dissolved to give a solution. Next, a DMAc solution containing 1.1 mol of 4,4'-MDI and ethylene glycol (EG) as a chain extender is simultaneously added to 1 mol of the copolymerized tetramethylene ether diol and sufficiently stirred. Next, a DMAc solution containing butanol as a terminal blocking 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 3800 poise at 40 ° C. The polymer had an intrinsic viscosity of 0.90 when measured at 25 ° C. at a solution concentration of 0.5 g / 100 ml in DMAc.

  Thereafter, to this polyurethane solution pu1, an addition polymer of divinylbenzene and p-cresol as a stabilizer (“METACROL (registered trademark)” 2390 manufactured by DuPont), and t-butyldiethanolamine and methylene-bis- ( Polyurethane having a structure starting from 4-cyclohexyl isocyanate) (“Megachlor (registered trademark)” 2462 manufactured by DuPont) was added in an amount of 2% by mass relative to the solid content of pu1 to prepare pu12. This polyurethane solution is discharged from a spinneret into a high-temperature (350 ° C) inert gas (nitrogen gas) with four filaments, dried by passing through this high-temperature gas, and air jet so that the yarns in the middle of drying are twisted together. Through a type twisting machine, 2 filaments were joined, wound at a speed of 600 m / min, and 22 dtex polyurethane elastic fiber (PU1) was produced by 2 filaments joining.

  The polyurethane elastic fiber (PU12) had a soft segment melting point (SSTm) of 0 ° C., a long period in the fiber direction (meridian direction) in small-angle X-ray scattering measurement of 49 nm, and a tertiary nitrogen content of 1.6 meq / kg. It was.

[Production of polyurethane elastic fibers PU14 and PU16 used in Examples]
Polyurethane having a structure starting from t-butyldiethanolamine and methylene-bis- (4-cyclohexyl isocyanate), which is a dyeing site blended in pu1 in PU12 (“METACROL (registered trademark)” 2462 manufactured by DuPont) Only the addition amount of) was changed to the formulation described in Table 1 and prepared.
Table 1 shows the soft segment melting point (SSTm), the long period in the fiber direction (meridian direction) in the small-angle X-ray scattering measurement, and the tertiary nitrogen content.

[Production of polyurethane elastic fiber PU22 used in Examples]
4,4′-MDI was charged to 1.67 mol per mol of PTMG having a number average molecular weight of 2000 and reacted at 70 ° C., and the resulting reaction product was converted to N, N-dimethylacetamide (DMAc). Were sufficiently stirred and dissolved to obtain a solution. Next, 0.34 mol of 4,4′-MDI is added to 1 mol of PTMG having a number average molecular weight of 2000, sufficiently stirred, and then a DMAc solution containing ethylene glycol (EG) as a chain extender is added. The mixture was sufficiently stirred, and a DMAc solution containing butanol as an end-capping 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 2800 poise at 40 ° C. The polymer had an intrinsic viscosity of 0.82 when measured at 25 ° C. at a solution concentration of 0.5 g / 100 ml in DMAc.

  Thereafter, to this polyurethane solution pu2, an addition polymer of divinylbenzene and p-cresol (“METACROL (registered trademark)” 2390 manufactured by DuPont) as a stabilizer and t-butyldiethanolamine and methylene-bis- ( Polyurethane having a structure starting from 4-cyclohexyl isocyanate) (“Methacryl (registered trademark)” 2462 manufactured by DuPont) was added in an amount of 2% by mass with respect to each solid content of pu2 to prepare pu22. This polyurethane solution is discharged from a spinneret into a high-temperature (350 ° C) inert gas (nitrogen gas) with four filaments, dried by passing through this high-temperature gas, and air jet so that the yarns in the middle of drying are twisted together. Through a type twisting machine, 2 filaments were joined, wound at a speed of 600 m / min, and 22 dtex polyurethane elastic fiber (PU22) was produced by 2 filaments joining.

  The polyurethane elastic fiber (PU22) had a soft segment melting point (SSTm) of 5 ° C., a long period in the fiber direction (meridian direction) in small-angle X-ray scattering measurement of 30 nm, and a tertiary nitrogen content of 1.6 meq / kg. It was.

[Production of polyurethane elastic fibers PU24 and PU26 used in Examples]
Polyurethane having a structure starting from t-butyldiethanolamine and methylene-bis- (4-cyclohexylisocyanate), which are dyeing sites to be incorporated into pu2 in PU22 (“METACROL (registered trademark)” 2462 manufactured by DuPont) Only the addition amount of) was changed to the formulation described in Table 1 and prepared.

  Table 1 shows the soft segment melting point (SSTm), the long period in the fiber direction (meridian direction) in the small-angle X-ray scattering measurement, and the tertiary nitrogen content.

[Production of polyurethane elastic fiber PU3X2 used in comparative example]
4,4′-MDI was charged to 2.01 mol per mol of PTMG having a number average molecular weight of 2000 and reacted at 70 ° C., and the resulting reaction product was converted to N, N-dimethylacetamide (DMAc). Were sufficiently stirred and dissolved to obtain a solution. Next, a DMAc solution containing ethylene glycol (EG) as a chain extender is added, sufficiently stirred, and further a DMAc solution containing butanol as an end-capping agent is added to obtain a polyurethane solution having a polymer solid content of 35% by mass. pu3x was prepared. The resulting solution had a viscosity of about 4000 poise at 40 ° C. The polymer had an intrinsic viscosity of 0.88 when measured at 25 ° C. at a solution concentration of 0.5 g / 100 ml in DMAc.

  Thereafter, to this polyurethane solution pu3x, an addition polymer of divinylbenzene and p-cresol (“METACROL (registered trademark)” 2390 manufactured by DuPont) as a stabilizer and t-butyldiethanolamine and methylene-bis- ( Polyurethane having a structure starting from 4-cyclohexyl isocyanate) (“Megachlor (registered trademark)” 2462 manufactured by DuPont) was added in an amount of 2% by mass with respect to each pu3x solid content. This polyurethane solution is discharged from a spinneret into a high-temperature (350 ° C) inert gas (nitrogen gas) with four filaments, dried by passing through this high-temperature gas, and air jet so that the yarns in the middle of drying are twisted together. Through a type twisting machine, 2 filaments were bonded together, wound at a speed of 600 m / min, and 22 dtex polyurethane elastic fiber (PU3X2) was manufactured by 2 filament bonding.

  The soft segment melting point (SSTm) of this polyurethane elastic fiber (PU3X2) is 3 ° C., the long period in the fiber direction (meridian direction) in the small-angle X-ray scattering measurement is 11.7 nm, and the tertiary nitrogen content is 1.6 meq / kg. Met.

[Production of polyurethane elastic fibers PU3X4 and PU3X6 used in comparative examples]
Polyurethane having a structure starting from t-butyldiethanolamine and methylene-bis- (4-cyclohexyl isocyanate), which is a dyeing site blended with pu3x in PU3X2, (“METACROL (registered trademark)” 2462 manufactured by DuPont) Only the addition amount of) was changed to the formulation described in Table 1 and prepared.

  Table 1 shows the soft segment melting point (SSTm), the long period in the fiber direction (meridian direction) in the small-angle X-ray scattering measurement, and the tertiary nitrogen content.

[Production of polyurethane elastic fiber PU1X0 used in comparative example]
Polyurethane having a structure starting from t-butyldiethanolamine and methylene-bis- (4-cyclohexyl isocyanate), which is a dyeing site blended in pu1 in PU12 (“METACROL (registered trademark)” 2462 manufactured by DuPont) Only the addition amount of) was changed to the formulation described in Table 1 and prepared.

In other words, it was prepared by changing to a prescription not adding only the dyeing locus in PU12 preparation.
Table 1 shows the soft segment melting point (SSTm), the long period in the fiber direction (meridian direction) in the small-angle X-ray scattering measurement, and the tertiary nitrogen content.

[Production of polyurethane elastic fiber PU2X0 used in comparative example]
Polyurethane having a structure starting from t-butyldiethanolamine and methylene-bis- (4-cyclohexylisocyanate), which are dyeing sites to be incorporated into pu2 in PU22 (“METACROL (registered trademark)” 2462 manufactured by DuPont) Only the addition amount of) was changed to the formulation described in Table 1 and prepared.

That is, it was created by changing to a prescription that does not add only the dyeing locus in PU22 creation.
Table 1 shows the soft segment melting point (SSTm), the long period in the fiber direction (meridian direction) in the small-angle X-ray scattering measurement, and the tertiary nitrogen content.

[Production of polyurethane elastic fiber PU3X0 used in comparative example]
Polyurethane having a structure starting from t-butyldiethanolamine and methylene-bis- (4-cyclohexyl isocyanate), which is a dyeing site blended with pu3x in PU3X2, (“METACROL (registered trademark)” 2462 manufactured by DuPont) Only the addition amount of) was changed to the formulation described in Table 1 and prepared.

That is, it was created by changing to a prescription not adding only the dyeing locus in the PU3X2 creation.
Table 1 shows the soft segment melting point (SSTm), the long period in the fiber direction (meridian direction) in the small-angle X-ray scattering measurement, and the tertiary nitrogen content.

[Examples 1 to 12]
Polyurethane fibers PU12 to PU26 were used to fabricate fiber structures with combinations of fiber contents shown in Table 2.

  The fiber structure 1 was manufactured by processing step-L in Table 3, and the fiber structure 2 was manufactured by processing step-L2 in Table 3.

[Comparative Examples 1 to 12]
Polyurethane fibers PU3X2 to PU3X6 and PU1X to PU1X3 were used to fabricate fiber structures with combinations of fiber contents shown in Table 2.
The fiber structure 1X was manufactured by processing step-L in Table 3, and the fiber structure 2X was manufactured by processing step-L2 in Table 3.

  The fiber structure of the present invention has heat set properties, heat resistance, dyeability, recoverability, and elongation. Therefore, clothes, nonwoven fabrics, and the like using this fiber structure are excellent in detachability, fit, wear feeling, heat retention, appearance quality, and the like.

  Because of 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. It is suitable for. Specific usable applications include socks, stockings, tights, circular knitting, tricots, ski trousers, work clothes, smoke fire clothes, golf trousers, wet suits, bras, girdles, gloves, various textile products, fastening materials, Further examples include fastening materials for preventing sanitary items such as paper diapers, waterproofing materials, imitation baits, artificial flowers, electrical insulation materials, wiping cloths, copy cleaners, and gaskets.

2 Equatorial Line r Distance from the equator line to the peak of the scattering intensity maximum

Claims (11)

A fiber structure including a polyurethane elastic fiber, 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 and contains a tertiary nitrogen compound. . There are two types of long periods in the fiber direction in small-angle X-ray scattering measurement of polyurethane elastic fibers, and there is a second long period (J2) whose scattering intensity for detecting the long period is smaller than the first long period (J1). The fiber structure according to claim 1. The fiber structure according to claim 1 or 2, wherein the second long period (J2) is 7 to 19 nm. 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 the above. The fiber structure using the polyurethane elastic fiber according to any one of claims 1 to 4, wherein the long period in the equator 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 content of the tertiary nitrogen compound is 0.05 to 7 meq / kg as a tertiary amine nitrogen atom. The fiber structure according to any one of claims 1 to 6, wherein the tertiary nitrogen compound is a polyurethane or polyurethane urea having a structure starting from a tertiary nitrogen-containing diol, a tertiary nitrogen-containing diamine and an organic diisocyanate. . The tertiary nitrogen compound is a polyurethane or polyurethane urea having a structure starting from a tertiary nitrogen-containing diol, a tertiary nitrogen-containing diamine and an organic diisocyanate, and the terminal group is a dialkyl semicarbazide. The fiber structure according to any one of the above. The fiber structure in any one of Claims 1-8 containing synthetic fibers other than a polyurethane elastic fiber. The fiber structure according to any one of claims 1 to 9, comprising a polyurethane elastic fiber as a bare thread (bare). The fiber structure according to any one of claims 1 to 10, wherein the fastness to washing according to JIS L 0848: 2011 A-2 method is 4 or more.