JP6934954B2 - Polyurethane elastic fiber and its winding body - Google Patents

Description

The present invention relates to polyurethane elastic fibers and their winding bodies.

Since polyurethane elastic fibers have excellent elastic properties, they are used in various products that require elasticity and fit, such as innerwear, stockings, compression wear, and diapers. The processing speed of polyurethane elastic fibers in manufacturing these products is increasing year by year, and there is a strong demand for polyurethane elastic fibers and their winding bodies that do not break during processing.

Further, the polyurethane elastic fiber has an appropriate fineness depending on the application, and is often manufactured as a multifilament yarn in which a plurality of filaments are bundled according to the fineness.

However, when processing polyurethane elastic fibers of multifilament yarn, the single yarn is loosened during running, the yarn is entangled with guides due to fluctuations in tension, etc., and the dyeing process and heat setting when processing into fabric There is a problem that the single yarn is easily broken due to the heat breaking in the process where heat is applied, such as the process and the process of applying a high-temperature adhesive at the time of manufacturing diapers.

Many improved techniques have been proposed to solve this thread breakage during processing, but the difficulty of loosening the single yarn, the small fluctuation of tension during running, and the difficulty of breaking due to the heat of the single yarn have been made. It is difficult to produce a polyurethane elastic fiber having a combination, and it cannot be said that the effect of suppressing yarn breakage is sufficient.

For example, in the polyurethane elastic fiber described in Patent Document 1 below, it is possible to make it difficult for the single yarns to come apart by adjusting the strength of the false twist and joining the single yarns together, but the tension fluctuation during running is large. Therefore, the effect of suppressing thread breakage is not sufficient.

Further, in the polyurethane elastic fiber described in Patent Document 2 below, the single yarn is made difficult to disperse by reducing the molecular weight of a part of the polyurethane polymer, but the melting point of the polymer is also lowered, so that the heat resistance is improved. It is not good, and there is a problem that thread breakage easily occurs due to heat during processing.

Japanese Patent Publication No. 47-50005 Japanese Unexamined Patent Publication No. 2006-118102

In view of the above-mentioned problems of the prior art, the problems to be solved by the present invention are that the single yarn does not easily come apart, the tension fluctuation during running is small, and the single yarn does not easily break even with heat. It is an object of the present invention to provide a polyurethane elastic fiber that can be sufficiently suppressed and a yarn body thereof.

｛式中、Ｒ_１は、炭素数５〜３０の２価の炭化水素基であり、Ｒ_２、及びＲ_３は、互いに独立に、炭素数１〜１０の２価の炭化水素基であり、そしてＲ_４は、炭素数１〜１０の１価の炭化水素基である。｝で表される繰り返し単位を有するウレタン化合物である、前記［８］に記載のポリウレタン弾性繊維。
［１０］前記３級アミンを含むウレタン化合物が、以下の式（１）：

｛式中、Ｒ_１は、炭素数５〜３０の２価の炭化水素基であり、Ｒ_２、及びＲ_３は、互いに独立に、炭素数１〜１０の２価の炭化水素基であり、そしてＲ_４は、炭素数１〜１０の１価の炭化水素基である。｝で表される繰り返し単位と、式（２）：

｛式中、Ｒ_５は炭素数５〜３０の２価の炭化水素基であり、そしてＲ_６は、炭素数１〜１０の２価の炭化水素基又はポリオキシアルキレン基である。｝で表される繰り返し単位とを有するウレタン化合物である、前記［８］に記載のポリウレタン弾性繊維。
［１１］前記３級アミンを含むウレア化合物が、以下の式（３）：

｛式中、Ｒ_７、及びＲ_８は、互いに独立に、炭素数１〜１０の１価の炭化水素基であり、そしてＲ_９は、炭素数５〜３０の２価の炭化水素基である。｝で表されるウレア化合物である、前記［８］に記載のポリウレタン弾性繊維。
［１２］前記３級アミンを含むウレタン又はウレア化合物の含有量が、前記化合物Ａと化合物Ｂとが縮合したエステル又はリン酸エステルの含有量より多い、前記［８］〜［１１］のいずれかに記載のポリウレタン弾性繊維。
［１３］前記３級アミンを含むウレタン又はウレア化合物の含有量が、前記化合物Ａと化合物Ｂとが縮合したエステル又はリン酸エステルの含有量の２０倍以上１５０倍以下である、前記［１２］に記載のポリウレタン弾性繊維。
［１４］前記［１］〜［１３］のいずれかに記載のポリウレタン弾性繊維の巻糸体。
［１５］前記巻糸体中のポリウレタン弾性繊維の伸長率が５％以下である、前記［１４］に記載の巻糸体。As a result of diligent studies and experiments to solve the above problems, the present inventors have unexpectedly found that the above problems can be solved by containing a predetermined amount of ester or phosphoric acid ester in the polyurethane elastic fiber. This is the result of completing the present invention.
That is, the present invention is as follows.
[1] A polyurethane elastic fiber that is a multifilament yarn, wherein the content of an ester or a phosphoric acid ester in which compound A and compound B are condensed is 50 ppm or more and 5% or less with respect to the weight of the polyurethane elastic fiber. The compound A is any one of a monocarboxylic acid having 4 to 30 carbon atoms, a dicarboxylic acid having 4 to 30 carbon atoms, a tricarboxylic acid having 4 to 30 carbon atoms, or a phosphoric acid, and the compound B is A polyurethane elastic fiber characterized by being any one of a monool having 1 to 30 carbon atoms, a diol having a molecular weight of 3000 or less, and a triol having a molecular weight of 3000 or less.
[2] The polyurethane elastic fiber according to the above [1], wherein the ratio of the maximum value to the minimum value of the diameter of the single yarn constituting the polyurethane elastic fiber which is the multifilament yarn is 1.1 or more and 2.0 or less. ..
[3] The polyurethane elastic fiber according to the above [1] or [2], wherein the outflow start temperature of the polyurethane elastic fiber by the flow tester is 200 ° C. or higher.
[4] The polyurethane elastic fiber according to any one of [1] to [3], wherein the content of the ester or phosphoric acid ester is 50 ppm or more and 1.5% or less with respect to the weight of the polyurethane elastic fiber.
[5] The compound A is any one of a monocarboxylic acid having 4 to 30 carbon atoms, a dicarboxylic acid having 4 to 30 carbon atoms, and a tricarboxylic acid having 4 to 30 carbon atoms. ] To [4]. The polyurethane elastic fiber according to any one of [4].
[6] The compound A is either a dicarboxylic acid having 4 or more and 30 or less carbon atoms or a tricarboxylic acid having 4 or more and 30 or less carbon atoms, or the compound B is a diol having a molecular weight of 3000 or less. The polyurethane elastic fiber according to any one of the above [1] to [5], which is any one of triols having a molecular weight of 3000 or less.
[7] The polyurethane elastic fiber according to any one of [1] to [6] above, wherein the ester or phosphoric acid ester obtained by condensing the compound A and the compound B has an aromatic ring.
[8] The polyurethane elastic fiber according to any one of [1] to [7] above, further containing a urethane or urea compound containing a tertiary amine in an amount of 0.01% or more and 5% or less.
[9] The urethane compound containing the tertiary amine has the following formula (1):

{In the formula, R ₁ is a divalent hydrocarbon group having 5 to 30 carbon atoms, and R _{2 and R 3} are divalent hydrocarbon groups having 1 to 10 carbon atoms independently of each other. R ₄ is a monovalent hydrocarbon group having 1 to 10 carbon atoms. } The polyurethane elastic fiber according to the above [8], which is a urethane compound having a repeating unit represented by.
[10] The urethane compound containing the tertiary amine has the following formula (1):

{In the formula, R ₁ is a divalent hydrocarbon group having 5 to 30 carbon atoms, and R _{2 and R 3} are divalent hydrocarbon groups having 1 to 10 carbon atoms independently of each other. R ₄ is a monovalent hydrocarbon group having 1 to 10 carbon atoms. } And the repeating unit represented by Equation (2):

{In the formula, R ₅ is a divalent hydrocarbon group having 5 to 30 carbon atoms, and R ₆ is a divalent hydrocarbon group or a polyoxyalkylene group having 1 to 10 carbon atoms. } The polyurethane elastic fiber according to the above [8], which is a urethane compound having a repeating unit represented by.
[11] The urea compound containing the tertiary amine has the following formula (3):

{In the formula, R ₇ and R ₈ are monovalent hydrocarbon groups having 1 to 10 carbon atoms independently of each other, and R ₉ is a divalent hydrocarbon group having 5 to 30 carbon atoms. .. } The polyurethane elastic fiber according to the above [8], which is a urea compound represented by.
[12] Any of the above [8] to [11], wherein the content of the urethane or urea compound containing the tertiary amine is larger than the content of the ester or phosphoric acid ester in which the compound A and the compound B are condensed. The polyurethane elastic fiber described in.
[13] The content of the urethane or urea compound containing the tertiary amine is 20 times or more and 150 times or less the content of the ester or phosphoric acid ester obtained by condensing the compound A and the compound B. [12] The polyurethane elastic fiber described in.
[14] The wound body of the polyurethane elastic fiber according to any one of the above [1] to [13].
[15] The winding body according to the above [14], wherein the elongation rate of the polyurethane elastic fiber in the winding body is 5% or less.

In the polyurethane elastic fiber of the present invention, by incorporating a specific ester or phosphoric acid ester in the polyurethane elastic fiber, the single yarn does not easily come apart, the tension fluctuation during running is small, and the single yarn does not easily break due to heat. Therefore, thread breakage during processing can be sufficiently suppressed.

It is the schematic of the apparatus which measures the tension fluctuation at the time of running of a polyurethane elastic fiber. It is the schematic of the apparatus which measures the antistatic property at the time of running of a polyurethane elastic fiber.

Hereinafter, embodiments for carrying out the present invention (hereinafter, referred to as “the present embodiment”) will be described in detail. The present invention is not limited to the following embodiments, and can be modified in various ways within the scope of the gist thereof.

The polyurethane elastic fiber of the present embodiment is a polyurethane elastic fiber which is a multifilament yarn composed of a plurality of single yarns, and the content of the ester or phosphoric acid ester in which compound A and compound B are condensed is the polyurethane elastic fiber. Compound A is a monocarboxylic acid having 4 or more and 30 or less carbon atoms, a dicarboxylic acid having 4 or more and 30 or less carbon atoms, a tricarboxylic acid having 4 or more and 30 or less carbon atoms, or a phosphoric acid. The compound B is one of a monool having 1 or more and 30 or less carbon atoms, a diol having a molecular weight of 3000 or less, or a triol having a molecular weight of 3000 or less.

In the present embodiment, the polyurethane constituting the polyurethane elastic fiber is not particularly limited as long as it has a structure polymerized from, for example, diisocyanate, polymer polyol, diol, diamine and the like. Further, the polymerization method is not particularly limited. The polyurethane may be, for example, a polyurethane polymerized from a diisocyanate, a polymer polyol, a low molecular weight diamine as a chain extender, or the like (also referred to as "polyurethane urea"), and a diisocyanate, a polymer polyol, and a chain. Polyurethane (also referred to as "polyurethane urethane") polymerized from a low molecular weight diol or the like as an extender may be used. Glycols and isocyanates having trifunctionality or higher may be used as long as they do not interfere with the desired effect.

Examples of the diisocyanate include aromatic diisocyanates, alicyclic diisocyanates, and aliphatic diisocyanates. The aromatic diisocyanate is not limited to the following, and examples thereof include diphenylmethane diisocyanate (hereinafter, also referred to as “MDI”), tolylene diisocyanate, 1,4-diisocyanate benzene, xylylene diisocyanate, and 2,6-naphthalene diisocyanate. Can be mentioned. Examples of the alicyclic diisocyanate and aliphatic diisocyanate include methylenebis (cyclohexylisocyanate) (hereinafter, also referred to as “H12MDI”), isophorone diisocyanate, methylcyclohexane2,4-diisocyanate, methylcyclohexane2,6-diisocyanate, and cyclohexane1. , 4-Diisocyanate, Hexahydroxylylene diisocyanate, Hexahydrotolylene diisocyanate, Octahydro 1,5-naphthalene diisocyanate and the like. These diisocyanates may be used alone or in combination of two or more. In particular, from the viewpoint of elasticity recovery of the elastic yarn, the diisocyanate is preferably an aromatic diisocyanate, and more preferably MDI.

Examples of the polymer polyol include, but are not limited to, polymer diols such as polyether diols, polyester diols, polycarbonate diols, polyacrylic diols, polythioester diols, and polyhydrocarbon diols. From the viewpoint of hydrolysis resistance, the polymer polyol is preferably a polyether-based polyol, and more preferably a polyether-based diol.

Examples of the polyether polyol include polyethylene oxide, polyethylene glycol, polyethylene glycol derivative, polypropylene glycol, polytetramethylene ether glycol (hereinafter, also referred to as “PTMG”), and a copolymer of tetrahydrofuran (THF) and neopentyl glycol. Examples thereof include modified PTMG (hereinafter, also referred to as “PTXG”) and diol, which is a copolymer of THF and 3-methylTHF. These polyether polyols may be used alone or in combination of two or more. The number average molecular weight of the polymer diol is preferably 1000 or more and 8000 or less. By using a polymer diol in this range, elastic fibers having excellent elongation, stretch recovery, and heat resistance can be easily obtained. From the viewpoint of UV embrittlement, the polyether polyol is preferably PTMG, PTXG, or a polyol obtained by blending these.

The chain extender is preferably at least one selected from the group consisting of low molecular weight diamines and low molecular weight diols. The chain extender may have both a hydroxyl group and an amino group in the molecule, such as ethanolamine.

The low molecular weight diamine as a chain extender is not limited to the following, and includes, for example, hydrazine, ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 2-methyl-1,5-pentanediamine, 1, 2-diaminobutane, 1,3-diaminobutane, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, 2,2-dimethyl-1,3-diaminopropane, 1,3-diamino-2 , 2-Dimethylbutane, 2,4-diamino-1-methylcyclohexane, 1,3-pentanediamine, 1,3-cyclohexanediamine, bis (4-aminophenyl) phosphine oxide, hexamethylenediamine, 1,3-cyclohexyl Examples thereof include diamine, hexahydrometaphenylenediamine, 2-methylpentamethylenediamine, and bis (4-aminophenyl) phosphine oxide. One of these low molecular weight diamines may be used alone, or two or more thereof may be used in combination. From the viewpoint of elasticity recovery of the elastic yarn, the low molecular weight diamine is preferably a diamine having 2 to 5 carbon atoms, and more preferably ethylenediamine.

The low molecular weight diol is not limited to the following, but is limited to ethylene glycol, 1,3-propanediol, 1,4-butanediol, bishydroxyethoxybenzene, bishydroxyethylene terephthalate, 1-methyl-1,2-ethanediol and the like. Can be mentioned. One of these low molecular weight diols may be used alone, or two or more thereof may be used in combination.

The polymerization method of polyurethane polymerized from the above diisocyanate, polymer polyol, diol, diamine and the like is not particularly limited, and may be a melt polymerization method or a solution polymerization method. In the case of the solution polymerization method, for example, a polyurethane solution can be obtained by polymerizing using raw materials such as diisocyanate, polymer polyol, diol, and diamine in a solvent such as DMAc, DMF, DMSO, and NMP. .. The reaction method for polymerizing polyurethane is also not particularly limited, but is a one-shot method in which each raw material is put into a solvent and reacted at an appropriate temperature, or after diisocyanate and a polymer polyol are reacted to form a prepolymer. , Prepolymer method for synthesizing polyurethane by chain extension reaction with diol or diamine.

Further, the polyurethane elastic fiber is a known organic or inorganic compound used for the polyurethane elastic fiber, for example, a polymer other than polyurethane, an antioxidant, a heat stabilizer, an antistatic agent, as long as the desired effect is not impaired. It may contain an agent, a light-resistant agent, an ultraviolet absorber, a gas discoloration inhibitor, a dye, an activator, a matting agent, a colorant, a filler, an anti-adhesive agent, a lubricant and the like.

The method for spinning polyurethane elastic fibers is not particularly limited. Examples of the spinning method include a method in which polyurethane is dissolved in a solvent and spun by a wet method or a dry method, and a method in which polyurethane is heated and melted and spun by a melting method.

The polyurethane elastic fiber of the present embodiment may be attached with an oil for polyurethane elastic fiber from the outside by a conventionally known method at the time of spinning. Examples of the method for adhering the oil agent include a method using an oiling roller. The oil component used here is not limited to the following, but for example, silicone-based oils such as dimethyl silicone, polyether-modified silicone, and polyamino-modified silicone, mineral oil-based oils, talc, silica, and mineral fine particles such as colloidal alumina. Various substances such as higher fatty acid metal salt powder such as magnesium stearate and calcium stearate, higher fatty acid carboxylic acid, higher fatty alcohol, and wax solid at room temperature such as paraffin polyethylene may be used in combination.

In the present embodiment, by containing the ester or phosphoric acid ester in the polyurethane elastic fiber at 50 ppm or more and 5% or less with respect to the weight of the polyurethane elastic fiber, the single yarn is hard to come apart and the tension fluctuation during running is small. , The single yarn is hard to break due to heat, and the effect of sufficiently suppressing the yarn breakage during processing can be exhibited.

As described above, the ester or phosphoric acid ester contained in the polyurethane elastic fiber of the present embodiment is the following compound A:
Any one of a monocarboxylic acid having 4 to 30 carbon atoms, a dicarboxylic acid having 4 to 30 carbon atoms, a tricarboxylic acid having 4 to 30 carbon atoms, or phosphoric acid, and the following compound B:
It is a condensation product of any one of a monool having 1 to 30 carbon atoms, a diol having a molecular weight of 3000 or less, or a triol having a molecular weight of 3000 or less.

It is sufficient that such an ester or a phosphoric acid ester is contained in a predetermined amount in the polyurethane elastic fiber, and the form of "containing" is not particularly limited. It may be contained by adhering to the surface. The method of adding the polyurethane polymer to the inside is not particularly limited, and various means such as a method using a static mixer, a method by stirring, a method using a homomixer, and a method using a twin-screw extruder can be adopted. The method to be included in the treatment agent such as an oil agent is not particularly limited, but for example, a method in which such an ester or a phosphoric acid ester is contained in the oil agent in advance and adhered to the polyurethane elastic fiber together with the oil agent using an oiling roller, a nozzle, or a spray is used. Various means can be adopted.

Although it is not yet clear why the single yarn can be made difficult to loosen by adding the ester or phosphoric acid ester to the polyurethane elastic fiber, the inventors presume as follows. Since the ester or phosphoric acid ester has poor compatibility with the polyurethane polymer, it is considered that the ester is likely to bleed from the elastic fiber and is easily localized on the surface of the single yarn regardless of the method of inclusion in the polyurethane elastic fiber. In the ester or phosphate ester localized on the surface in this way, it is considered that the single yarns are less likely to come apart because similar structures such as ester groups are attracted to each other by intermolecular force.

In the present embodiment, the compound A which is the raw material before the condensation reaction of the ester or the phosphoric acid ester includes a monocarboxylic acid having 4 or more and 30 or less carbon atoms, a dicarboxylic acid having 4 or more and 30 or less carbon atoms, and 4 or more and 30 or less carbon atoms. It may be any one of the tricarboxylic acid and the phosphoric acid. By using compound A as a monocarboxylic acid having 4 to 30 carbon atoms, a dicarboxylic acid having 4 to 30 carbon atoms, a tricarboxylic acid having 4 to 30 carbon atoms, or phosphoric acid, the loosening of single yarn is suppressed. be able to. Further, there is no particular limitation on the presence or absence of branching or substituents of monocarboxylic acid, dicarboxylic acid and tricarboxylic acid. The fact that the compound A may have a substituent means that if the compound A has a monocarboxylic acid, a dicarboxylic acid, or a tricarboxylic acid structure, it may have any other bond or a substituent. For example, an ester. Bonds such as bonds, amide bonds, ether bonds, sulfide bonds, disulfide bonds, urethane bonds, epoxy groups, nitro groups, cyano groups, ketone groups, formyl groups, acetal groups, thioacetal groups, sulfonyl groups, etc. You may have. Examples of monocarboxylic acids having 4 to 30 carbon atoms, dicarboxylic acids having 4 to 30 carbon atoms, and tricarboxylic acids having 4 to 30 carbon atoms include benzoic acid, phthalic acid, terephthalic acid, trimellitic acid, and adipic acid. , Sebasic acid, azelaic acid, maleic acid, citric acid, lauric acid, mystic acid, stearic acid, oleic acid, epoxidized vegetable oil and the like.

In the present embodiment, the compound B as a raw material before the condensation reaction of the ester or phosphoric acid ester is any one of monool having 1 to 30 carbon atoms, diol having a molecular weight of 3000 or less, and triol having a molecular weight of 3000 or less. Anything is fine. By making compound B a monool having 30 or less carbon atoms, a diol having a molecular weight of 3000 or less, or a triol having a molecular weight of 3000 or less, it is possible to suppress the loosening of single yarns. Further, there is no particular limitation on the presence or absence of branching or substituents. The fact that the compound B may have a substituent means that if the compound B has a monool, diol, or triol structure, it may have any other bond or substituent, for example, an ester bond or an amide. It has bonds such as bonds, ether bonds, sulfide bonds, disulfide bonds, urethane bonds, and groups such as epoxy groups, nitro groups, cyano groups, ketone groups, formyl groups, acetal groups, thioacetal groups, and sulfonyl groups. You may. Examples of compound B include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-hexanol, 2-hexanol, 3-hexanol, cyclohexyl alcohol, 2-ethyl-1-hexanol, and the like. Monools such as 1-nonanol, isodecyl alcohol, phenol, benzyl alcohol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butane Diole, 1,4-butanediol, 1,6-hexanediol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol and other diols, glycerin, 1,2,4-butanetriol and other triols And so on.

In the present embodiment, from the viewpoint of more effectively suppressing the loosening of the single yarn, the compound B is more preferably a monool having 15 or less carbon atoms, a diol having a molecular weight of 1500 or less, or a triol having a molecular weight of 1500 or less. , A monool having 15 or less carbon atoms, a diol having a molecular weight of 500 or less, or a triol having a molecular weight of 500 or less is more preferable, and a monool having 15 or less carbon atoms or a diol having a molecular weight of 500 or less is more preferable. Most preferably, it is a diol of 500 or less. Examples of the diol having a molecular weight of 500 or less include ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol. It is considered that the ester or phosphoric acid ester composed of the compound B as described above is more likely to bleed from the elastic fiber and is more likely to be localized on the surface of the single yarn.

In the present embodiment, from the viewpoint of more effectively suppressing the tension fluctuation during traveling, the compound A is a monocarboxylic acid having 4 or more and 30 or less carbon atoms, a dicarboxylic acid having 4 or more and 30 or less carbon atoms, and 4 or more and 30 or less carbon atoms. It is preferably any one of the tricarboxylic acids of. When compound A is one of a monocarboxylic acid having 4 to 30 carbon atoms, a dicarboxylic acid having 4 to 30 carbon atoms, and a tricarboxylic acid having 4 to 30 carbon atoms, it is more effective during traveling. The reason why the tension fluctuation can be suppressed is not clear, but the inventors presume as follows. As described above, the compound A is one of a monocarboxylic acid having 4 or more and 30 or less carbon atoms, a dicarboxylic acid having 4 or more and 30 or less carbon atoms, and a tricarboxylic acid having 4 or more and 30 or less carbon atoms. It is considered that the tension variation of the thread during traveling can be reduced because the viscosity of the thread becomes low and the magnitude and fluctuation of the frictional resistance between the guide or roller in the traveling path of the thread and the thread can be reduced.

In the present embodiment, from the viewpoint of more effectively suppressing the loosening of the single yarn, the compound A is any one of a dicarboxylic acid having 4 or more and 30 or less carbon atoms and a tricarboxylic acid having 4 or more and 30 or less carbon atoms. Alternatively, the compound B is preferably any one of a diol having a molecular weight of 3000 or less or a triol having a molecular weight of 3000 or less. Either compound A is one of a dicarboxylic acid having 4 to 30 carbon atoms and a tricarboxylic acid having 4 to 30 carbon atoms, or compound B is a diol having a molecular weight of 3000 or less, or a triol having a molecular weight of 3000 or less. Although it is not clear why the single yarn can be more effectively made difficult to disperse due to the fact that the ester is polyvalent, that is, the ester is polyvalent, the inventors presume as follows. .. As described above, compound A is one of a dicarboxylic acid having 4 to 30 carbon atoms and a tricarboxylic acid having 4 to 30 carbon atoms, or compound B is a diol having a molecular weight of 3000 or less, or a molecular weight of 3000. By being one of the following triols, the condensed compound of compound A and compound B is likely to bleed from the elastic fiber and is easily localized on the surface of the single yarn, so that the attractive force between the single yarns is increased. It is thought that it becomes stronger and the single yarn is less likely to come apart.

In the present embodiment, from the viewpoint of more effectively suppressing the loosening of the single yarn, the compound A is a monocarboxylic acid having 4 or more and 30 or less carbon atoms including an aromatic ring, a dicarboxylic acid having 4 or more and 30 or less carbon atoms, and a carbon number of carbon atoms. It is preferably a tricarboxylic acid of 4 or more and 30 or less, and is a monocarboxylic acid having 4 or more and 15 or less carbon atoms including an aromatic ring, a dicarboxylic acid having 4 or more and 15 or less carbon atoms, and a tricarboxylic acid having 4 or more and 15 or less carbon atoms. Is most preferable, and specific examples thereof include benzoic acid, phthalic acid, terephthalic acid, and trimellitic acid. Although it is not yet clear why the compound A has an aromatic ring, which makes it more effective to prevent the single yarn from loosening, the inventors presume as follows. As described above, since the compound A has an aromatic ring, the intermolecular force between the aromatic rings also acts, so that the attractive force between the single yarns becomes stronger and it is considered that the single yarns are less likely to come apart. ..

In the present embodiment, the content of the ester or phosphoric acid ester with respect to the weight of the polyurethane elastic fiber may be 50 ppm or more and 5% or less, more preferably 50 ppm or more and 2% or less, and further preferably 100 ppm or more and 2% or less. It is more preferably 100 ppm or more and 1.5% or less, and most preferably 100 ppm or more and 1% or less. The content in the present embodiment means% by weight with respect to the total weight of the polyurethane elastic fiber. When the ester or phosphoric acid ester is contained in the polyurethane polymer or in a treatment agent such as an oil agent by a plurality of methods, the content rate is the total value thereof. Say. Further, a plurality of types of the ester or phosphoric acid ester may be contained in the polyurethane elastic fiber at the same time. By setting the content of the ester or phosphoric acid ester to 5% or less, the effect of plasticizing the polymer of the ester or phosphoric acid ester can be suppressed, and the tension fluctuation during running can be reduced. The effect of suppressing the tension fluctuation becomes more effective when the content is 2% or less, more effective when the content is 1.5% or less, and most effective when the content is 1% or less. Become. Further, by setting the content of the ester or phosphoric acid ester to 50 ppm or more, there is an effect of suppressing the loosening of the single yarn. This effect becomes more effective when the content is 100 ppm or more.

In the present embodiment, the ester or phosphoric acid ester contained in the polyurethane elastic fiber preferably has a melting point of 60 ° C. or lower. By setting the melting point to 60 ° C. or lower, it is possible to more effectively suppress the loosening of the single yarn. It is considered that by setting the melting point of the ester or phosphoric acid ester to 60 ° C. or lower, the ester or phosphoric acid ester is likely to bleed from the elastic fiber and is easily localized on the surface of the single yarn.

In this embodiment, a boiling point at atmospheric pressure 1.013 × 10 5 ^Pa of the ester or phosphoric acid ester is contained in the polyurethane elastic fiber is preferably at 100 ° C. or higher. Wherein by more than 100 ° C. The boiling point at ester or phosphoric acid ester of pressure 1.013 × 10 5 ^Pa, the ester or phosphoric acid ester is hardly volatilized, because tends to remain in the polyurethane elastic fiber, more effective It is possible to suppress the loosening of the single yarn.

In the present embodiment, the ester or phosphoric acid ester contained in the polyurethane elastic fiber preferably has a molecular weight of 5000 or less, more preferably 2000 or less, from the viewpoint of effectively suppressing the loosening of single yarn. , More preferably 1000 or less. By reducing the molecular weight of the ester or phosphoric acid ester, the fluidity of the ester or phosphoric acid ester is increased, and bleeding from a single yarn becomes easy.

In the present embodiment, the ester or phosphoric acid ester contained in the polyurethane elastic fiber preferably has an oxygen atom other than the ester group. By having an oxygen atom other than the ester group, it is possible to more effectively suppress the loosening of the single yarn. When the ester or phosphoric acid ester has an oxygen atom other than the ester group, the intermolecular force between oxygen atoms other than the ester group acts on the ester or phosphoric acid ester, so that the attractive force between the single yarns is increased. It becomes stronger and the single yarn is less likely to come apart.

In the present embodiment, the ester or phosphoric acid ester may be a condensate of compound A and compound B, but from the viewpoint of more effectively suppressing the loosening of the single yarn, the ester or phosphoric acid ester may be used. , It is preferable to have an aromatic ring. Examples of the ester or phosphate ester having no aromatic ring include bis (2-cyclohexyl) adipate, trimethyl citrate, bis (2-ethylhexyl) adipate, bisoctyl adipate, dibutyl sebacate, and dioctyl sebacate. and so on. Examples of the ester or phosphate having an aromatic ring include methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, hexyl benzoate, phenyl benzoate (2-ethylhexyl), phenyl benzoate, and benzoic acid. Benzyl ester, ethylene glycol benzoate, propylene glycol benzoate, diethylene glycol benzoate, dipropylene glycol benzoate, ethylene glycol dibenzoate, propylene glycol dibenzoate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, 1,4 -Benzoic acid esters such as cyclohexanedimethanol dibenzoate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, bis (2-ethylhexyl) phthalate, diisononyl phthalate, dibenzyl phthalate, phthalate Phtate esters such as dicyclohexyl acid, bisbutylbenzyl phthalate, dimethyl terephthalate, diethyl terephthalate, dibutyl terephthalate, diisobutyl terephthalate, dihexyl terephthalate, bis (2-ethylhexyl) terephthalate, diisononyl terephthalate, dibenzyl terephthalate , Telephthalates such as dicyclohexyl terephthalate, butylbenzyl terephthalate, trimethyl trimellitic acid, trioctyl trimellitic acid, trimellitic acid esters such as tristrimeritate (2-ethylhexyl), triphenyl phosphate, tricresyl phosphate, There are aromatic phosphate esters such as trixylenyl phosphate, cresildiphenyl phosphate, and diphenyl (2-ethylhexyl) phosphate. From the viewpoint of more effectively suppressing the loosening of single yarn, the ester or phosphate ester is methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, hexyl benzoate, benzoic acid (2-ethylhexyl). , Phenylbenzoate, benzyl benzoate, ethylene glycol benzoate, propylene glycol benzoate, diethylene glycol benzoate, dipropylene glycol benzoate, ethylene glycol dibenzoate, propylene glycol dibenzoate, diethylene glycol dibenzoate, di-diethylene glycol dibenzoate Benzoic acid esters such as propylene glycol and 1,4-cyclohexanedimethanol dibenzoate are more preferred. From the viewpoint of most effectively suppressing the loosening of single yarn, the ester or phosphate ester is preferably a benzoic acid ester having a plurality of aromatic rings, and specifically, dibenzoic acid ethylene glycol and dibenzoic acid. Propylene glycol, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, and 1,4-cyclohexanedimethanol dibenzoate are most preferred.

In the present embodiment, the fineness of the polyurethane elastic fiber is preferably 100 dtex or more. By setting the fineness to 100 dtex or more, it is possible to more effectively suppress yarn breakage due to heat.
In the present embodiment, the number of filaments of the polyurethane elastic fiber, which is a multifilament yarn, is preferably 20 or more. By setting the number of filaments to 20 or more, it becomes easy to obtain polyurethane elastic fibers having high stretchability.
In the present embodiment, the single yarn fineness of the polyurethane elastic fiber is preferably 30 dtex or less. By setting the single yarn fineness to 30 dtex or less, the solvent can be efficiently evaporated when produced by the dry spinning method.

In the present embodiment, the ratio of the maximum value to the minimum value of the single yarn diameters which contain the ester or phosphoric acid ester at 50 ppm or more and 5% or less and constitute the multifilament with respect to the weight of the polyurethane elastic fiber is 1.1. When it is 2.0 or more, it is preferable because the effect of single yarn loosening is further enhanced. The ratio of the maximum value to the minimum value of the single yarn diameter is more preferably 1.2 or more and 2.0 or less, and further preferably 1.2 or more and 1.9 or less. By setting the ratio of the maximum value to the minimum value of the single yarn diameter to 2.0 or less, the bias of the tension of each single yarn is reduced, and the tension fluctuation during running can be suppressed, so that the yarn breakage is reduced. be able to. This effect becomes more effective by setting the ratio of the maximum value to the minimum value of the single yarn diameter to 1.9 or less. In addition, by setting the ratio of the maximum value to the minimum value of the single yarn diameter to 1.1 or more, the single yarn is less likely to come apart, and this effect is to make the ratio of the maximum value to the minimum value of the single yarn diameter 1.2 or more. By making it more effective. Although it is not yet clear why the yarns can be made difficult to loosen by setting the ratio of the single yarn diameters to 1.1 or more in this way, the inventors presume as follows. In multifilament elastic fibers, single yarns are often twisted in a false twisting process or a winding process during manufacturing, and the single yarns are often intricately entangled with each other. By setting the ratio of the maximum value to the minimum value of the single yarn diameter to 1.1 or more, the entanglement between the single yarns becomes more complicated, so that the effect of the ester or the phosphoric acid ester is further enhanced, and the single yarns are separated. It is thought that it can be made difficult to scratch. The method of controlling the ratio of the maximum value to the minimum value of the single yarn diameter is not particularly limited, but a method of producing polyurethane elastic fibers by arranging yarns discharged from two spuns having different numbers of holes is preferably used. Be done. Specifically, the polyurethane stock solution is extruded from two spun yarns having different numbers of holes so as to have the same weight to evaporate the solvent to form two yarns having the same fineness but different numbers of filaments, and then false twisted. There is a method of producing one polyurethane elastic fiber by aligning the steps. More specifically, for example, the polyurethane stock solution was extruded from the spuns having 48 and 24 holes with a weight of 310 dtex threads to form two threads, which were aligned in the false twisting process. In this case, the polyurethane elastic fiber has 620 dtex as a whole and the number of filaments is 72, but the single yarn derived from the spun with 24 holes has a single yarn diameter about 1.5 times that of the single yarn derived from 48 holes. Therefore, the ratio of the maximum value and the minimum value of the single yarn diameter can be set to about 1.5. Another method of controlling the ratio of the maximum value to the minimum value of the single yarn diameter is to adjust the temperature inside the spinning cylinder during spinning to moderately shake the yarn, or to control the speed of the Gode roller during winding. A method of adjusting and controlling the tension of elastic fibers in the spinning cylinder is also preferably used.

In the present embodiment, the outflow start temperature of the polyurethane elastic fiber by the flow tester is preferably 200 ° C. or higher. By setting the outflow start temperature to 200 ° C. or higher, sufficient heat resistance that does not cause thread breakage due to heat can be obtained even if there is a step of applying high temperature heat to the polyurethane elastic fiber during processing. The method for producing the polyurethane elastic fiber whose outflow disclosure temperature is 200 ° C. or higher is not particularly limited, and for example, a method for increasing the number average molecular weight of the polyurethane polymer to a certain level or higher, a method for increasing the hard segment content in the polymer, and a known heat resistance. There is a method of adding a sex improver. Further, the chain extender constituting the polyurethane elastic fiber may be selected from the group consisting of low molecular weight diamines and low molecular weight diols, but when low molecular weight diamines are used, hard segments composed of urea groups can be formed. Since a stronger hydrogen bond force acts than the hard segment composed of urethane groups when a low molecular weight diol is used, the outflow start temperature becomes high, and the outflow start temperature tends to be 200 ° C. or higher.

In the present embodiment, the tertiary amine is used from the viewpoint of more effectively suppressing the loosening of the single yarn and more effectively improving the antistatic property (that is, the difficulty of generating static electricity) during running. The urethane or urea compound contained is preferably contained in an amount of 0.01% or more and 5% or less, more preferably 0.01% or more and 3% or less, and 0.03% or more and 3% or more, based on the weight of the polyurethane elastic fiber. It is more preferable to contain% or less. The urethane or urea compound containing a tertiary amine may contain a tertiary amine group and a urethane or urea group in the molecule, and may be located at the position of the tertiary amine group and the urethane or urea group in the molecule. There is no limitation, it may be at the end, and it may be inside the molecule instead of the end. Further, as long as the molecule contains a tertiary amine group and a urethane or urea group, the number thereof is not limited, and the presence or absence of a substituent in the molecule and the molecular weight are not particularly limited. The reason why it is possible to make it more effective to prevent the single yarn from loosening by containing 0.01% or more and 5% or less of urethane or urea compound containing a tertiary amine is not yet clear, but the inventors have stated as follows. I'm estimating. By containing a urethane or urea compound containing a tertiary amine in the polyurethane elastic fiber, the effect of the ester or phosphoric acid ester bleeding from the elastic fiber is promoted, and the ester or phosphoric acid ester is localized on the surface of the single yarn. It is considered that the attractive force between the single yarns becomes stronger and the single yarns are less likely to come apart. This effect becomes more effective when 0.03% or more of a urethane or urea compound containing a tertiary amine is contained. From an economic point of view, the content of the urethane or urea compound containing the tertiary amine is preferably 5% or less. Further, the reason why the antistatic property during running can be more effectively exhibited by containing 0.01% or more and 5% or less of urethane or urea compound containing a tertiary amine is not yet clear, but the inventors have It is estimated as follows. By containing a urethane or urea compound containing a tertiary amine in the polyurethane elastic fiber, oxygen atoms and nitrogen atoms, which are polar portions of the ester group of the urethane or urea compound and the ester compound, interact with each other to form an electron path. It is probable that the polyurethane became less likely to be charged. This effect becomes more effective when 0.03% or more of a urethane or urea compound containing a tertiary amine is contained.

｛式中、Ｒ_１は、炭素数５〜３０の２価の炭化水素基であり、Ｒ_２、及びＲ_３は、互いに独立に、炭素数１〜１０の２価の炭化水素基であり、そしてＲ_４は、炭素数１〜１０の１価の炭化水素基である。｝で表される繰り返し単位を有するウレタン化合物、又は、以下の式（１）：

｛式中、Ｒ_１は、炭素数５〜３０の２価の炭化水素基であり、Ｒ_２、及びＲ_３は、互いに独立に、炭素数１〜１０の２価の炭化水素基であり、そしてＲ_４は、炭素数１〜１０の１価の炭化水素基である。｝で表される繰り返し単位と、式（２）：

｛式中、Ｒ_５は炭素数５〜３０の２価の炭化水素基であり、そしてＲ_６は、炭素数１〜１０の２価の炭化水素基又はポリオキシアルキレン基である。｝で表される繰り返し単位とを有するウレタン化合物であることが好ましい。また、３級アミンを含むウレア化合物は、以下の式（３）：

｛式中、Ｒ_７、及びＲ_８は、互いに独立に、炭素数１〜１０の１価の炭化水素基であり、そしてＲ_９は、炭素数５〜３０の２価の炭化水素基である。｝で表されるウレア化合物であることが好ましい。
Ｒ_１、及びＲ_５は、互いに独立に、炭素数５〜１５の２価の炭化水素基であることがより好ましく、脂環式炭化水素構造を有することが更に好ましく、６員環である脂環式炭化水素構造を有することが最も好ましい。
Ｒ_２、Ｒ_３は、炭素数１〜５の炭化水素基であることが更に好ましい。炭素数１〜５の炭化水素基としては、下記に限定されないが、例えば、メチレン基、エチレン基、プロピレン基、トリメチレン基、ブチレン基、２−メチルプロピレン基、ペンチレン基などがある。
Ｒ_４は、炭素数１〜５の炭化水素基であることが更に好ましい。炭素数１〜５の炭化水素基としては、下記に限定されないが、例えば メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔ−ブチル基、ペンチル基、イソペンチル基、ｔ−ペンチル基などがある。
Ｒ_６は、炭素数２〜４の２価の炭化水素基、オキシエチレン基、オキシプロピレン基、オキシテトラメチレン基、ポリオキシエチレン基、ポリオキシプロピレン基、ポリオキシテトラメチレン基であることがより好ましい。また、オキシテトラメチレン基、ポリオキシエチレン基、ポリオキシプロピレン基、ポリオキシテトラメチレン基の分子量は特に限定されない。
３級アミンを含むウレタン化合物に含まれる、式（１）で表される繰り返し単位の繰り返し数、及び式（２）で表される繰り返し単位の繰り返し数は特に制限はなく、また、分子内のいずれの位置に式（１）で表される繰り返し単位、および、式（２）で表される繰り返し単位があってもよい。
Ｒ_７、Ｒ_８は、炭素数１〜５の炭化水素基であることがより好ましい。炭素数１〜５の炭化水素基としては、下記に限定されないが、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔ−ブチル基、ペンチル基、イソペンチル基、ｔ−ペンチル基などがある。
Ｒ_９は、炭素数５〜１５の炭化水素基であることがより好ましく、芳香環構造を有することが更に好ましい。芳香環構造を有する構造としては、下記に限定されないが、例えばベンゼン構造やジフェニルメタン構造などがある。In the present embodiment, from the viewpoint of more effectively suppressing the loosening of the single yarn and more effectively improving the antistatic property during running, the urethane compound containing the tertiary amine is described by the following formula (1). ):

{In the formula, R ₁ is a divalent hydrocarbon group having 5 to 30 carbon atoms, and R _{2 and R 3} are divalent hydrocarbon groups having 1 to 10 carbon atoms independently of each other. R ₄ is a monovalent hydrocarbon group having 1 to 10 carbon atoms. } Or a urethane compound having a repeating unit represented by the following formula (1):

{In the formula, R ₁ is a divalent hydrocarbon group having 5 to 30 carbon atoms, and R _{2 and R 3} are divalent hydrocarbon groups having 1 to 10 carbon atoms independently of each other. R ₄ is a monovalent hydrocarbon group having 1 to 10 carbon atoms. } And the repeating unit represented by Equation (2):

{In the formula, R ₅ is a divalent hydrocarbon group having 5 to 30 carbon atoms, and R ₆ is a divalent hydrocarbon group or a polyoxyalkylene group having 1 to 10 carbon atoms. } Is preferably a urethane compound having a repeating unit represented by. Further, the urea compound containing a tertiary amine is described by the following formula (3) :.

{In the formula, R ₇ and R ₈ are monovalent hydrocarbon groups having 1 to 10 carbon atoms independently of each other, and R ₉ is a divalent hydrocarbon group having 5 to 30 carbon atoms. .. } Is preferably a urea compound.
R ₁ and R ₅ are more preferably divalent hydrocarbon groups having 5 to 15 carbon atoms independently of each other, further preferably having an alicyclic hydrocarbon structure, and a 6-membered ring fat. Most preferably, it has a cyclic hydrocarbon structure.
It is more preferable that R ₂ and R ₃ are hydrocarbon groups having 1 to 5 carbon atoms. The hydrocarbon group having 1 to 5 carbon atoms is not limited to the following, and includes, for example, a methylene group, an ethylene group, a propylene group, a trimethylene group, a butylene group, a 2-methylpropylene group, a pentylene group and the like.
R ₄ is more preferably a hydrocarbon group having 1 to 5 carbon atoms. The hydrocarbon group having 1 to 5 carbon atoms is not limited to the following, but for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, an isopentyl group, t- There is a pentyl group and so on.
R ₆ is a divalent hydrocarbon group having 2 to 4 carbon atoms, an oxyethylene group, an oxypropylene group, an oxytetramethylene group, a polyoxyethylene group, a polyoxypropylene group, and a polyoxytetramethylene group. preferable. The molecular weights of the oxytetramethylene group, the polyoxyethylene group, the polyoxypropylene group, and the polyoxytetramethylene group are not particularly limited.
The number of repetitions of the repeating unit represented by the formula (1) and the number of repetitions of the repeating unit represented by the formula (2) contained in the urethane compound containing a tertiary amine are not particularly limited, and are also within the molecule. At any position, there may be a repeating unit represented by the formula (1) and a repeating unit represented by the formula (2).
More preferably, R ₇ and R ₈ are hydrocarbon groups having 1 to 5 carbon atoms. The hydrocarbon group having 1 to 5 carbon atoms is not limited to the following, but for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, an isopentyl group, t. -There are pentyl groups and so on.
R ₉ is more preferably a hydrocarbon group having 5 to 15 carbon atoms, and further preferably has an aromatic ring structure. The structure having an aromatic ring structure is not limited to the following, but includes, for example, a benzene structure and a diphenylmethane structure.

で表される繰り返し単位をもつ、イソホロンジイソシアネートとＮ−ブチルジエタノールアミンを共重合した化合物４、以下の式（５）：

で表される繰り返し単位をもつ、ジシクロヘキシルメタン４，４’−ジイソシアネートと１，１’−（Ｎ−メチルイミノ）ジ−２−プロパノールを共重合した化合物５、又は以下の式（６）：

で表される繰り返し単位をもつ、イソホロンジイソシアネートと１，１’−｛Ｎ−（ｔ−ブチル）イミノ｝ジ−２−プロパノールを共重合した化合物６が挙げられる。
また、式（１）で表される繰り返し単位と式（２）で表される繰り返し単位をもつウレタン化合物の具体例としては、特に限定はされないが、ジシクロヘキシルメタン４，４’−ジイソシアネートとＮ−（ｔ−ブチル）ジエタノールアミンと１，４−ブタンジオールを共重合した以下の式（７）：

で表される繰り返し単位と、以下の式（８）：

で表される繰り返し単位をもつ化合物７が挙げられる。Specific examples of the urethane compound having a repeating unit represented by the formula (1) are not particularly limited, but the following formula (4):

Compound 4, which is a copolymer of isophorone diisocyanate and N-butyldiethanolamine, having a repeating unit represented by the following formula (5):

Compound 5 obtained by copolymerizing dicyclohexylmethane 4,4'-diisocyanate and 1,1'-(N-methylimino) di-2-propanol having a repeating unit represented by, or the following formula (6):

Examples thereof include compound 6 obtained by copolymerizing isophorone diisocyanate and 1,1'-{N- (t-butyl) imino} di-2-propanol having a repeating unit represented by.
Further, specific examples of the urethane compound having the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) are not particularly limited, but dicyclohexylmethane 4,4'-diisocyanate and N-. The following formula (7): in which (t-butyl) diethanolamine and 1,4-butanediol are copolymerized:

The repeating unit represented by and the following equation (8):

Examples thereof include compound 7 having a repeating unit represented by.

で表される化合物８、以下の式（１０）：

で表される化合物９が挙げられる。The specific example of the compound represented by the formula (3) is not particularly limited, but the following formula (9):

Compound 8 represented by the following formula (10):

The compound 9 represented by is mentioned.

In the present embodiment, from the viewpoint of more effectively suppressing the loosening of the single yarn and more effectively improving the antistatic property during running, the content of the urethane or urea compound containing the tertiary amine is the ester. Alternatively, the content is preferably higher than the content of the phosphoric acid ester, and the content of the urethane or urea compound containing the tertiary amine is more preferably 5 times or more and 200 times or less the content of the ester or phosphoric acid ester, and is 10 times or more. It is more preferably 150 times or less, further preferably 20 times or more and 150 times or less, and most preferably 30 times or more and 150 times or less.

In the present embodiment, the elongation rate of the polyurethane elastic fiber on the winding body is preferably 5% or less. Normally, polyurethane elastic fibers are wound around a paper tube in a stretched state rather than in a relaxed state to form a wound yarn body. In the state of the winding body, the rate at which the polyurethane elastic fiber is stretched with respect to the relaxed state is called the elongation rate on the winding body. By setting the elongation rate to 5% or less, the stress fluctuation required when unwinding the elastic fiber from the winding body becomes small, so that the tension fluctuation during running can be suppressed more effectively. The method of reducing the elongation rate to 5% or less is not particularly limited, and for example, there is a method of adjusting the speed ratio between the Gode roller and the winding bobbin when winding the polyurethane elastic fiber.

The polyurethane elastic fiber of the present embodiment has a single yarn that does not easily come apart, has a small tension fluctuation during running, and has excellent antistatic properties during running. Therefore, natural fibers such as cotton, silk, and wool, nylon 6 and nylon. Polyester fiber such as 66, polyethylene terephthalate, polytrimethylene terephthalate, polyester fiber such as polytetramethylene terephthalate, cationic dyeable polyester fiber, copper ammonia regenerated rayon, viscous rayon, acetate rayon, etc. When these fibers are used to form processed yarns by coating, entanglement, twisting, etc., and then cross-knitted to obtain a fabric, the yarns are less likely to break and high productivity can be obtained.

The fabric using the polyurethane elastic fiber of the present embodiment includes various stretch foundations such as swimwear, girdles, brassieres, intimate products, and underwear, tights, pantyhose, waistbands, body suits, spats, stretch sportswear, stretch outerwear, and so on. It can be suitably used for medical wear, stretch lining and the like. The fabric using the polyurethane elastic fiber of the present embodiment can suppress the occurrence of defective products because the single yarn of the polyurethane elastic fiber in the fabric is hard to be cut by heat even after undergoing heat processing processes such as presetting, dyeing, and final setting. Therefore, high productivity can be obtained.

The polyurethane elastic fiber of the present embodiment has a single yarn that does not easily come apart, has a small tension fluctuation during running, has excellent antistatic properties during running, and does not easily break even with heat. Since it can be suppressed, it is possible to manufacture sanitary materials such as sanitary products and paper diapers with high productivity, and further, there are few thread breakages and thread omissions in the members, and it is possible to suppress the occurrence of defective products of these products.

The present invention will be specifically described with reference to the following Examples and Comparative Examples, but the scope of the present invention is not limited to the Examples.
First, the evaluation method used in the following examples will be described.

<Measurement method and evaluation method>
<Content rate of ester or phosphoric acid ester in which compound A and compound B are condensed>
As a method for detecting the ester or phosphoric acid ester, for example, a predetermined amount of polyurethane elastic fiber is immersed in a solvent to extract the ester or phosphoric acid ester, and then a known analysis method such as GC / MS or NMR is used. There are ways to apply it. More specifically, for example, 1 g of polyurethane elastic fiber is soxhlet-extracted with 120 mL of chloroform for 8 hours. This extract is concentrated to dryness at 40 ° C. using an evaporator, and further vacuum dried at room temperature for 1 hour to analyze a dried sample obtained by a known method such as GC / MS or NMR. For details of the analysis conditions, for example, the following devices and conditions can be selected.

<NMR measurement>
A predetermined amount of the dried sample and the internal standard dimethyl sulfoxide were measured, and NMR was measured under the following conditions to specify the structure of the ester or the phosphate ester and calculate the content. The content of the ester or phosphate ester can be calculated from the integral value of the hydrogen signal with dimethyl sulfoxide, which is an internal standard. For example, when calculating the content of diethylene glycol benzoate, it can be calculated by comparing the integral value of hydrogen of the phenyl group of diethylene glycol benzoate with the integral value of hydrogen of the methyl group of dimethylsulfoxide. When the content could not be measured due to overlapping peaks or the like in the NMR measurement, the content was measured by the following GC / MS analysis measurement.
Measuring device: JEOL ECS400
Measurement nucleus: ¹ H
Resonance frequency: 400MHz
Number of integrations: 256 Measurement temperature: Room temperature Solvent: Dimethylformamide deuterated Measurement concentration: 1.5% by weight
Chemical shift criteria: Dimethylformamide (8.0233 ppm)

<GC / MS analysis measurement>
The dry sample is dissolved in 5 mL of methanol for analysis. The concentration of the ester or phosphate is compared with the area of the ester or phosphate in the dry sample by separately preparing a calibration line of the ester or phosphate whose structure has been identified by NMR measurement using GC. By doing so, the weight% can be calculated.
GC device: Agilent Technologies 7890A
Injection port temperature: 320 ° C
Column: DB-1MS (30m x 0.25mmφ), liquid phase thickness 0.25μm
Column temperature: 40 ° C (holding time 5 minutes), 20 ° C / min temperature rise, 320 ° C (holding for 11 minutes)
MS device: Agilent Technologies 5975C MSD
Ion source temperature: 230 ° C
Ionization method: Electron ionization method

<Content rate of urethane or urea compound containing tertiary amine>
As a method for detecting the urethane or urea compound, for example, a predetermined amount of polyurethane elastic fiber is immersed in a solvent to extract the urethane or urea compound, and then a known analytical method such as GC / MS or NMR is applied. The method can be mentioned. More specifically, for example, 1 g of polyurethane elastic fiber is soxhlet-extracted with 120 mL of chloroform for 8 hours. This extract is concentrated to dryness at 40 ° C. using an evaporator, and further vacuum dried at room temperature for 1 hour to analyze a dried sample obtained by a known method such as GC / MS or NMR. For details of the analysis conditions, for example, the following devices and conditions can be selected.

<NMR measurement>
A predetermined amount of dimethyl sulfoxide, which is an internal standard, was measured from a dry sample, and NMR was measured under the following conditions to identify the structure of the urethane or urea compound and calculate the content. The content of the urethane or urea compound can be calculated from the integral value of the hydrogen signal with dimethyl sulfoxide, which is an internal standard. When the content could not be measured due to overlapping peaks or the like in the NMR measurement, the content was measured by the following GC / MS analysis measurement.
Measuring device: JEOL ECS400
Measurement nucleus: ¹ H
Resonance frequency: 400MHz
Number of integrations: 256 Measurement temperature: Room temperature Solvent: Dimethylformamide deuterated Measurement concentration: 1.5% by weight
Chemical shift criteria: Dimethylformamide (8.0233 ppm)

<GC / MS analysis measurement>
The dry sample is dissolved in 5 mL of methanol for analysis. The concentration of the urethane or urea compound is determined by separately preparing a calibration curve of the urethane or urea compound whose structure has been identified by NMR measurement using GC and comparing it with the area of the urethane or urea compound in the dried sample. Weight% can be calculated.
GC device: Agilent Technologies 7890A
Injection port temperature: 320 ° C
Column: DB-1MS (30m x 0.25mmφ), liquid phase thickness 0.25μm
Column temperature: 40 ° C (holding time 5 minutes), 20 ° C / min temperature rise, 320 ° C (holding for 11 minutes)
MS device: Agilent Technologies 5975C MSD
Ion source temperature: 230 ° C
Ionization method: Electron ionization method

<Measurement of the ratio of the maximum value to the minimum value of the single yarn diameter>
Polyurethane elastic fibers were sampled at 1 m, the diameters of all single yarns were measured at five arbitrarily selected cross sections, and the ratio of the maximum value to the minimum value was defined as the ratio of the maximum value to the minimum value of the single yarn diameter. .. The diameter of each single yarn was measured by observing the cross section of the polyurethane elastic fiber using an electron microscope JSM-6510 manufactured by JEOL Ltd. If the cross-sectional shape of the single yarn is not circular but irregular, such as an ellipse or dumbbell, a circle with the smallest diameter (hereinafter, also referred to as "minimum inclusion circle") that completely includes the cross section is drawn and the minimum. The diameter of the inclusion circle was defined as the single yarn diameter.

<Measurement of outflow start temperature of polyurethane elastic fiber>
The outflow start temperature of the polyurethane elastic fiber is measured using a flow tester CFT-500D type (manufactured by Shimadzu Corporation). The outflow start temperature of the polyurethane elastic fiber is measured by sampling 1.5 g for each measurement without performing pretreatment such as removing a treatment agent such as an oil agent. Use a die (nozzle) with a diameter of 0.5 mm and a thickness of 1.0 mm, apply an extrusion load of 30 kg, preheat at an initial set temperature of 120 ° C. for 240 seconds, and then reach 250 ° C. at a rate of 3 ° C./min. Obtain the stroke length (mm) and temperature curve when the temperature rises rapidly. As the temperature rises, the polymer in the toner is heated and the polymer begins to flow out of the die. The temperature at this time is defined as the outflow start temperature.

<Polyurethane elastic fiber elongation rate on the winding body>
The elongation rate (%) of the polyurethane elastic fiber on the winding body was measured and calculated by the following procedure.
-The polyurethane elastic fiber was unwound from the polyurethane elastic fiber winding body by 0.5 m with a relaxed length (hereinafter, also simply referred to as "relaxed length") to prepare a sample, and the sample weight (g) was measured. From the following formula, the fineness (relaxed fineness A (dtex)) of the polyurethane elastic yarn in the relaxed state was calculated. The measurement was performed 4 times, and the average value was taken. The "relaxed state" refers to a state in which the yarn is unwound from cheese and then left unloaded for 2 hours or more.
Relaxing fineness A (dtex) = sample weight (g) x 10000 / relaxing length (m)
-The polyurethane elastic yarn was unwound by feeding out 50 m from the polyurethane elastic yarn wound body by a delivery roll while maintaining the elongation rate. The weight (g) of the unwound yarn was measured. From the following formula, the fineness (print fineness B (dtex)) of the polyurethane elastic yarn in the stretched state was calculated.
Print fineness B (dtex) = total weight of unwound yarn (g) x 10000/50 (m)
・ The following formula:
Elongation rate (%) = (A / B-1) x 100
From this, the elongation rate (%) of the polyurethane elastic yarn on the winding body was calculated.

<Dismemberment of single thread>
Using a tensile tester (RTG-1210 type Tensilon manufactured by Orientec Co., Ltd.), a test thread with a sample length of 50 mm is pulled at a rate of 500 mm / min under the conditions of 20 ° C. and 65% relative humidity, and is elastic. The broken part of the fiber was observed, and it was observed whether the single yarn was loosened. Regarding the loosening of the single yarn, it was judged that the single yarn was loosened when there was a single yarn independent of 1 cm or more from the fractured portion. The measurement was performed 10 times for each test yarn, the number of single yarns separated was recorded, and the evaluation was made according to the following 6 evaluation criteria:
During the 6:10 times, the number of pieces scattered was 0 to 1.
During the 5:10 times, the number of pieces scattered was 2 to 3.
Among the 4:10 times, the number of pieces scattered was 4 to 5.
Among the 3:10 times, the number of pieces scattered was 6 to 7.
During the 2:10 times, the number of loose pieces was 8-9.
Of the 1:10 times, the number of pieces scattered was 10.

<Tension fluctuation during running>
As shown in FIG. 1, a winding body 1 in which 1000 m of polyurethane elastic fiber is wound around a paper tube is applied to an apparatus, and the elastic fiber delivery roll 2 is stretched at a speed of 10 m / min and the take-up roll 3 is stretched at a speed of 30 m / min. The fiber was run at a magnification of 3 times, and the stress (mg) during thread running was measured with a tension meter 4 at 0.1 second intervals for 3 minutes. The standard deviation (mg) of the obtained fluctuation of the stress value was divided by the fineness of the elastic fiber, and the value was evaluated as the tension fluctuation value (mg / dtex) during running according to the following 6 evaluation criteria:
6: The tension fluctuation value during running was less than 5 (mg / dtex).
5: The tension fluctuation value during running was 5 (mg / dtex) or more and less than 7 (mg / dtex).
4: The tension fluctuation value during running was 7 (mg / dtex) or more and less than 10 (mg / dtex).
3: The tension fluctuation value during running was 10 (mg / dtex) or more and less than 12 (mg / dtex).
2: The tension fluctuation value during running was 12 (mg / dtex) or more and less than 15 (mg / dtex).
1: The tension fluctuation value during running was 15 (mg / dtex) or more.

<Antistatic property during driving>
As shown in FIG. 2, a winding body 1 in which 10000 m of polyurethane elastic fiber is wound on a paper tube is applied to an apparatus, and the elastic fiber delivery roll 2 is stretched at a speed of 50 m / min and the take-up roll 3 is stretched at a speed of 100 m / min. It was run at a magnification of 2 times, and 1 hour after the start of running, the amount of static electricity generated at 2 mm above the thread during running was measured with a digital low potential measuring device (manufactured by Kasuga Electric Co., Ltd.) 5. The average value of the obtained static electricity was evaluated as the generated static electricity (kV) during running according to the following 6 evaluation criteria:
6: The absolute value of static electricity generated during running was less than 4 (kV).
5: The absolute value of static electricity generated during traveling was 4 (kV) or more and less than 4.5 (kV).
4: The absolute value of static electricity generated during running was 4.5 (kV) or more and less than 5 (kV).
3: The absolute value of static electricity generated during running was 5 (kV) or more and less than 5.5 (kV).
2: The absolute value of static electricity generated during running was 5.5 (kV) or more and less than 6 (kV).
1: The absolute value of static electricity generated during running was 6 (kV) or more.

<Heat resistance of single yarn>
The test yarn with an initial length of 7 cm is stretched by 200% to 21 cm, pressed against a cylindrical hot body with a surface temperature of 180 ° C. and a diameter of 6 cm (contact portion 1 cm), and the number of seconds until cutting is measured. Evaluated on a 6-point scale:
6: The number of seconds until disconnection was 60 seconds or more.
5: The number of seconds until disconnection was 45 seconds or more and less than 60 seconds.
4: The number of seconds until disconnection was 30 seconds or more and less than 45 seconds.
3: The number of seconds until disconnection was 10 seconds or more and less than 30 seconds.
2: The number of seconds until disconnection was 5 seconds or more and less than 10 seconds.
1: The number of seconds until disconnection was less than 5 seconds.

<Resistance to thread breakage during processing>
The frequency of thread breakage when polyurethane elastic fibers were used in the processing process was evaluated according to the following six evaluation criteria.
6: Dispersion of single yarn, tension fluctuation during running, heat resistance of single yarn, and antistatic property during running are all evaluated as 6, and yarn breakage does not occur in the processing process.
5: There is an evaluation of 5 in any of the loosening of the single yarn, the tension fluctuation during running, the heat resistance of the single yarn, and the antistatic property during running, but the evaluations 4, 3, 2, and 1 are not found. Thread breakage does not occur in the processing process.
4: There is an evaluation 4 in any of the loosening of the single yarn, the tension fluctuation during running, the heat resistance of the single yarn, and the antistatic property during running, but the evaluations 3, 2, and 1 are not found. Almost no thread breakage occurs in the processing process.
3: Evaluation 3 is given to any of the loosening of the single yarn, the tension fluctuation during running, the heat resistance of the single yarn, and the antistatic property during running, but evaluations 2 and 1 are not seen. Almost no thread breakage occurs in the processing process.
2: Evaluation 2 is given to any of the loosening of the single yarn, the tension fluctuation during running, the heat resistance of the single yarn, and the antistatic property during running, but the evaluation 1 is not found. Thread breakage rarely occurs in the processing process.
1: There is an evaluation of 1 in any of the loosening of the single yarn, the tension fluctuation during running, the heat resistance of the single yarn, and the antistatic property during running, and the yarn breakage frequently occurs in the processing process.

In Examples and Comparative Examples, polyurethane elastic fibers and wound yarns thereof were manufactured by the following manufacturing methods unless otherwise specified.
2000 g of polytetramethylene ether glycol having a number average molecular weight of 2000 and 400 g of 4,4'-diphenylmethane diisocyanate are reacted in a dry nitrogen atmosphere at 60 ° C. for 3 hours under stirring, and the end is capped with isocyanate. A prepolymer was obtained. After cooling this to room temperature, dimethylacetamide was added and dissolved to prepare a polyurethane prepolymer solution. On the other hand, a solution prepared by dissolving 33.8 g of ethylenediamine and 5.4 g of diethylamine in dry dimethylacetamide was added to the prepolymer solution at room temperature, and the polyurethane solid content concentration was 30% by mass and the viscosity was 450 Pa · s. A polyurethane solution PA1 at (30 ° C.) was obtained. If necessary, an ester or phosphoric acid ester or a urethane or urea compound containing a tertiary amine is added to and mixed with this PA1 to prepare a uniform solution, which is then defoamed at room temperature and under reduced pressure. It was used as a spinning stock solution. This undiluted spinning solution is extruded from a spinneret having a number of pores according to the desired number of filaments, and the temperature inside the spinning cylinder is appropriately adjusted in order to adjust the ratio between the maximum value and the minimum value of the single yarn diameter. Is spun in a dry manner by shaking moderately, and the multifilament is focused by a false twisting device using compressed air of 0.20 MPa, and then an oil containing an ester or a phosphate ester is applied to the polyurethane elastic fiber as necessary, and the paper is applied. The yarn was wound on a paper tube made of polyurethane to obtain a wound yarn made of polyurethane elastic fiber.

[Examples 1 to 8]
Diethylene glycol dibenzoate (manufactured by Tokyo Kasei Kogyo Co., Ltd .: with an aromatic ring in the compound) is contained in the oil or polymer so as to be 200 ppm with respect to the total weight of the polyurethane elastic fiber, and the maximum and minimum values of the single yarn diameter are obtained. The ratio of As shown in Table 1 of the above, the polyurethane elastic yarn winding bodies of Examples 1 to 8 were produced. The results are shown in Table 1 below.

[Examples 9 to 15]
The fineness of the yarn is 620 dtex, the number of filaments is 72, the ratio of the maximum value to the minimum value of the single yarn diameter is 1.48 to 1.56, the elongation rate is 2%, and the benzoic acid contained in the oil or the polymer. The content of diethylene glycol acid acid (manufactured by Tokyo Kasei Kogyo Co., Ltd .: having an aromatic ring in the compound) with respect to the total weight of the polyurethane elastic fiber and the outflow start temperature are changed as shown in Table 1 below, and urethane containing a tertiary amine or Polyurethane elastic yarn winding bodies of Examples 9 to 15 were produced without containing a urea compound.
It was found that by containing an ester or a phosphoric acid ester in the polyurethane elastic fiber, yarn breakage during processing can be suppressed. The results are shown in Table 1 below.

[Examples 16 to 21]
The yarn fineness is 620 dtex, the number of filaments is 72, and the ester or phosphoric acid ester is contained in the oil agent so as to be 200 ppm with respect to the total weight of the polyurethane elastic fiber, and the ratio of the maximum value to the minimum value of the single yarn diameter is 1. Table 2 below shows the esters or phosphates at 46-1.53, with an outflow start temperature of 200 ° C. or higher, no tertiary amine-containing urethane or urea compounds, and an elongation of 2%. The polyurethane elastic yarn winding bodies of Examples 16 to 21 were produced. Esters or phosphates include methyl benzoate (manufactured by Tokyo Kasei Kogyo Co., Ltd .: having an aromatic ring in the compound), benzyl benzoate (manufactured by Tokyo Kasei Kogyo Co., Ltd .: having an aromatic ring in the compound), and trimethyl trimellitic acid (Tokyo). Kasei Kogyo Co., Ltd .: Aromatic ring in the compound), Tricredil phosphate (Tokyo Kasei Kogyo Co., Ltd .: Aromatic ring in the compound), Diphenyl2-ethylhexyl phosphate (Tokyo Kasei Kogyo Co., Ltd .: Aromatic ring in the compound) ), Dibutyl phthalate (manufactured by Tokyo Kasei Kogyo Co., Ltd .: there is an aromatic ring in the compound) was used.
It was found that by containing an ester or a phosphoric acid ester in the polyurethane elastic fiber, yarn breakage during processing can be suppressed. The results are shown in Table 2 below.

[Examples 22 to 33]
The fineness of the yarn is 620 dtex, the number of filaments is 72, and diethylene glycol dibenzoate (manufactured by Tokyo Kasei Kogyo Co., Ltd .: with an aromatic ring in the compound) is added in an oil or polymer so as to be 200 ppm with respect to the total weight of the polyurethane elastic fiber. The ratio of the maximum value to the minimum value of the single yarn diameter is shown in Table 2 below without containing urethane or urea compound containing tertiary amine, with an elongation rate of 2% and an outflow start temperature of 200 ° C. or higher. The polyurethane elastic yarn winding bodies of Examples 22 to 33 were produced by changing as shown in.
It was found that the yarn breakage during machining can be suppressed by controlling the ratio of the maximum value and the minimum value of the single yarn diameter. The results are shown in Table 2 below.

[Examples 34 and 35]
The fineness of the yarn is 620 dtex, the number of filaments is 72, and diethylene glycol dibenzoate (manufactured by Tokyo Kasei Kogyo Co., Ltd .: with an aromatic ring in the compound) is added in an oil or polymer so as to be 200 ppm with respect to the total weight of the polyurethane elastic fiber. A urethane or urea compound containing a tertiary amine having a ratio of the maximum value to the minimum value of the single yarn diameter of 1.49 to 1.52, an elongation rate of 2%, an outflow start temperature of less than 200 ° C. Polyurethane elastic yarn winding bodies of Examples 34 and 35 were produced without containing them. In the production of the polyurethane elastic fiber of this example, since the outflow start temperature is less than 200 ° C., the polyurethane solution PU1 separately synthesized by the following method is added to PA1 with PA1: PU1 = 90: 10-60: Mix to a weight ratio of 40, and if necessary, add / mix an ester or phosphoric acid ester or a urethane or urea compound containing a tertiary amine to make a uniform solution, and then at room temperature under reduced pressure. The foam was defoamed with, and this was used as a spinning stock solution. In PU1, 2000 g of polytetramethylene ether glycol having a number average molecular weight of 2000 and 400 g of toluenediisocyanate are reacted in a dry nitrogen atmosphere at 60 ° C. for 3 hours under stirring, and the end is capped with isocyanate. A prepolymer was obtained, cooled to room temperature, and then dimethylacetamide was added and dissolved to obtain a polyurethane prepolymer solution. On the other hand, a solution prepared by dissolving 110 g of 1,4-butanediol in dry dimethylacetamide was prepared. Was added to the prepolymer solution at room temperature and reacted at 80 ° C. for 3 hours under stirring for synthesis. It was found that the yarn breakage during processing can be suppressed by controlling the outflow start temperature. The results are shown in Table 3 below.

[Examples 36 and 37]
The yarn fineness is 620 dtex, the number of filaments is 72, and the ester or phosphoric acid ester is contained in the oil so as to be 200 ppm with respect to the total weight of the polyurethane elastic fiber, and the ratio of the maximum value to the minimum value of the single yarn diameter is 1. At 50-1.53, the runoff start temperature is 200 ° C. or higher, the elongation is 2%, without the inclusion of urethane or urea compounds containing tertiary amines, and the ester is varied as shown in Table 3 below. The polyurethane elastic yarn winding bodies of Examples 36 and 37 were produced. As the ester, bis (2-ethylhexyl) adipate (manufactured by Tokyo Chemical Industry Co., Ltd .: no aromatic ring in the compound) and trimethyl citrate (manufactured by Tokyo Chemical Industry Co., Ltd .: no aromatic ring in the compound) were used.
It was found that the inclusion of the ester in the polyurethane elastic fiber can suppress yarn breakage during processing. The results are shown in Table 3 below.

[Examples 38 and 39]
The yarn fineness was 620 dtex, the number of filaments was 72, and diethylene glycol dibenzoate (manufactured by Tokyo Kasei Kogyo Co., Ltd .: with an aromatic ring in the compound) was contained in the oil so as to be 200 ppm with respect to the total weight of the polyurethane elastic fiber. The ratio of the maximum value to the minimum value of the single yarn diameter is 1.48 to 1.56, the outflow start temperature is 200 ° C. or higher, and the elongation rate is as follows without containing urethane or urea compound containing tertiary amine. The polyurethane elastic yarn winding bodies of Examples 38 and 39 were produced by changing as shown in Table 3.
It was found that by controlling the elongation rate, thread breakage during processing can be suppressed. The results are shown in Table 3 below.

Urethane or urea compounds containing a tertiary amine were synthesized according to Production Examples 1 to 6 below.
[Manufacturing Example 1]
In a separable flask equipped with a stirrer and a thermometer, 100 mmol of N-butyldiethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.), 90 mmol of isophorone diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.), 100 mL of DMAc (manufactured by Tokyo Chemical Industry Co., Ltd.), and dibutyltin dilaurate as a catalyst. 0.1 mL was added, and the mixture was stirred at 60 ° C. for 2 hours to synthesize compound 4.
[Manufacturing Example 2]
In a separable flask equipped with a stirrer and a thermometer, 100 mmol of 1,1'-(N-methylimino) di-2-propanol (manufactured by BASF) and 90 mmol of dicyclohexylmethane 4,4'-diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) , DMAc 100 mL (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.1 mL of dibutyltin dilaurate as a catalyst were added, and the mixture was stirred at 60 ° C. for 2 hours to synthesize compound 5.
[Manufacturing Example 3]
In a separable flask equipped with a stirrer and a thermometer, 1,1'-{N- (t-butyl) imino} di-2-propanol 100 mmol, isophorone diisocyanate 90 mmol (manufactured by Tokyo Chemical Industry Co., Ltd.), DMAc 100 mL (Tokyo Chemical Industry Co., Ltd.) , 0.1 mL of dibutyltin dilaurate was added as a catalyst, and the mixture was stirred at 60 ° C. for 2 hours to synthesize compound 6.
[Manufacturing Example 4]
In a separable flask equipped with a stirrer and a thermometer, 60 mmol of N- (t-butyl) diethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.), 40 mmol of 1,4-butanediol (manufactured by Tokyo Chemical Industry Co., Ltd.), dicyclohexylmethane 4,4' -Diisocyanate 90 mmol (manufactured by Tokyo Chemical Industry Co., Ltd.), DMAc 100 mL (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.1 mL of dibutyltin dilaurate as a catalyst were added, and the mixture was stirred at 60 ° C. for 2 hours to synthesize compound 7.
[Manufacturing Example 5]
In a separable flask equipped with a stirrer and a thermometer, 100 mmol of N, N-dimethylhydrazine (manufactured by Tokyo Chemical Industry Co., Ltd.), 50 mmol of diphenylmethane diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.), and 100 mL of DMAc (manufactured by Tokyo Chemical Industry Co., Ltd.) are placed, and 60 Compound 8 was synthesized by stirring at ° C. for 2 hours.
[Manufacturing Example 6]
Put 100 mmol of N, N-dimethylhydrazine (manufactured by Tokyo Chemical Industry Co., Ltd.), 50 mmol of hexamethylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.), and 100 mL of DMAc (manufactured by Tokyo Chemical Industry Co., Ltd.) in a separable flask equipped with a stirrer and a thermometer. Compound 9 was synthesized by stirring at 60 ° C. for 2 hours.

[Examples 40 to 45]
The yarn fineness is 620 dtex, the number of filaments is 72, and diethylene glycol dibenzoate (manufactured by Tokyo Kasei Kogyo Co., Ltd .: with an aromatic ring in the compound) is contained in the oil agent so as to be 200 ppm with respect to the total weight of the polyurethane elastic fiber. The ratio of the maximum value to the minimum value of the thread diameter is 1.46 to 1.55, the elongation rate is 2%, the outflow start temperature is 200 ° C. or higher, and 2% of urethane or urea compound containing a tertiary amine is contained. The polyurethane elastic yarn winding bodies of Examples 40 to 45 were produced by incorporating the urethane or urea compound containing a tertiary amine so that the content was 100 times the content of the ester or phosphoric acid ester. As the urethane or urea compound containing the tertiary amine, the compounds 4 to 9 prepared in Production Examples 1 to 6 were used.
It was found that yarn breakage during processing can be suppressed by containing a urethane or urea compound containing a tertiary amine. The results are shown in Table 4 below.

[Examples 46 to 51]
The yarn fineness is 620 dtex, the number of filaments is 72, and diethylene glycol dibenzoate (manufactured by Tokyo Kasei Kogyo Co., Ltd .: with an aromatic ring in the compound) is contained in the oil agent so as to be 200 ppm with respect to the total weight of the polyurethane elastic fiber. The ratio of the maximum value to the minimum value of the yarn diameter is 1.46 to 1.56, the elongation rate is 2%, the outflow start temperature is 200 ° C. or higher, and the content of the compound 4 produced in Production Example 1 is as follows. Polyurethanes of Examples 46 to 51 were changed as shown in Table 4 so that the content of the urethane or urea compound containing the tertiary amine was 0.75 to 200 times the content of the ester or phosphate ester. An elastic thread winding body was manufactured.
It was found that yarn breakage during processing can be suppressed by controlling the ratio of the content of the urethane or urea compound containing the tertiary amine to the content of the ester. The results are shown in Table 4 below.

[Comparative Example 1]
Without containing ester or phosphoric acid ester in the polyurethane elastic fiber, the yarn fineness is 620 dtex, the number of filaments is 72, the ratio of the maximum value to the minimum value of the single yarn diameter is 1.47, and the outflow start temperature is 212 ° C. A polyurethane elastic yarn winding body of Comparative Example 1 having an elongation rate of 2% was produced without containing a urethane or urea compound containing a tertiary amine.
The thread was easily loosened, and thread breakage occurred frequently during processing. The results are shown in Table 4 below.

[Comparative Examples 2 to 5]
The fineness of the yarn is 620 dtex, the number of filaments is 72, the ratio of the maximum value to the minimum value of the single yarn diameter is 1.49 to 1.57, and the elongation rate without containing urethane or urea compound containing a tertiary amine. The content of diethylene glycol dibenzoate (manufactured by Tokyo Kasei Kogyo Co., Ltd .: with an aromatic ring in the compound) to be contained in the oil or polymer at 2% with respect to the total weight of the polyurethane elastic fiber and the outflow start temperature are shown in the table below. The polyurethane elastic yarn winding bodies of Comparative Examples 2 to 5 were produced by changing as shown in 4.
Thread breakage occurred frequently during processing. The results are shown in Table 4 below.

The polyurethane elastic fiber of the present invention contains a specific ester or phosphoric acid ester in the polyurethane elastic fiber, so that the single yarn does not easily come apart, the tension fluctuation during running is small, and the single yarn does not easily break due to heat. Thread breakage during processing can be sufficiently suppressed. Therefore, the polyurethane elastic fibers of the present invention can be suitably used in the manufacture of innerwear, stockings, compression wear, diapers and the like.

1 Elastic fiber winding body 2 Feeding roll 3 Winding roll 4 Tension meter 5 Digital low potential measuring instrument

Claims (14)

The polyurethane elastic fiber which is a multifilament yarn has a content of an ester or a phosphoric acid ester in which compound A and compound B are condensed is 50 ppm or more and 5% or less based on the weight of the polyurethane elastic fiber, and the compound A. Is one of a monocarboxylic acid having 4 to 30 carbon atoms, a dicarboxylic acid having 4 to 30 carbon atoms, a tricarboxylic acid having 4 to 30 carbon atoms, or a phosphoric acid, and the compound B has 1 carbon dioxide. to 30 of the mono-ol having a molecular weight of 3,000 or less of the diol, or Ri any one Tsudea molecular weight of 3,000 or less triol, and the maximum value of the diameter of the single yarn of the polyurethane elastic fiber is said multifilament yarn the ratio of the minimum value, the polyurethane elastic fiber characterized der Rukoto 1.1 to 2.0. The polyurethane elastic fiber according to claim 1, wherein the outflow start temperature of the polyurethane elastic fiber by the flow tester is 200 ° C. or higher. The polyurethane elastic fiber according to claim 1 or 2 , wherein the content of the ester or phosphoric acid ester is 50 ppm or more and 1.5% or less with respect to the weight of the polyurethane elastic fiber. The compound A is any one of a monocarboxylic acid having 4 to 30 carbon atoms, a dicarboxylic acid having 4 to 30 carbon atoms, and a tricarboxylic acid having 4 to 30 carbon atoms, according to claims 1 to 3 . The polyurethane elastic fiber according to any one item. The compound A is either a dicarboxylic acid having 4 to 30 carbon atoms or a tricarboxylic acid having 4 to 30 carbon atoms, or the compound B is a diol having a molecular weight of 3000 or less, or a molecular weight of 3000. The polyurethane elastic fiber according to any one of claims 1 to 4 , which is any one of the following triols. The polyurethane elastic fiber according to any one of claims 1 to 5 , wherein the ester or phosphoric acid ester obtained by condensing the compound A and the compound B has an aromatic ring. The polyurethane elastic fiber according to any one of claims 1 to 6 , further containing a urethane or urea compound containing a tertiary amine in an amount of 0.01% or more and 5% or less. The urethane compound containing the tertiary amine has the following formula (1):

{In the formula, R ₁ is a divalent hydrocarbon group having 5 to 30 carbon atoms, and R _{2 and R 3} are divalent hydrocarbon groups having 1 to 10 carbon atoms independently of each other. R ₄ is a monovalent hydrocarbon group having 1 to 10 carbon atoms. } The polyurethane elastic fiber according to claim 7 , which is a urethane compound having a repeating unit represented by. The urethane compound containing the tertiary amine has the following formula (1):

{In the formula, R ₁ is a divalent hydrocarbon group having 5 to 30 carbon atoms, and R _{2 and R 3} are divalent hydrocarbon groups having 1 to 10 carbon atoms independently of each other. R ₄ is a monovalent hydrocarbon group having 1 to 10 carbon atoms. } And the following formula (2):

{In the formula, R ₅ is a divalent hydrocarbon group having 5 to 30 carbon atoms, and R ₆ is a divalent hydrocarbon group or a polyoxyalkylene group having 1 to 10 carbon atoms. } The polyurethane elastic fiber according to claim 7 , which is a urethane compound having a repeating unit represented by. The urea compound containing the tertiary amine has the following formula (3):

{In the formula, R ₇ and R ₈ are monovalent hydrocarbon groups having 1 to 10 carbon atoms independently of each other, and R ₉ is a divalent hydrocarbon group having 5 to 30 carbon atoms. .. } The polyurethane elastic fiber according to claim 7 , which is a urea compound represented by. The polyurethane according to any one of claims 7 to 10 , wherein the content of the urethane or urea compound containing the tertiary amine is larger than the content of the ester or phosphoric acid ester obtained by condensing the compound A and the compound B. Elastic fiber. The polyurethane according to claim 11 , wherein the content of the urethane or urea compound containing the tertiary amine is 20 times or more and 150 times or less the content of the ester or phosphoric acid ester obtained by condensing the compound A and the compound B. Elastic fiber. The winding body of the polyurethane elastic fiber according to any one of claims 1 to 12. The winding body according to claim 13 , wherein the elongation rate of the polyurethane elastic fiber in the winding body is 5% or less.

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