JP5659781B2 - Polyurethane elastic yarn and method for producing the same - Google Patents

Description

  The present invention relates to a polyurethane elastic yarn and a method for producing the same.

         When a swimsuit using a fabric obtained by knitting or weaving polyurethane elastic fibers and polyamide fibers or polyester fibers is repeatedly exposed to chlorine water having an active chlorine concentration of 0.5 to 3 ppm in a pool, It is known that the elastic function of the elastic fiber is remarkably impaired and the thread breaks or the dye dyed on the polyamide fiber is discolored.

  In order to improve the chlorine resistance of the polyurethane elastic fiber, a polyester polyurethane elastic fiber using an aliphatic polyester diol as a raw material is preferable, but the chlorine resistance is still insufficient. Moreover, since aliphatic polyester is highly biologically active, polyester-based polyurethane elastic fibers have the disadvantage of being easily attacked by wrinkles, and the elastic function of the swimsuit is reduced during use or storage, and yarn breakage tends to occur. There is a point.

         On the other hand, polyether-based polyurethane elastic fibers using polyether diol with extremely low biological activity as a raw material are less likely to be embrittled by wrinkles, but have a problem that their chlorine resistance is inferior to that of polyester-based polyurethane elastic fibers.

  Therefore, in order to improve the chlorine resistance of the polyether-based polyurethane elastic fiber, various additives, that is, inorganic chlorine deterioration preventing agents have been proposed.

  For example, zinc oxide (see Patent Document 1), magnesium oxide, aluminum oxide, etc. (see Patent Document 2), magnesium hydroxide, aluminum hydroxide, hydrotalcite, etc. (see Patent Document 3) as inorganic chlorine degradation inhibitors A solid solution of magnesium oxide and zinc oxide (see Patent Document 4), a zinc oxide solid solution in which aluminum is dissolved in a zinc oxide crystal (see Patent Document 5), a composite oxide of zinc and aluminum (see Patent Document 6), Further, a mineral mixture of huntite and hydromagnesite (see Patent Document 7) is disclosed.

         Among these chlorine-resistant agents, those containing zinc such as zinc oxide are the highest in terms of chlorine resistance, and the time until thread breakage when immersed continuously in chlorine water is the longest. However, these zinc-containing compounds such as zinc oxide show outflow of zinc components in the dyeing process, and zinc ions react with other lubricants and chemicals dissolved in the dyeing bath to make the dyeing uneven. Sometimes. There is also concern about environmental problems due to waste water contaminated with these zinc compounds. In order to prevent these, when adding hydrotalcite or other metal carbonates, oxides or the like, the chlorine water resistance performance is not satisfactory compared to zinc oxide or the like. In addition, these inorganic chlorine-resistant agents including zinc oxide are difficult to uniformly disperse in a solvent and a spinning polymer solution in common, so that the spinnability is deteriorated and the fineness of the spun yarn becomes nonuniform. Therefore, the quality of the fabric may be deteriorated.

  On the other hand, a technique of adding polyvinyl alcohol and / or a copolymer thereof to polyurethane elastic fibers has been disclosed (see Patent Document 8). According to this, there is a description of a technique of simultaneously adding polyvinyl alcohol and / or a copolymer thereof and other inorganic substances, but even if this is used, it does not lead to an increase in dispersibility of the inorganic chlorine-resistant agent described above, It has not yet reached a satisfactory level of spinnability and fabric quality.

Further, a technique for improving the elongation, recoverability, heat resistance, and chemical resistance by containing a polymer containing a sulfonic acid group and a metal compound is also disclosed (see Patent Document 9), but the dispersibility of the metal compound is also disclosed. However, there was room for further improvement in spinnability and fabric quality.
Japanese Patent Publication No. 60-43444 Japanese Examined Patent Publication No. 61-35283 JP 2008-196067 A Japanese Patent No. 3228351 JP 2002-121537 A Japanese Patent Laid-Open No. 10-292225 Japanese National Patent Publication No. 10-508916 JP 2002-249929 A JP 2010-150677 A

  The present invention solves the above-mentioned problems of the prior art, and provides a fabric that can be stably spun for a long period of time, has excellent chlorine resistance, and has a good quality with little unevenness such as stitches and uneven dyeing. An object of the present invention is to provide a possible polyurethane elastic yarn and a method for producing the same.

In order to achieve the above object, the polyurethane elastic yarn of the present invention employs any of the following means.
(1) A polyurethane elastic yarn comprising polyurethane starting from a polymer diol and a diisocyanate, wherein at least one copolymer (a) selected from the group consisting of the following (a-1) to (a-3): And at least one metal compound (b) selected from the group consisting of the following (b-1) to (b-4).
(A-1) Copolymer of vinyl alcohol and vinyl acetal (a-2) Copolymer of vinyl acetate and vinyl acetal (a-3) Copolymer of vinyl alcohol, vinyl acetate and vinyl acetal (b -1) Hydrotalcite compound (b-2) Mixture of huntite and hydromagnesite (b-3) Carbonate, oxide and hydroxide of metal selected from Ca, Mg, Al or Ba (b) -4) Composite oxide comprising two or more metals selected from Ca, Mg, Al or Ba (2) Component ratio (weight% ratio) between the copolymer (a) and the metal compound (b) The polyurethane elastic yarn according to (1), wherein is (a) / (b) = 1/9 to 4/6 .

(3 ) A dispersing agent containing at least one copolymer (a) selected from the group consisting of the following (a-1) to (a-3) in a spinning dope containing a polyurethane starting from a polymer diol and a diisocyanate. A method for producing a polyurethane elastic yarn, which contains a dispersion of at least one metal compound (b) selected from the group consisting of the following (b-1) to (b-4).
(A-1) Copolymer of vinyl alcohol and vinyl acetal (a-2) Copolymer of vinyl acetate and vinyl acetal (a-3) Copolymer of vinyl alcohol, vinyl acetate and vinyl acetal (b -1) Hydrotalcite compound (b-2) Mixture of huntite and hydromagnesite (b-3) Carbonate, oxide and hydroxide of metal selected from Ca, Mg, Al or Ba (b) -4) Composite oxide comprising two or more metals selected from Ca, Mg, Al or Ba ( 4 ) The polyurethane elastic yarn according to (1) or (2) above or the production method according to ( 3 ) above A fabric formed by using the polyurethane elastic yarn obtained by the above.

  According to the present invention, stable continuous spinning is possible, excellent resistance to chlorine embrittlement, and a fabric having a good quality with little unevenness such as stitches and unevenness in dyeing can be provided, particularly suitable for swimsuit applications. It is possible to provide a polyurethane-based elastic yarn used in the present invention.

  The polyurethane in the present invention is not particularly limited as long as it is an elastic yarn made of polyurethane starting from a polymer diol and diisocyanate. Also, the synthesis method is not particularly limited.

  That is, for example, it may be a polyurethane urea composed of a polymer diol, diisocyanate and a low molecular weight diamine, or may be a polyurethane urethane composed of a polymer diol, diisocyanate and a low molecular weight diol. 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 in the present invention will be described.

  As the polymer diol of the structural unit constituting the polyurethane, polyether diol, polyester diol, polycarbonate diol and the like are preferable. In particular, a polyether diol is preferably used from the viewpoint of imparting flexibility and elongation to the yarn.

  The polyether-based diol preferably contains a copolymerized diol compound containing a unit represented by the following general formula.

(Where a and c are integers of 1 to 3, b is an integer of 0 to 3, R1 and R2 are H or an alkyl group of 1 to 3 carbon atoms)
Specific examples of the polyether diol compound include polyethylene glycol, modified polyethylene glycol, polypropylene glycol, polytrimethylene ether glycol, polytetramethylene ether glycol (hereinafter abbreviated as PTMG), tetrahydrofuran (hereinafter abbreviated as THF). ) And 3-methyl-THF copolymer modified PTMG, THF and 2,3-dimethyl-THF copolymer modified PTMG, THF and neopentyl glycol copolymer modified PTMG, THF and Examples thereof include random copolymers in which ethylene oxide and / or propylene oxide are irregularly arranged. One kind of these polyether glycols may be used, or two or more kinds may be mixed or copolymerized. Among these, PTMG or modified PTMG is preferable.

   Further, from the viewpoint of enhancing the abrasion resistance and light resistance of polyurethane yarn, 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 ester units derived from a polyester glycol such as a polyester diol having a side chain and a dicarboxylic acid component consisting of 3,8-dimethyldecanedioic acid and / or 3,7-dimethyldecanedioic acid and a diol component A polycarbonate diol containing bismuth is preferably used.

   Moreover, such polymer diol may be used independently and may be used by mixing or copolymerizing 2 or more types.

   The molecular weight of the polymer diol used in the present invention is preferably 1000 to 8000, more preferably 1800 to 6000 in terms of number average molecular weight in order to obtain desired levels of elongation, strength, heat resistance and the like when elastic yarn is formed. . By using a polymer diol having a molecular weight within this range, an elastic yarn excellent in elongation, strength, elastic recovery, and heat resistance can be obtained.

  Next, as the diisocyanate of the structural unit constituting the polyurethane, aromatic diisocyanates such as diphenylmethane diisocyanate (hereinafter abbreviated as MDI), tolylene diisocyanate, 1,4-diisocyanate benzene, xylylene diisocyanate, 2,6-naphthalene diisocyanate, etc. However, it is particularly suitable for synthesizing polyurethane having high heat resistance and high strength. Furthermore, as alicyclic diisocyanate, for example, methylene bis (cyclohexyl isocyanate), isophorone diisocyanate, methylcyclohexane 2,4-diisocyanate, methylcyclohexane 2,6-diisocyanate, cyclohexane 1,4-diisocyanate, hexahydroxylylene diisocyanate, hexahydrotolylene diisocyanate Isocyanate, octahydro 1,5-naphthalene diisocyanate and the like are preferable. Aliphatic diisocyanates can be used effectively particularly when suppressing yellowing of polyurethane yarns. And these diisocyanates may be used independently and may use 2 or more types together.

  Next, it is preferable to use at least one of a low molecular weight diamine and a low molecular weight diol as the chain extender of the structural unit constituting the polyurethane. In addition, you may have a hydroxyl group and amino groups in a molecule 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. It is also preferred that one or more of these are used. Particularly preferred is ethylenediamine. By using ethylenediamine, it is possible to obtain a yarn excellent in elongation, elastic recovery, and heat resistance. A triamine compound capable of forming a crosslinked structure such as diethylenetriamine may be added to these chain extenders to such an extent that the effect is not lost.

  The low molecular weight diol includes ethylene glycol (hereinafter abbreviated as EG), 1,3 propanediol, 1,4 butanediol, bishydroxyethoxybenzene, bishydroxyethylene terephthalate, 1-methyl-1,2-ethanediol. Etc. are typical ones. It is also preferred that one or more of these are used. Particularly preferred are ethylene glycol, 1,3 propanediol, and 1,4 butanediol. When these are used, a diol-extended polyurethane has a high heat resistance and a high strength yarn can be obtained.

         Furthermore, it is also preferable for the polyurethane in the present invention to use one or more end blockers. As end-capping agents, dimethylamine, diisopropylamine, ethylmethylamine, diethylamine, methylpropylamine, isopropylmethylamine, diisopropylamine, butylmethylamine, isobutylmethylamine, isopentylmethylamine, dibutylamine, diamylamine and other monoamines, ethanol Monools such as propanol, butanol, isopropanol, allyl alcohol and cyclopentanol, and monoisocyanates such as phenyl isocyanate are preferred.

  Moreover, in this invention, it is preferable that the molecular weight of a polyurethane is the range of 40000 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. The molecular weight is measured by GPC and is a value converted by polystyrene.

  And, particularly preferred as the polyurethane constituting the elastic yarn of the present invention, including the process passability, there is no practical problem, and from the viewpoint of obtaining an excellent high heat resistance, consisting of diol and diisocyanate, Moreover, the melting point on the high temperature side is in the range of 150 ° C. or higher and 300 ° C. or lower. Here, the melting point on the high temperature side corresponds to the melting point of so-called hard segment crystals of polyurethane or polyurethane urea as measured by DSC.

  That is, PTMG having a molecular weight in the range of 1000 to 8000 as a polymer diol, MDI as a diisocyanate, ethylene glycol, 1,3 propanediol, 1,4 butanediol, ethylenediamine, 1,2-propanediamine, 1 An elastic yarn produced from polyurethane having a melting point on the high temperature side in the range of 150 ° C. or higher and 300 ° C. or lower, wherein a polyurethane is synthesized using at least one selected from the group consisting of 1,3-propanediamine. In particular, the elongation is high, and as described above, there are no practical problems including process passability and excellent heat resistance.

The polyurethane elastic yarn of the present invention comprises at least one copolymer (a) selected from the group consisting of the following (a-1) to (a-3), and the following (b-1) to (b-4). And at least one metal compound (b) selected from the group consisting of:
<Copolymer (a)>
(A-1) Copolymer of vinyl alcohol and vinyl acetal (a-2) Copolymer of vinyl acetate and vinyl acetal (a-3) Copolymer of vinyl alcohol, vinyl acetate and vinyl acetal <Metal Compound (b)>
(B-1) Hydrotalcite compound (b-2) Mixture of huntite and hydromagnesite (b-3) Carbonate, oxide, and hydroxide of metal selected from Ca, Mg, Al, or Ba (B-4) A composite oxide (a-1) to (a-3) composed of two or more kinds of metals selected from Ca, Mg, Al or Ba, A vinyl alcohol-vinyl acetate copolymer produced by converting some or all of the acetyl groups of polyvinyl acetate into hydroxyl groups by hydrolysis is obtained by acetalization with aldehyde.

  Specifically, it is preferable to have a structure represented by the following general formula, for example, vinyl alcohol-vinyl acetate-vinyl formal copolymer, vinyl alcohol-vinyl acetate-vinyl butyral copolymer. Etc. are more preferable.

(However, R is hydrogen or an alkyl group. Each structural unit may be block copolymerization or random copolymerization.)
In the substance represented by the above general formula, it is preferable that x + y ≧ 70 mol% and x ≧ 40 mol% in order to improve the affinity for the solvent and to disperse the metal compound more uniformly.

  Furthermore, the number average molecular weight of the copolymer (a) is preferably in the range of 1,000 or more and 100,000 or less in order to disperse the metal compound more uniformly. The number average molecular weight here can be determined by measurement by GPC, and is a polystyrene equivalent value.

On the other hand, as described above, the metal compound (b) needs to contain at least one of (b-1) to (b-4). For example, as the hydrotalcite compound, Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O, Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ .3.5H ₂ O, or the like is preferable. A mixture of Mg ₂ Ca (CO ₃ ) ₄ and Mg ₄ (CO ₃ ) ₄ .Mg (OH) ₃ .4H ₂ O, which is a mixture of huntite and hydromagnesite, is also preferable. Further, as the metal carbonate selected from Ca, Mg, Al or Ba, calcium carbonate, magnesium carbonate, barium carbonate and the like are preferable. As the oxide, magnesium oxide, aluminum oxide and the like are preferable, and as the hydroxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide and the like are preferable. As the composite oxide, MgO.Al ₂ O ₃ or the like is preferable.

Among the metal compounds (b), hydrotalcite compounds Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O, a mixture of huntite and hydromagnesite, and a composite oxide MgO · Al ₂ O ₃ are particularly preferable. preferable. By containing such a metal compound (b), the effect of chlorine water resistance can be enhanced.

  Here, in the present invention, by simultaneously containing the copolymer (a) together with the metal compound (b), the metal compound (b) is uniformly dispersed while increasing the content of the metal compound (b). Can be blended. For this reason, the polyurethane elastic yarn is excellent in chlorine resistance, can suppress dyeing unevenness by being stably spun for a long time, and can provide a fabric having good quality. From the viewpoint of making this effect sufficient and not adversely affecting the physical properties of the fiber, the component ratio (weight% ratio) of the copolymer (a) and the metal compound (b) is (a) / ( b) = 1/9 to 4/6 is preferable, and (a) / (b) = 1.5 / 8.5 to 3/7 is more preferable. For the same reason, the metal compound (b) is preferably contained in an amount of 0.1 to 10% by weight, more preferably 1 to 6% by weight, based on the weight of the polyurethane elastic yarn.

  Since the metal compound (b) is blended in the spinning solution of the polyurethane-based elastic yarn, it is preferably a fine powder having an average particle diameter of 2 μm or less and a fine powder having an average particle diameter of 1 μm or less from the viewpoint of spinning stability. More preferable powder.

  Further, for the purpose of further improving the dispersibility of the metal compound (b) in the yarn and stabilizing the spinning, for example, organic substances such as fatty acids, fatty acid esters, phosphate esters, polyol organic substances, silane series It is also preferable to use a metal compound (b) surface-treated with a coupling agent, a titanate coupling agent, water glass, a fatty acid metal salt, or a mixture thereof.

  Furthermore, in the present invention, various stabilizers and pigments may be contained in the polyurethane elastic yarn or polyurethane spinning solution. For example, hindered phenolic agents such as 2,6-di-t-butyl-p-cresol (BHT) and “Sumilyzer GA-80” (product name) manufactured by Sumitomo Chemical Co. Various benzotriazole and benzophenone drugs such as “Chinubin” (registered trademark) manufactured by Ciba Geigy, phosphorous drugs such as “Sumilyzer P-16” (product name) manufactured by Sumitomo Chemical Co., Ltd., and various hindered amine drugs Various inorganic pigments such as iron oxide, titanium oxide, and carbon black, fluorine or silicone resin powders, metal soaps such as magnesium stearate, and bactericides, deodorants, and the like containing silver and these compounds Contains lubricants such as silicone and mineral oil, various antistatic agents such as barium sulfate, cerium oxide, betaine and phosphate. It is also preferred that, It is also preferred to react the these with polymers. 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 (such as bamboo charcoal, charcoal, carbon black, porous mud, clay, diatomaceous earth, coconut shell activated carbon, coal-based activated carbon, zeolite, pearlite, etc.) , And may be added within a range that does not impair the effects of the present invention.

  These other additives may be added when the spinning solution is prepared by mixing the polyurethane solution with the copolymer (a) and the metal compound (b), or the polyurethane solution before mixing. You may make it contain previously in the inside or dispersion liquid. The content of these additives is appropriately determined according to the purpose and the like.

  Next, the method for producing the polyurethane elastic yarn of the present invention will be described in detail.

  In the production method of the present invention, at least one copolymer selected from the group consisting of the above (a-1) to (a-3) is added to a spinning dope containing polyurethane starting from a polymer diol and diisocyanate ( Spinning is performed by containing a dispersion of at least one metal compound (b) selected from the group of (b-1) to (b-4), which contains a) as a dispersant.

  The dispersion of the metal compound (b) containing such a copolymer (a) as a dispersant is preferably prepared in advance as a spinning solution containing polyurethane, and then the dispersion is added to the spinning solution. .

  The method for producing a polyurethane solution and polyurethane as a solute in the solution may be either a melt polymerization method or a solution polymerization method, or may be another method. However, the solution polymerization method is more preferable. In the case of the solution polymerization method, since the generation of foreign matters such as gels is small in the polyurethane, it is easy to spin and it is easy to produce a polyurethane yarn with a low fineness. Further, in the case of solution polymerization, there is an advantage that the operation of making a solution can be omitted.

  As a polyurethane particularly suitable for the present invention, PTMG having a molecular weight of 1000 to 8000 is used as a polymer diol, MDI is used as a diisocyanate, ethylene glycol, 1,3 propanediol, 1,4 butane is used as a chain extender. Examples include those synthesized using at least one of diol, ethylenediamine, 1,2-propanediamine, and 1,3-propanediamine, and having a melting point on the high temperature side in the range of 200 ° C to 300 ° C. .

  Such polyurethane can be obtained, for example, by synthesizing using the above-mentioned raw materials in DMAc, DMF, DMSO, NMP, or the like or a solvent containing these as a main component. For example, each raw material is charged in such a solvent, dissolved, heated to an appropriate temperature and reacted to form polyurethane, a so-called one-shot method, or polymer diol and diisocyanate are first melt-reacted and then reacted. A particularly preferable method is a method in which a product is dissolved in a solvent and reacted with the above-mentioned diol to form polyurethane.

  When using a diol as the chain extender, the typical method for controlling the high temperature melting point of the polyurethane within the range of 150 ° C. to 300 ° C. is to control the type and ratio of the polymer diol, MDI, and diol. Is mentioned. For example, when the molecular weight of the polymer diol is low, a polyurethane having a high melting point on the high temperature side can be obtained by relatively increasing the proportion of MDI. Similarly, when the molecular weight of the diol is low, a polyurethane having a high melting point on the high temperature side can be obtained by relatively reducing the proportion of the polymer diol. When the molecular weight of the polymer diol is 1800 or more, in order to make the melting point on the high temperature side 150 ° C. or more, the polymerization is advanced at a ratio of (number of moles of MDI) / (number of moles of polymer diol) = 1.5 or more. Is 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-dimethylamido 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 polyurethane in the polyurethane solution thus obtained is usually preferably in the range of 30% by weight to 80% by weight.

  In the present invention, a dispersion of the metal compound (b) containing the copolymer (a) as a dispersant is added to the polyurethane solution. As a method for adding the dispersion to the polyurethane solution, 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. In addition, after adding the said dispersion liquid, the phenomenon in which the solution viscosity of a mixed solution becomes higher than expected compared with the solution viscosity of the polyurethane before addition may generate | occur | produce. 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.

  In addition, when the dispersion liquid is added to the polyurethane solution, for example, the above-mentioned chemicals such as a light resistance agent and an antioxidant and a pigment may be added simultaneously.

  The polyurethane elastic yarn of the present invention can be obtained by, for example, dry-spinning, wet-spinning, or melt-spinning and winding up the spinning stock solution configured as described above. 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 yarn of 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 yarn of the present invention are particularly easily influenced by the speed ratio of the godet roller and the winder, and therefore it is preferable to be determined appropriately according to the intended use of the yarn. That is, from the viewpoint of obtaining a polyurethane elastic yarn 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 yarn 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 polyurethane elastic yarn as described above is suitable for knitting, weaving, and string processing, and can be used as an excellent stretch fabric by being used alone or in combination with various fibers. In particular, the polyurethane elastic yarn contains the metal compound (b) together with the copolymer (a) so that the metal compound (b) is uniformly dispersed and blended while increasing the content of the metal compound (b). can do. Therefore, it is excellent in chlorine resistance and can be stably spun for a long time. When a fabric is made using this fiber, unevenness such as stitches and dyeing unevenness can be suppressed, and a fabric having good quality can be provided.

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

  A method for measuring the strength, elongation, permanent strain rate, stress relaxation, chlorine embrittlement resistance, and appearance quality of the dyed stretch fabric will be described.

[Permanent distortion, stress relaxation, breaking strength, breaking elongation]
A permanent elastic modulus, stress relaxation, breaking strength, and breaking elongation were measured by tensile testing polyurethane elastic yarn 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 subjected to 300% elongation at a tensile speed of 50 cm / min five times, and the stress at the time of the third 300% elongation was defined as (G1). 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 length of the sample when the elongation of the sample was recovered and 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)
Stress relaxation (%) = 100 × ((G1) − (G2)) / (G1)
Permanent distortion rate (%) = 100 × ((L2) − (L1)) / (L1)
Elongation at break (%) = 100 × ((L3) − (L1)) / (L1).

[Chlorine embrittlement resistance]
Diluting sodium hypochlorite solution with ion-exchanged water to obtain an effective chlorine concentration of 3 ppm, further a urea concentration of 3 ppm, and adjusting the pH of the chlorine water adjusted to pH 7.2 with a buffer solution of sulfuric acid to 28 ° C. Was immersed under a load of 5 g, and the time until the sample yarn was broken was evaluated.
The measurement was performed at n = 5, and the average value was adopted.

[Amount of chlorine-resistant agent falling off]
The bath adjusted to pH 5.7 is heated to 130 ° C., and 5 g of the sample yarn is immersed for 60 minutes. Next, a bath to which hydrosulfite, NaOH, and a refining agent Sanmor WX-24 are added is heated to 80 ° C. and immersed for 20 minutes. The treated sample yarn is incinerated in an electric furnace at 900 ° C., and the weight is measured. From the weight of the ashed product, it is converted into the weight (W1) of the metal compound, and the amount of the chlorine-resistant agent falling off is calculated by the following formula. The measurement was performed at n = 2, and the average value was adopted.
Dropout amount (%) = 100 × (W0−W1) / (W0)
W0: Theoretical content of metal compound [Appearance quality of dyed stretch fabric]
The stretch fabric was allowed to stand on a flat work table so as not to be wrinkled, visually observed, and scored with reference to the following criteria. In addition, the determination was performed by five or more people, and an average score was adopted.
5 points: No sagging, streaks, thread breakage, no problem in actual use.
3 points: There is some slack, but there is no streak or thread breakage, and there seems to be no problem in actual use.
0 point: There are slack, thread breakage and streaks, and it cannot be used.

[Example 1]
A DMAc solution (35% by weight) of polyurethane urea polymer (P1) composed of PTMG, MDI, ethylenediamine having a molecular weight of 1800, and diethylamine as a terminal blocking agent was polymerized by a conventional method to obtain a polymer solution P1.

  Next, a polyvinyl alcohol / vinyl butyral copolymer obtained by acetalizing a part of polyvinyl alcohol obtained by hydrolyzing polyvinyl acetate as a copolymer (a) with butanol = 3/7 (the above ( corresponding to a-1), and preparing the DMAc solution, further adding hydrotalcite (NAOX-19 manufactured by Toda Kogyo Co., Ltd., (b-1) above to the DMAc solution as the metal compound (b). Applicable) was added to obtain a metal compound dispersion A1 (35% by weight). The component ratio (weight% ratio) of the copolymer (a) and the metal compound (b) was set to a ratio of (a) / (b) = 2/8. For the adjustment, horizontal mill WILLY A. Using DYNO-MIL KDL manufactured by BACHOFEN, 85% zirconia beads were filled and uniformly dispersed under the condition of a flow rate of 50 g / min.

         Further, as an antioxidant, a polyurethane solution ("METACROL" (registered trademark) 2462, c1 manufactured by DuPont) produced by a reaction of t-butyldiethanolamine and methylene-bis- (4-cyclohexyl isocyanate), and , P-cresol and a condensation polymer of divinylbenzene ("Metacral" (registered trademark) 2390, c2 manufactured by DuPont) were mixed in a ratio of 2 to 1 (weight ratio) to prepare an antioxidant DMAc solution (concentration 35). % By weight), and this was used as the other additive solution C1 (35% by weight).

  Polymer solution P1, metal compound dispersion A1, and other additive solution C1 were uniformly mixed at 90.75 wt%, 6.25 wt%, and 3 wt%, respectively, to obtain spinning solution D1.

  This spinning solution was dry-spun at a spinning speed of 600 m / min at a speed ratio of 1.20 between the godet roller and the winder, and wound to produce a 40 dtex, 4-filament multifilament polyurethane elastic yarn (500 g wound yarn). did. The composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1.

  Further, stretch fabrics were produced by the following method, and the appearance quality was evaluated. Polyurethane elastic yarns and polyamide fibers (50 denier / 17 filaments) obtained by melt spinning polyhexamethylene adipamide were knitted using a tricot machine to produce warp knitted 2-way tricots. The knitting structure was half, and knitting was performed under the conditions of 28 gauge, front runner 160 cm, and back runner 80 cm, with polyamide fibers on the front and polyurethane elastic fibers on the back.

  The obtained 2-way tricot raw machine was refined, relaxed, dried, and heat-set and dyed. For dyeing, Irgalan Black BGK (CHIBA Specialty Chemicals Co., Ltd., trade name) 4.0% owf as a dye, Newbon SZ (Nikka Chemical Co., Ltd., trade name) 2.0% owf as a leveling agent, pH control It was treated at 98 ° C. for 40 minutes in a 0.3 g / L bath of NC Acid W (Nikka Chemical Co., Ltd., trade name) as an agent. The dyed 2-way tricot was fixed with natural tannin. Fix treatment is treatment with Hifix SL (a blend of natural tannic acid and tartarite, manufactured by Dainippon Pharmaceutical Co., Ltd.) in a 5% owf bath at 80 ° C. for 20 minutes, and a 2-way tricot dyed fabric is obtained. Created.

  Table 2 shows the evaluation results of the spinnability, breaking elongation, breaking strength, permanent set rate, stress relaxation, chlorine embrittlement resistance, amount of chlorine-resistant agent falling off, and appearance quality of stretch fabric of this polyurethane elastic yarn.

[Example 2]
Using the polyvinyl alcohol / vinyl butyral copolymer = 3/7 (corresponding to the above (a-1)) used in Example 1 as the copolymer (a), the DMAc solution was prepared. Further, calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd., corresponding to the above (b-3)) was added as the metal compound (b) to obtain a metal compound dispersion A2 (35% by weight).

  The polymer solution P1, the metal compound dispersion A2, and the other additive solution C1 prepared in Example 1 were uniformly mixed at 90.75 wt%, 6.25 wt%, and 3 wt%, respectively, to obtain a spinning solution D2. .

  This spinning solution was dry-spun at a spinning speed of 600 m / min at a speed ratio of 1.20 between the godet roller and the winder, and wound to produce a 40 dtex, 4-filament multifilament polyurethane elastic yarn (500 g wound yarn). did. Moreover, the textile fabric was produced similarly to Example 1 and the external appearance quality was evaluated.

  The composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1. Table 2 shows the evaluation results of the spinnability, breaking elongation, breaking strength, permanent set rate, stress relaxation, chlorine embrittlement resistance, amount of chlorine-resistant agent falling off, and appearance quality of stretch fabric of this polyurethane elastic yarn.

[Example 3]
Polyvinyl acetate / vinyl butyral copolymer obtained by acetalizing polyvinyl alcohol of polyvinyl acetate / polyvinyl alcohol copolymer obtained by hydrolysis of polyvinyl acetate as copolymer (a) = 4 / 6 (corresponding to the above (a-2)), a DMAc solution thereof was prepared, and the DMAc solution was further mixed with huntite and hydromagnesite = 50/50 as a metal compound (b) (UK Microfine Minerals Ltd. Manufactured, (corresponding to (b-2)) was added to obtain a metal compound dispersion A3 (35 wt%).

  Polymer solution P1, metal compound dispersion A3, and other additive solution C1 prepared in Example 1 were uniformly mixed at 90.75 wt%, 6.25 wt%, and 3 wt%, respectively, to obtain spinning solution D3. .

  This spinning solution was dry-spun at a spinning speed of 600 m / min at a speed ratio of 1.20 between the godet roller and the winder, and wound to produce a 40 dtex, 4-filament multifilament polyurethane elastic yarn (500 g wound yarn). did. Moreover, the textile fabric was produced similarly to Example 1 and the external appearance quality was evaluated.

  The composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1. Table 2 shows the evaluation results of the spinnability, breaking elongation, breaking strength, permanent set rate, stress relaxation, chlorine embrittlement resistance, amount of chlorine-resistant agent falling off, and appearance quality of stretch fabric of this polyurethane elastic yarn.

[Example 4]
Using the polyvinyl acetate / vinyl butyral copolymer = 4/6 (corresponding to the above (a-2)) used in Example 3 as the copolymer (a), the DMAc solution was prepared. Furthermore, it corresponds to the composite oxide MgO.Al ₂ O ₃ obtained by firing hydrotalcite (NAOX-19 manufactured by Toda Kogyo Co., Ltd.) at 900 ° C. as the metal compound (b) (above (b-4)). ) To obtain a metal compound dispersion A4 (35 wt%).

  Polymer solution P1, metal compound dispersion A4, and other additive solution C1 prepared in Example 1 were uniformly mixed at 90.75 wt%, 6.25 wt%, and 3 wt%, respectively, to obtain spinning solution D4. .

  This spinning solution was dry-spun at a spinning speed of 600 m / min at a speed ratio of 1.20 between the godet roller and the winder, and wound to produce a 40 dtex, 4-filament multifilament polyurethane elastic yarn (500 g wound yarn). did. The composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1. Moreover, the textile fabric was produced similarly to Example 1 and the external appearance quality was evaluated.

  The composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1. Table 2 shows the evaluation results of the spinnability, breaking elongation, breaking strength, permanent set rate, stress relaxation, chlorine embrittlement resistance, amount of chlorine-resistant agent falling off, and appearance quality of stretch fabric of this polyurethane elastic yarn.

[Example 5]
As the copolymer (a), a polyvinyl alcohol / vinyl acetate / vinyl formal copolymer having a molar ratio of each composition of 2/3/5 (Denka formal manufactured by Denki Kagaku Kogyo Co., Ltd., (a-3) above) The corresponding DMAc solution is prepared, hydrotalcite (NAOX-19 manufactured by Toda Kogyo Co., Ltd., corresponding to the above (b-1)) is further added as a metal compound (b) to the DMAc solution, Metal compound dispersion A5 (35% by weight) was obtained. The component ratio (weight% ratio) of the copolymer (a) and the metal compound (b) was set to a ratio of (a) / (b) = 2/8.

  Polymer solution P1, metal compound dispersion A5, and other additive solution C1 were uniformly mixed at 90.75 wt%, 6.25 wt%, and 3 wt%, respectively, to obtain spinning solution D5.

  This spinning solution was dry-spun at a spinning speed of 600 m / min at a speed ratio of 1.20 between the godet roller and the winder, and wound to produce a 40 dtex, 4-filament multifilament polyurethane elastic yarn (500 g wound yarn). did. Moreover, the textile fabric was produced similarly to Example 1 and the external appearance quality was evaluated.

  The composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1. Table 2 shows the evaluation results of the spinnability, breaking elongation, breaking strength, permanent set rate, stress relaxation, chlorine embrittlement resistance, amount of chlorine-resistant agent falling off, and appearance quality of stretch fabric of this polyurethane elastic yarn.

[Example 6]
As a copolymer (a), a polyvinyl alcohol / vinyl acetate / vinyl butyral copolymer having a molar ratio of each composition of 1/4/5 (Denka Butyral manufactured by Denki Kagaku Kogyo Co., Ltd., corresponding to (a-3) above) ) As a dispersant, and hydrotalcite (NAOX-19 manufactured by Toda Kogyo Co., Ltd., corresponding to the above (b-1)) was used as the metal compound (b), and the DMAc was prepared in the same manner as in Example 1. A dispersion was prepared and used as DMAc solution A6 (35% by weight). The component ratio (weight% ratio) of the copolymer (a) and the metal compound (b) was set to a ratio of (a) / (b) = 2/8.

         Polymer solution P1 prepared in Example 1, dispersion A6 of the above metal compound, and other additive solution C1 were mixed uniformly at 90.75 wt%, 6.25 wt%, and 3 wt%, respectively. A spinning solution D6 was obtained.

  This spinning solution was dry-spun at a spinning speed of 600 m / min at a speed ratio of 1.20 between the godet roller and the winder, and wound to produce a 40 dtex, 4-filament multifilament polyurethane elastic yarn (500 g wound yarn). did. Moreover, the textile fabric was produced similarly to Example 1 and the external appearance quality was evaluated.

The composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1. Table 2 shows the evaluation results of the spinnability, breaking elongation, breaking strength, permanent set rate, stress relaxation, chlorine embrittlement resistance, amount of chlorine-resistant agent falling off, and appearance quality of stretch fabric of this polyurethane elastic yarn.
[Example 7]
As a copolymer (a), a polyvinyl alcohol / vinyl acetate / vinyl butyral copolymer having a molar ratio of each composition of 1/4/5 (Denka Butyral manufactured by Denki Kagaku Kogyo Co., Ltd., corresponding to (a-3) above) ) As a dispersant, and as a metal compound (b), a mixture of huntite and hydromagnesite = 50/50 (manufactured by Microfine Minerals Ltd., UK, corresponding to (b-2)) is used. The DMAc dispersion was prepared to prepare DMAc solution A7 (35% by weight). The component ratio (weight% ratio) of the copolymer (a) and the metal compound (b) was set to a ratio of (a) / (b) = 2/8.

         The polymer solution P1 prepared in Example 1, the metal compound dispersion A7, and the other additive solution C1 were uniformly mixed at 90.75 wt%, 6.25 wt%, and 3 wt%, respectively. A spinning solution D7 was obtained.

  This spinning solution was dry-spun at a spinning speed of 600 m / min at a speed ratio of 1.20 between the godet roller and the winder, and wound to produce a 40 dtex, 4-filament multifilament polyurethane elastic yarn (500 g wound yarn). did. Moreover, the textile fabric was produced similarly to Example 1 and the external appearance quality was evaluated.

  The composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1. Table 2 shows the evaluation results of the spinnability, breaking elongation, breaking strength, permanent set rate, stress relaxation, chlorine embrittlement resistance, amount of chlorine-resistant agent falling off, and appearance quality of stretch fabric of this polyurethane elastic yarn.

[Example 8]
As a copolymer (a), a polyvinyl alcohol / vinyl acetate / vinyl butyral copolymer having a molar ratio of each composition of 1/4/5 (Denka Butyral manufactured by Denki Kagaku Kogyo Co., Ltd., corresponding to (a-3) above) ) As a dispersant, and further using calcium carbonate (Shiraishi Calcium Co., Ltd., corresponding to the above (b-3)) as the metal compound (b), and preparing the DMAc dispersion in the same manner as in Example 1. DMAc solution A8 (35% by weight). The component ratio (weight% ratio) of the copolymer (a) and the metal compound (b) was set to a ratio of (a) / (b) = 2/8.

         The polymer solution P1 prepared in Example 1, the dispersion A8 of the above metal compound, and the other additive solution C1 were mixed uniformly at 90.75 wt%, 6.25 wt%, and 3 wt%, respectively. A spinning solution D8 was obtained.

  This spinning solution was dry-spun at a spinning speed of 600 m / min at a speed ratio of 1.20 between the godet roller and the winder, and wound to produce a 40 dtex, 4-filament multifilament polyurethane elastic yarn (500 g wound yarn). did. Moreover, the textile fabric was produced similarly to Example 1 and the external appearance quality was evaluated.

  The composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1. Table 2 shows the evaluation results of the spinnability, breaking elongation, breaking strength, permanent set rate, stress relaxation, chlorine embrittlement resistance, amount of chlorine-resistant agent falling off, and appearance quality of stretch fabric of this polyurethane elastic yarn.

[Example 9]
As a copolymer (a), a polyvinyl alcohol / vinyl acetate / vinyl butyral copolymer having a molar ratio of each composition of 1/4/5 (Denka Butyral manufactured by Denki Kagaku Kogyo Co., Ltd., corresponding to (a-3) above) ) As a dispersant, and as a metal compound (b), a composite oxide MgO.Al ₂ O ₃ (above) obtained by firing hydrotalcite (NAOX-19 manufactured by Toda Kogyo Co., Ltd.) at 900 ° C. (Corresponding to (b-4)), the DMAc dispersion was prepared in the same manner as in Example 1 to obtain DMAc solution A9 (35% by weight). The component ratio (weight% ratio) of the copolymer (a) and the metal compound (b) was set to a ratio of (a) / (b) = 2/8.

         The polymer solution P1 prepared in Example 1, the above dispersion A9 of metal compound, and the other additive solution C1 were mixed uniformly at 90.75 wt%, 6.25 wt%, and 3 wt%, respectively. A spinning solution D9 was obtained.

  This spinning solution was dry-spun at a spinning speed of 600 m / min at a speed ratio of 1.20 between the godet roller and the winder, and wound to produce a 40 dtex, 4-filament multifilament polyurethane elastic yarn (500 g wound yarn). did. Moreover, the textile fabric was produced similarly to Example 1 and the external appearance quality was evaluated.

  The composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1. Table 2 shows the evaluation results of the spinnability, breaking elongation, breaking strength, permanent set rate, stress relaxation, chlorine embrittlement resistance, amount of chlorine-resistant agent falling off, and appearance quality of stretch fabric of this polyurethane elastic yarn.

[Example 10]
As the copolymer (a), a polyvinyl alcohol / vinyl acetate / vinyl butyral copolymer (Denka Butyral manufactured by Denki Kagaku Kogyo Co., Ltd.) having a molar ratio of each composition of 1/4/5 is used as a dispersant, and a metal As compound (b), hydrotalcite (NAOX-19 manufactured by Toda Kogyo Co., Ltd.) was added to prepare a dispersion, which was designated as DMAc dispersion A10 (35% by weight). The component ratio (weight% ratio) of the copolymer (a) and the metal compound (b) was set to a ratio of (a) / (b) = 1.2 / 8.8.

  The polymer solution P1, the metal compound dispersion A10 and the other additive solution C1 prepared in Example 1 were uniformly mixed at 91.3 wt%, 5.7 wt%, and 3 wt%, respectively, and the spinning solution D10 and did.

  This spinning solution D10 was dry-spun at a spinning speed of 600 m / min at a speed ratio of 1.20 between the godet roller and the winder, and wound to obtain 40 dtex, 4-filament multifilament polyurethane elastic yarn (500 g wound body). Produced. Moreover, the textile fabric was produced similarly to Example 1 and the external appearance quality was evaluated.

  The composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1. Table 2 shows the evaluation results of the spinnability, breaking elongation, breaking strength, permanent set rate, stress relaxation, chlorine embrittlement resistance, amount of chlorine-resistant agent falling off, and appearance quality of stretch fabric of this polyurethane elastic yarn.

[Example 11]
As the copolymer (a), a polyvinyl alcohol / vinyl acetate / vinyl butyral copolymer (Denka Butyral manufactured by Denki Kagaku Kogyo Co., Ltd.) having a molar ratio of each composition of 1/4/5 is used as a dispersant, and a metal As compound (b), hydrotalcite (NAOX-19 manufactured by Toda Kogyo Co., Ltd.) was added to prepare a dispersion, which was designated as DMAc dispersion A11 (35% by weight). The component ratio (weight% ratio) of the copolymer (a) and the metal compound (b) was set to a ratio of (a) / (b) = 3.8 / 6.2.

  The polymer solution P1, the metal compound dispersion A11 and the other additive solution C1 prepared in Example 1 were uniformly mixed at 88.9 wt%, 8.1 wt%, and 3 wt%, respectively, and the spinning solution D11 and did.

  This spinning solution D11 is dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and winder of 1.20, wound up, and is made of 40 dtex, 4-filament multifilament polyurethane elastic yarn (500 g wound body). Was made. Moreover, the textile fabric was produced similarly to Example 1 and the external appearance quality was evaluated.

The composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1. Table 2 shows the evaluation results of the spinnability, breaking elongation, breaking strength, permanent set rate, stress relaxation, chlorine embrittlement resistance, amount of chlorine-resistant agent falling off, and appearance quality of stretch fabric of this polyurethane elastic yarn.
[Example 12]
As the copolymer (a), a polyvinyl alcohol / vinyl acetate / vinyl butyral copolymer (Denka Butyral manufactured by Denki Kagaku Kogyo Co., Ltd.) having a molar ratio of each composition of 1/4/5 is used as a dispersant, and a metal As compound (b), hydrotalcite (NAOX-19 manufactured by Toda Kogyo Co., Ltd.) was added to prepare a dispersion, which was designated as DMAc dispersion A12 (35% by weight). The component ratio (weight% ratio) of the copolymer (a) and the metal compound (b) was set to a ratio of (a) / (b) = 0.8 / 9.2.

  The polymer solution P1, the metal compound dispersion A12 and the other additive solution C1 prepared in Example 1 were uniformly mixed at 91.6 wt%, 5.4 wt%, and 3 wt%, respectively, and the spinning solution D12 and did.

  This spinning solution D12 was dry-spun at a spinning speed of 600 m / min with a speed ratio of 1.20 between the godet roller and the winder, and wound to obtain 40 dtex, 4-filament multifilament polyurethane elastic yarn (500 g wound body). Produced. Moreover, the textile fabric was produced similarly to Example 1 and the external appearance quality was evaluated.

  The composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1. Table 2 shows the evaluation results of the spinnability, breaking elongation, breaking strength, permanent set rate, stress relaxation, chlorine embrittlement resistance, amount of chlorine-resistant agent falling off, and appearance quality of stretch fabric of this polyurethane elastic yarn.

[Example 13]
As the copolymer (a), a polyvinyl alcohol / vinyl acetate / vinyl butyral copolymer (Denka Butyral manufactured by Denki Kagaku Kogyo Co., Ltd.) having a molar ratio of each composition of 1/4/5 is used as a dispersant, and a metal Hydrotalcite (NAOX-19, manufactured by Toda Kogyo Co., Ltd.) was added as the compound (b) to prepare a dispersion, which was designated as DMAc dispersion A13 (35% by weight). The component ratio (weight% ratio) of the copolymer (a) and the metal compound (b) was set to a ratio of (a) / (b) = 4.4 / 5.6.

  The polymer solution P1, the metal compound dispersion A13, and the other additive solution C1 prepared in Example 1 were uniformly mixed at 88.0 wt%, 9.0 wt%, and 3 wt%, respectively, and the spinning solution D13 and did.

  This spinning solution D13 was dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and the winder of 1.20, wound up, and 40 decitex, 4-filament multifilament polyurethane elastic yarn (500 g wound body). Was made. Moreover, the textile fabric was produced similarly to Example 1 and the external appearance quality was evaluated.

  The composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1. Table 2 shows the evaluation results of the spinnability, breaking elongation, breaking strength, permanent set rate, stress relaxation, chlorine embrittlement resistance, amount of chlorine-resistant agent falling off, and appearance quality of stretch fabric of this polyurethane elastic yarn.

[Example 14]
As a copolymer (a), a molar ratio of each composition is 4/3/3, and a polyvinyl alcohol / vinyl acetate / vinyl butyral copolymer (Denka Butyral manufactured by Denki Kagaku Kogyo Co., Ltd., corresponding to the above (a-3) ) As a dispersant, and hydrotalcite (NAOX-19 manufactured by Toda Kogyo Co., Ltd.) was added as a metal compound (b) to prepare a dispersion, which was designated as DMAc dispersion A14 (35% by weight). The component ratio (weight% ratio) of the copolymer (a) and the metal compound (b) was set to a ratio of (a) / (b) = 2/8.

  The polymer solution P1, the metal compound dispersion A14 and the other additive solution C1 prepared in Example 1 were uniformly mixed at 88.0 wt%, 9.0 wt%, and 3 wt%, respectively, and the spinning solution D14 and did.

  This spinning solution D14 was dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and winder of 1.20, wound up, 40 decitex, 4-filament multi-filament polyurethane elastic yarn (500 g wound body) Was made. Moreover, the textile fabric was produced similarly to Example 1 and the external appearance quality was evaluated.

  The composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1. Table 2 shows the evaluation results of the spinnability, breaking elongation, breaking strength, permanent set rate, stress relaxation, chlorine embrittlement resistance, amount of chlorine-resistant agent falling off, and appearance quality of stretch fabric of this polyurethane elastic yarn.

[Comparative Example 1]
The polymer solution P1 prepared in Example 1 and the other additive solution C1 prepared in Example 1 were uniformly mixed at a ratio of 97% by weight and 3% by weight, respectively, to obtain a spinning solution E1. This spinning solution E1 was dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and the winder of 1.20, wound up, 40 decitex, 4-filament multi-filament polyurethane elastic yarn (500 g wound body) Was made. Moreover, the textile fabric was produced similarly to Example 1 and the external appearance quality was evaluated.

  The composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1. Table 2 shows the evaluation results of the spinnability, breaking elongation, breaking strength, permanent set rate, stress relaxation, chlorine embrittlement resistance, amount of chlorine-resistant agent falling off, and appearance quality of stretch fabric of this polyurethane elastic yarn.

[Comparative Example 2]
Zinc oxide (manufactured by Honjo Chemical Co., Ltd.) was used as the metal compound (b), and a polyether ester acid amine salt was used as a dispersant, which was dispersed in DMAc to obtain a dispersion A15 (35% by weight). The polymer solution P1 prepared in Example 1, the metal compound dispersion A15 described above, and the other additive solution additive solution C1 prepared in Example 1 were 90.75% by weight, 6.25% by weight, and 3% by weight, respectively. % Was uniformly mixed to obtain a spinning solution E2.

  The spinning solution E2 was dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and the winder of 1.20, wound up, and 40 decitex, 4-filament multifilament polyurethane elastic yarn (500 g wound body). Was made. Moreover, the textile fabric was produced similarly to Example 1 and the external appearance quality was evaluated.

  The composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1. Table 2 shows the evaluation results of the spinnability, breaking elongation, breaking strength, permanent set rate, stress relaxation, chlorine embrittlement resistance, amount of chlorine-resistant agent falling off, and appearance quality of stretch fabric of this polyurethane elastic yarn.

[Comparative Example 3]
Hydrotalcite (NAOX-19 manufactured by Toda Kogyo Co., Ltd.) was used as the metal compound (b), polyvinyl alcohol was used as a dispersant, and the resultant was dispersed in DMAc to obtain dispersion A16 (35% by weight). The polymer solution P1 prepared in Example 1, the above metal compound dispersion A16, and the other additive solution additive solution C1 prepared in Example 1 were 90.75% by weight, 6.25% by weight, and 3% by weight, respectively. % Was uniformly mixed to obtain a spinning solution E3.

  This spinning solution E3 was dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and winder of 1.20, wound up, 40 decitex, 4-filament multifilament polyurethane elastic yarn (500 g wound body) Was made. Moreover, the textile fabric was produced similarly to Example 1 and the external appearance quality was evaluated.

  The composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1. Table 2 shows the evaluation results of the spinnability, breaking elongation, breaking strength, permanent set rate, stress relaxation, chlorine embrittlement resistance, amount of chlorine-resistant agent falling off, and appearance quality of stretch fabric of this polyurethane elastic yarn.

[Comparative Example 4]
Hydrotalcite (NAOX-19 manufactured by Toda Kogyo Co., Ltd.) is used as the metal compound (b), a polyvinyl alcohol sulfonic acid modified product is used as a dispersant, dispersed in DMAc, and dispersion A17 (35% by weight) did. The polymer solution P1 prepared in Example 1, the metal compound dispersion A17 and the other additive solution C1 prepared in Example 1 were 90.75% by weight, 6.25% by weight, and 3% by weight, respectively. To obtain a spinning solution E4.

  This spinning solution E4 was dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and the winder of 1.20, wound up, 40 decitex, 4-filament multi-filament polyurethane elastic yarn (500 g wound body) Was made. Moreover, the textile fabric was produced similarly to Example 1 and the external appearance quality was evaluated.

  The composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1. Table 2 shows the evaluation results of the spinnability, breaking elongation, breaking strength, permanent set rate, stress relaxation, chlorine embrittlement resistance, amount of chlorine-resistant agent falling off, and appearance quality of stretch fabric of this polyurethane elastic yarn.

  The polyurethane elastic yarn of the present invention has not only continuous spinning stability and chlorine resistance, but also high tensile elongation, high recovery, alkali resistance, resistance to various drugs, high heat resistance, and transparency. high. Therefore, the fabric using this elastic yarn is suitably used not only for swimwear but also for general clothing, etc., and they are excellent in detachability, fit, wearing feeling, dyeability, discoloration resistance, appearance quality, etc. It will be. Specific applications of the fabric include socks, stockings, circular knitting, tricots, swimwear, ski trousers, work clothes, smoke fire clothes, golf trousers, wet suits, bras, girdles, gloves, various textile products, fastening materials, 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.

Claims (4)

A polyurethane elastic yarn comprising a polyurethane starting from a polymer diol and a diisocyanate, wherein at least one copolymer (a) selected from the group consisting of the following (a-1) to (a-3): A polyurethane elastic yarn containing at least one metal compound (b) selected from the group consisting of (b-1) to (b-4).
(A-1) Copolymer of vinyl alcohol and vinyl acetal (a-2) Copolymer of vinyl acetate and vinyl acetal (a-3) Copolymer of vinyl alcohol, vinyl acetate and vinyl acetal (b -1) Hydrotalcite compound (b-2) Mixture of huntite and hydromagnesite (b-3) Carbonate, oxide and hydroxide of metal selected from Ca, Mg, Al or Ba (b) -4) A composite oxide composed of two or more metals selected from Ca, Mg, Al or Ba   The polyurethane elasticity of Claim 1 whose component ratio (weight% ratio) of the said copolymer (a) and the said metal compound (b) is (a) / (b) = 1 / 9-4 / 6. yarn. A spinning dope containing a polyurethane starting from a polymer diol and a diisocyanate contains at least one copolymer (a) selected from the group consisting of the following (a-1) to (a-3) as a dispersant. A process for producing a polyurethane elastic yarn, which comprises spinning a dispersion containing at least one metal compound (b) selected from the group of (b-1) to (b-4) below.
(A-1) Copolymer of vinyl alcohol and vinyl acetal (a-2) Copolymer of vinyl acetate and vinyl acetal (a-3) Copolymer of vinyl alcohol, vinyl acetate and vinyl acetal (b -1) Hydrotalcite compound (b-2) Mixture of huntite and hydromagnesite (b-3) Carbonate, oxide and hydroxide of metal selected from Ca, Mg, Al or Ba (b) -4) A composite oxide composed of two or more metals selected from Ca, Mg, Al or Ba A fabric using the polyurethane elastic yarn according to claim 1 or 2 or the polyurethane elastic yarn obtained by the production method according to claim 3 .