JP4899166B2 - Polyurethane elastic yarn and method for producing the same - Google Patents

Description

  The present invention relates to a polyurethane elastic yarn having high strength, high recovery, alkali resistance, resistance to various drugs, high heat resistance, and the like, and a method for producing the same.

  Elastic fibers are widely used for stretch clothing and industrial materials such as leg wear, inner wear, and sports wear due to their excellent stretch properties.

  As such elastic fibers, in particular, polyurethane elastic yarns are required to have high tensile elongation, high recoverability, high chemical resistance, and high heat resistance. In particular, chemical resistance has been strongly demanded in recent years when used in mixed fabrics in combination with polyester yarns. Chemical resistance that can withstand weight loss processing and extraction processing of polyester, that is, alkali, quaternary ammonium salt, Tolerance to unsaturated fatty acids is required.

  As a conventional technique for imparting such chemical resistance, for example, a technique of spinning by containing polyvinylidene fluoride in a polyurethane spinning solution is known (for example, see Patent Document 1).

  However, in the case of polyurethane elastic yarns containing polyvinylidene fluoride in this way, recovery and heat resistance are not sufficient, especially in the use of mixed fabrics with polyester yarns that require weight loss processing and extraction processing, and chemical resistance is also It is still unsatisfactory and usage may be limited.

Also known is a technique of spinning a polyurethane spinning solution containing a polyvinyl alcohol sulfonic acid modified product or a synthetic tannin of a sulfone compound (see, for example, Patent Documents 2 and 3). However, even if a compound having a sulfonic acid group is contained, its content is low, and chemical resistance is still unsatisfactory in the use of a mixed fabric with a polyester yarn that requires a biting process. In the latter case, the compound itself has a dark brown color, and the resulting yarn is also markedly colored, which may limit its use.
JP 2000-73233 A Japanese Patent No. 3826377 JP 2001-140167 A

  The present invention solves the above-mentioned problems of the prior art and provides a polyurethane elastic yarn having alkali resistance, resistance to various drugs, high recovery, high strength elongation, and high heat resistance, and a method for producing the same. Objective.

  The polyurethane elastic yarn of the present invention employs the following means in order to achieve the above object.

That is, an elastic yarn main constituent is composed of polyurethane polymers diols and diisocyanates, contains a polymer containing a sulfonic acid group state, and are the molar concentration of monomer 5 mol% or more with a scrollable sulfonic acid group and a polyurethane elastic yarn polymer Ru formaldehyde condensation polymer der containing sulfonic acid groups.

A method of manufacturing a polyurethane elastic yarn of the present invention, the solution of the polyurethane main component is a polymeric diol and a diisocyanate, by adding a polymer containing a sulfonic acid group, it der those spinning, sulfonic acid Ru der those polymers containing group is formaldehyde condensation polymers.

  The polyurethane elastic yarn of the present invention has alkali resistance, resistance to various drugs, high recovery, high strength elongation, and high heat resistance. Therefore, clothes using this elastic yarn can be attached and detached. It is excellent in properties, wear feeling, dyeability, discoloration resistance, appearance quality and the like.

  The polyurethane used in the present invention may be any polyurethane as long as the main components are a polymer diol and a diisocyanate, and is not particularly limited. Also, the synthesis method is not particularly limited.

  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 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.

  In the present invention, the “main constituent component” means a component occupying 50% by weight or more of the constituent components used when polymerizing polyurethane. In the present invention, the polymer diol and the diisocyanate total 50% by weight. It means to occupy more than%.

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

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

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

(Where a and c are integers of 1 to 3, b is an integer of 0 to 3, R1 and R2 are H or an alkyl group of 1 to 3 carbon atoms)
Specific examples of polyether diol compounds include polyethylene glycol, modified polyethylene glycol, polypropylene glycol, polytrimethylene ether glycol, polytetramethylene ether glycol (hereinafter abbreviated as PTMG), tetrahydrofuran (hereinafter abbreviated as THF). Modified PTMG, which is a copolymer of 3-methyl-THF, modified PTMG, which is a copolymer of THF and 2,3-dimethyl-THF, modified PTMG, which is a copolymer of THF and neopentyl glycol, THF and ethylene Examples thereof include random copolymers in which oxides 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. Further, as alicyclic diisocyanates, for example, methylene bis (cyclohexyl isocyanate), isophorone diisocyanate, methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate, cyclohexane-1,4-diisocyanate, hexahydroxylylene diisocyanate, hexa Hydrotolylene diisocyanate, 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.

  Examples of the low molecular weight diol include ethylene glycol (hereinafter abbreviated as EG), 1,3-propanediol, 1,4-butanediol, bishydroxyethoxybenzene, bishydroxyethylene terephthalate, 1-methyl-1,2- Ethanediol and the like are representative. 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.

  In addition, the molecular weight of the polyurethane elastic yarn of the present invention is preferably in the range of 40000 to 150,000 as the number average molecular weight from the viewpoint of obtaining fibers having high durability and strength. The number average molecular weight is a value measured by GPC and 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, In addition, 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 number average 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- An elastic yarn produced from a polyurethane synthesized using at least one selected from the group consisting of propanediamine and 1,3-propanediamine, and having a high-temperature melting point of 150 ° C. or more and 300 ° C. or less. 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 contains a polymer containing a sulfonic acid group. A polymer containing a sulfonic acid group has an anionic property and has a good interaction with a urea group or a urethane group in a polyurethane in the spinning solution, so that aggregation of hard segments in the spinning solution can be prevented. Viscosity change and gelation can be reduced. In addition, after the polymer containing the sulfonic acid group is formed into a polyurethane elastic yarn, it covers and protects the crystal mainly composed of the hard segment, and exhibits an antioxidant ability in the amorphous part mainly composed of the soft segment. Thus, the effects of the present invention such as chemical resistance, high recoverability, and high heat resistance can be exhibited. On the other hand, when the polyurethane elastic yarn does not contain a polymer containing a sulfonic acid group, it is difficult to increase alkali resistance, resistance to various drugs, recoverability, high elongation, and heat resistance.

The polymer containing a sulfonic acid group used in the present invention, Ri compound der the compound was polymerized monomer having a sulfonic acid group may be used only a compound having a sulfonic acid group as a monomer, including other monomers A copolymer may be used. From the viewpoint of obtaining a polyurethane yarn having high chemical resistance and high tensile elongation, the molar concentration of the monomer having a sulfonic acid group needs to be 5 mol% or more. When the molar concentration of the monomer having a sulfonic acid group in the polyurethane elastic yarn is 5 mol% or more, the antioxidant ability similar to that of the phenol-based antioxidant is exhibited, and high heat aging resistance is obtained. Preferably it is 10 mol% or more, More preferably, it is 20 mol% or more. As long as the spinning property of the polyurethane elastic yarn and the elongation of the polyurethane elastic yarn are not hindered, the amount may be 100 mol%.

  Further, from the viewpoint of suppressing high spinning speed and volatilization loss during spinning, the polymer containing a sulfonic acid group preferably has a number average molecular weight of 2,000 or more and 500,000 or less.

The amount of the polymer containing a sulfonic acid group contained in the polyurethane elastic yarn of the present invention is 0.5 wt% or more and less than 50 wt% from the viewpoint of obtaining good spinnability, balanced mechanical properties, and heat resistance. The range is preferable, and from the viewpoint of reducing the decrease in the recoverability of the polyurethane yarn, 1% by weight or more and 30% by weight or less is more preferable. More specifically, the SO ₃ H concentration preferably constitutes 0.12% to 3.6% by weight in the yarn.

  As the compound having a sulfonic acid group, an aromatic sulfonic acid is preferable from the viewpoint of obtaining a polyurethane yarn having a high strength and elongation. Among these, benzenesulfonic acid or phenolsulfonic acid is more preferable in order to efficiently exhibit high recoverability and high heat resistance.

  When the polymer containing a sulfonic acid group is a copolymer, there is no restriction on the molar ratio of the monomer having a sulfonic acid group and other constituent monomers, and the other constituent monomers are compatible with the stability of the compound and compatibility with polyurethane. From the viewpoint of the above, it can be selected as appropriate. From the viewpoint of enhancing stability, a compound having a sulfonyl group is preferred. In addition, a sulfonic acid is not contained in the compound which has a sulfonyl group here. As a compound having such a sulfonyl group (excluding sulfonic acid), it is a bulky compound for increasing the compatibility with polyurethane and not inhibiting the crystallization of the hard segment of polyurethane, and forming a high-strength polyurethane yarn. Are preferred, and compounds having an aromatic ring such as aromatic sulfone are suitable. Of these, bisphenols such as dihydroxydiphenylsulfone are particularly preferred. In the case of using bisphenols such as dihydroxydiphenyl sulfone, it contributes to high heat resistance because it exhibits a more remarkable antioxidant ability.

The polymer containing a sulfonic acid group, for example, formaldehyde condensation polymer sulfonic acid, formaldehyde condensation polymer of phenol sulfonic acid, formaldehyde condensation polymer of phenol sulfonic acid and cresol, base Nzensuruhon acid and 4,2 ' -Formaldehyde condensation polymer of dihydroxydiphenylsulfone, formaldehyde condensation polymer of phenolsulfonic acid and 4,2'-dihydroxydiphenylsulfone, formaldehyde condensation polymer of benzenesulfonic acid and 4,4'-dihydroxydiphenylsulfone, phenolsulfonic acid formaldehyde condensation polymers of 4,4'-dihydroxydiphenyl sulfone. From the viewpoint of high recovery and transparency and color of the yarn after spinning, a formaldehyde condensation polymer is preferred.

There is no limitation on the polymerization method of the polymer containing a sulfonic acid group, and (a) a styrene derivative having a sulfonic acid group such as styrene sulfonic acid and α-methylstyrene sulfonic acid, olefin sulfonic acids such as sulfonic acid, (c) diene sulfonic acids such as butadiene sulfonic acid, can be used as addition polymerization using a vinyl sulfonic acid, such as, essential to use the Chijimigokasane case of formaldehyde cross-linking It is . In order to protect the sulfonic acid group that expresses the anionic property of the polymer, a starting monomer is appropriately selected as a precursor such as a sulfonate or sulfoamide, the starting material is polymerized, and then the ion is exchanged with an acid. It is also preferred to derive some or all of them to sulfonic acid groups. Also in novolak in Chijimigokasane case obtained by condensation polymerization of formaldehyde in the presence of an acid catalyst formaldehyde crosslinking, preferably even synthesized resol under alkaline catalyst. Stability of a polymer containing a sulfonic acid group, that is, as a technique for suppressing viscosity change and discoloration, dimethylamine, diisopropylamine, ethylmethylamine, diethylamine, butylmethylamine, dibutylamine, which are polyurethane end-capping agents described later, It is also preferable to add and react a monoamine such as diamylamine in an amount equivalent to SO ₃ H equivalent.

  Among them, from the viewpoint of stabilizing the viscosity of the raw material spinning solution of polyurethane yarn, obtaining good spinnability, and obtaining a high chemical resistance yarn, the polymer having a sulfonic acid group is a compound having a sulfonic acid group and a sulfonyl group. A random or alternating copolymer of a group-containing compound (excluding sulfonic acid) is preferred. From the viewpoint of obtaining better mechanical properties as a polyurethane yarn, a copolymer having a monomer having a sulfonic acid group-containing compound and a sulfonyl group-containing compound (excluding sulfonic acid) is preferable. Examples thereof include benzenesulfonic acid and Examples include a formaldehyde condensation polymer of 4,4′-dihydroxydiphenylsulfone and a formaldehyde condensation polymer of phenolsulfonic acid and 4,4′-dihydroxydiphenylsulfone.

  Furthermore, the polymer containing a sulfonic acid group used in the present invention speeds up the dispersion and dissolution in polyurethane, makes the properties of the polyurethane yarn to be produced a target property, and obtains a polyurethane yarn with a more appropriate transparency. N, N′-dimethylacetamide at 20 ° C. from the viewpoint that the content of the polymer containing sulfonic acid groups does not decrease even when subjected to heat or the like in the spinning process and the yarn is not discolored. (Hereinafter abbreviated as DMAc) or N, N′-dimethylformamide (hereinafter abbreviated as DMF) in a liquid form having a viscosity of 10 cP or more and 10,000 P or less, and the polymer itself is not colored or Less is preferred.

  Furthermore, it is also preferable that one or more end blockers are used in the polyurethane used in the present invention. 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.

  In the present invention, various stabilizers, pigments, and the like may be contained in the polyurethane elastic yarn or polyurethane spinning solution. For example, hindered phenols such as 2,6-di-t-butyl-p-cresol (BHT) and “Sumizer GA-80” (product name) manufactured by Sumitomo Chemical Co. Drugs, various benzotriazoles such as “Chinubin” (registered trademark) manufactured by Ciba Geigy, benzophenone drugs, phosphorus drugs such as “Sumilyzer P-16” (product name) manufactured by Sumitomo Chemical Co., Ltd., and various hindered amines Chemicals, various pigments such as iron oxide and titanium oxide, inorganic substances such as zinc oxide, cerium oxide, magnesium oxide and carbon black, fluorine or silicone resin powder, metal soap such as magnesium stearate, silver and zinc And bactericides, deodorants, silicone, mineral oil and other lubricants, barium sulfate, acid Cerium, it is also preferred to include various kinds of antistatic agents such as betaine and phosphoric acid and also the reaction of these with polymers preferred. And in order to further improve the durability to light, various nitric oxides, and the like, it is also preferable to use a nitrogen oxide scavenger such as HN-150 manufactured by Nippon Hydrazine Co., Ltd.

  Further, from the viewpoint of easily increasing the spinning speed in the dry spinning process, fine particles of metal oxide such as titanium dioxide and zinc oxide may be added. 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 and the above-described modifier, or may be previously contained in the polyurethane solution or dispersion before mixing. You may keep it. 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, when producing an elastic yarn made of polyurethane whose main components are a polymer diol and a diisocyanate, the above-mentioned polymer containing a sulfonic acid group is contained. Such a polymer containing a sulfonic acid group may be added together in the polymerization stage of the polyurethane, but in the present invention, it is preferable that a polyurethane solution is first prepared and then added. 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 the polyurethane particularly suitable for the present invention, PTMG having a number average molecular weight of 1000 to 8000 is used as the polymer diol, MDI is used as the diisocyanate, ethylene glycol, 1,3-propanediol, 1 , 4-butanediol, ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, and a high temperature side melting point of 200 ° C. or higher and 300 ° C. or lower. Things.

  Such polyurethane can be obtained, for example, by synthesis using DMAc, DMF, dimethyl sulfoxide, N-methylpyrrolidone or the like or a solvent containing these as a main component, using the above raw materials. 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. In the case where the number average molecular weight of the polymer diol is 1000 or more, in order to make the melting point on the high temperature side 150 ° C. or more, the polymerization is carried out at a ratio of (MDI moles) / (polymer diol moles) = 1.5 or more. It is preferable to proceed.

  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 the polyurethane solution thus obtained is usually preferably in the range of 30% by weight to 80% by weight.

  In the present invention, it is preferable to add the above-mentioned polymer containing a sulfonic acid group to such a polyurethane solution. As a method for adding the polymer containing a sulfonic acid group 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. Here, the polymer containing a sulfonic acid group to be added is preferably added as a solution from the viewpoint of uniform addition to the polyurethane solution.

  The addition of a polymer containing a sulfonic acid group to a polyurethane solution may cause a phenomenon in which the solution viscosity of the mixed solution after the addition becomes higher than expected compared to the solution viscosity of the polyurethane before the addition. From the viewpoint of preventing the phenomenon, monoamines such as dimethylamine, diisopropylamine, ethylmethylamine, diethylamine, methylpropylamine, isopropylmethylamine, diisopropylamine, butylmethylamine, isobutylmethylamine, isopentylmethylamine, dibutylamine, diamylamine , Ethanol, propanol, butanol, isopropanol, allyl alcohol, monools such as cyclopentanol, and end-capping agents such as monoisocyanates such as phenyl isocyanate are used alone or in combination. It is it is also preferable to be.

  When the polymer containing a sulfonic acid group is added to the polyurethane solution, for example, a drug such as a light-resistant agent or an antioxidant and a pigment may be added at the same time.

  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 an arbitrary method, that is, by appropriately selecting a spinning condition suitable for desired characteristics and spinning equipment.

  For example, the setting properties 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 desired setting properties and stress relaxation, the speed ratio of the godet roller and the winder is preferably wound in a range of 1.15 to 1.65. And when obtaining a polyurethane elastic yarn having particularly low setability (permanent strain rate) and low stress relaxation, the speed ratio between the godet roller and the winder is more preferably in the range of 1.15 to 1.40. The range of 1.15 or more and 1.35 or less is more preferable.

  On the other hand, when obtaining a polyurethane elastic yarn having high setability and high stress relaxation, it is preferable that the speed ratio of the godet roller and the winder is wound in the range of 1.25 to 1.65. The range of 1.65 or less is more preferable.

  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.

  Furthermore, the polymer containing a sulfonic acid group may have a brown color depending on the type of monomer used, its purity, and the polymerization method. When a polymer containing a sulfonic acid group colored in advance is used, even when it becomes a polyurethane yarn, the coloring is large and the use may be limited. Therefore, in the present invention, it is preferable to use a constituent monomer that increases the purity of the sulfonic acid monomer to be used and is less colored. To that end, by examining the polymerization time and temperature in advance, The containing polymer is preferably colorless or nearly colorless. Specifically, since most of the colors are brownish, the b value of the polyurethane elastic yarn determined by a hunter-type color difference meter is preferably less than 15, more preferably less than 3. is there. The b value is measured by winding a yarn 24 hours after spinning with a minimum load so that the influence of the color of the sample plate does not appear, and using a hunter color difference meter.

The polyurethane elastic yarn of the present invention obtained as described above can be mixed with other fibers to constitute a stretchable fabric. The form of the stretchable cloth is not limited at all, and the mixing ratio, the raw material fibers to be combined, and the mixing method may be appropriately selected and formed into a cloth by a known means. The polyurethane elastic yarn may be used as a bare yarn as it is, or one or more kinds of conventionally known fibers such as polyamide fibers, polyester fibers and synthetic fibers such as acrylic fibers, and natural fibers such as cotton and wool. You may use what was combined freely or was coat | covered.
In addition, as a fiber to be combined with the polyurethane elastic yarn of the present invention in constituting the fabric, polyamide fiber such as nylon, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, and copolymer polyester fiber mainly composed of these are used. Polyester synthetic fiber, acrylic synthetic fiber, polypropylene synthetic fiber, semi-synthetic fiber typified by acetate fiber, natural fiber typified by cotton, hemp or wool, or a mixture of two or more Are preferably used.

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

A method for measuring the strength, elongation, setability (permanent strain rate), stress relaxation, chemical resistance, alkali resistance, heat resistance (thermal softening point, melting point), and color of the polyurethane elastic yarn in the present invention will be described.
[Setability (permanent strain rate), stress relaxation, strength, elongation]
The setability, stress relaxation, strength, and elongation were measured by tensile testing polyurethane elastic yarn using an Instron 4502 type tensile tester.

  A sample having a test length of 5 cm (L1) was repeatedly stretched 300% at a tensile rate of 50 cm / min five times. At this time, the stress at 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 fracture was (G3), and the sample length at the time of fracture was (L3). Hereinafter, the above characteristics are calculated by the following formula.

Strength (cN) = (G3)
Stress relaxation (%) = 100 × ((G1) − (G2)) / (G1)
Setability (%) = 100 × ((L2) − (L1)) / (L1)
Elongation (%) = 100 × ((L3) − (L1)) / (L1)
[chemical resistance]
The yarn was fixed at 100% elongation, and the following three types of exposure treatment were performed. First, it is immersed in a hexane solution of oleic acid (5% by weight) for 1 hour, then immersed in a prepared hypochlorous acid solution (chlorine concentration: 500 ppm) for 2 hours, and then exposed to UV for 2 hours. . The UV exposure treatment was performed using a carbon arc type fade meter manufactured by Suga Test Instruments Co., Ltd. as a device at 63 ° C. and 60% RH. After this exposure treatment was performed twice in total, the yarn was left free for 24 hours at room temperature, and the breaking strength (G4) was measured by the same method as described above. The ratio (retention rate) of the breaking strength (G4) after the treatment to the breaking strength (G3) of the untreated yarn was defined as chemical resistance.

Chemical resistance (%) = 100 × (G4) / (G3)
[Alkali resistance 1]
As an indicator of the alkali resistance of the polyurethane yarn, a treatment assuming the weight reduction processing of the polyester fiber is performed, and the breaking strength retention rate of the yarn is evaluated.

  The yarn is fixed in a 100% stretched state, sealed in a pressure vessel, and an aqueous solution (8.0% by weight each) containing a cationic weight loss accelerator (quaternary ammonium salt, DXN-10 manufactured by one company) and sodium hydroxide. After being treated at 100 ° C. for 120 minutes, the yarn was left free for 24 hours at room temperature, and the breaking strength (G5) was measured by the same method as described above. The ratio (retention rate) of the breaking strength (G5) after the treatment to the breaking strength (G3) of the untreated yarn was defined as alkali resistance.

Alkali resistance (%) = 100 × (G5) / (G3)
[Alkali resistance 2]
As an indicator of the alkali resistance of the polyurethane yarn, a treatment assuming the removal process of the polyester fiber is performed, and the breaking strength retention rate of the yarn is evaluated.

  The yarn was fixed in a stretched state of 100%, immersed in a 40% by weight aqueous solution of a cationic weight loss accelerator (quaternary ammonium salt, DXN-10 from one company) for 5 minutes, sealed in a pressure vessel, and hydroxylated. Filled with an aqueous solution containing sodium (containing 8.0% by weight), treated at 100 ° C. for 120 minutes, left the yarn free for 24 hours at room temperature, and measured the breaking strength (G6) by the same method as described above. did. The ratio (retention rate) of the breaking strength (G6) after the treatment to the breaking strength (G3) of the untreated yarn was defined as alkali resistance.

Alkali resistance (%) = 100 × (G6) / (G3)
[Thermal softening point]
The thermal softening point was measured as one of the heat resistance indicators of polyurethane yarn. The polyurethane yarn was measured for temperature dispersion of the dynamic storage elastic modulus E ′ at a heating rate of 10 ° C./min using a dynamic elastic modulus measuring device RSAII manufactured by Rheometric. The thermal softening point was determined from the intersection of the tangent line in the plateau region where the E ′ curve was 80 ° C. or higher and 130 ° C. or lower and the tangent line of the E ′ curve where E ′ decreased due to thermal softening at 160 ° C. or higher. Note that E ′ is a logarithmic axis, and temperature is a linear axis.
[Color tone of polyurethane elastic yarn]
In many cases, the determination is based on the b value because of brownish coloration. A yarn 24 hours after spinning was wound up on a 5 × 5 cm sample plate with a minimum load (1.05 in terms of draft rate) so as not to affect the color of the sample plate, and used as a sample. The front surface of the sample and the standard white surface of common use (JIS Z 8722: 2005, 4.3.4) were covered with a flat, transparent, approximately 1 mm glass plate in close contact.

The b value was measured according to JIS L 1013: 2005 method C (Hunter's method) using a Hunter-type color difference meter based on the following formula. The number of measurements was five, and the average value was adopted.
b = 7.0 (Y-0.847Z) / Y1 / ²
(However, X, Y and Z were calculated according to JIS Z 8701: 2005)
In the determination, b is less than 3;
[Example 1]
A DMAc solution (35% by weight) of a polyurethane polymer (a1) composed of PTMG, MDI and ethylene glycol having a number average molecular weight of 2900 was polymerized by a conventional method to obtain a polymer solution A1.

  Next, as a copolymer of a compound having a sulfonic acid group, formaldehyde degenerate having a molar ratio of phenol sulfonic acid represented by chemical formula (II) and 4,4′-dihydroxydiphenyl sulfone of 52 to 48 (containing molar concentration: 52%). The union (b1) was used to prepare the DMAc solution.

  For the preparation of the DMAc solution, a horizontal mill WILLY A. Using DYNO-MIL KDL manufactured by BACHOFEN, filled with 85% zirconia beads, uniformly finely dispersed at a flow rate of 50 g / min, and a copolymer of a compound having a sulfonic acid group, DMAc solution B1 (35 wt% ).

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 - Le and polymers of divinylbenzene (manufactured by DuPont "meta crawl" (registered trademark) 2390, c2) were mixed in 2: 1 (weight ratio), antioxidant DMAc solution (concentration 35 weight %), And this was used as the other additive solution C1 (35% by weight).

  The polymer solution A1, the copolymer solution B1 of the compound having a sulfonic acid group, and the other additive solution C1 were uniformly mixed at 94% by weight, 3% by weight, and 3% by weight, respectively, to obtain a spinning solution D1.

  This spinning solution was dry-spun at a spinning speed of 540 m / min with a speed ratio of 1.4 between the godet roller and the winder, wound up, and 20 decitex, a monofilament, a copolymer of a compound having a sulfonic acid group (with a sulfonic acid group). A polyurethane elastic yarn (200 g wound body) having a content of 3% by weight of a monomer having a molar concentration of 52 mol% was prepared.

  The composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1. The copolymer b1 of the compound having a sulfonic acid group had a number average molecular weight of about 80,000.

  Table 2 shows the elongation at break, breaking strength, setability, stress relaxation, alkali resistance 1, alkali resistance 2, chemical resistance, thermal softening point, and color tone of this polyurethane elastic yarn. The breaking strength was increased as compared with Comparative Example 1 (described later) in which the compound b1 of the compound having a sulfonic acid group was not blended. The elongation at break remained the same. The set property was reduced as compared with Comparative Example 1, and the recoverability was improved. The color tone was also good. Alkali resistance 1, alkali resistance 2 and chemical resistance were significantly increased as compared with Comparative Example 1 and showed 2 times, 3.7 times and 2 times, respectively. The heat softening point, which is an index of heat resistance, was also improved as compared with Comparative Example 1.

  In addition, stretch fabrics were produced by the following method, subjected to alkali weight loss and dyeing, and evaluated for appearance quality.

  First, the obtained polyurethane elastic yarn was covered. A regular polyester fiber 168 dtex-48 filament was used as the covering yarn, and it was processed using a covering machine under the conditions of twist number = 450 T / m, draft = 3.0, to produce a weft covering yarn. . Similarly, a regular polyester fiber 168 decitex-48 filament is used as a covering yarn, and it is processed using a covering machine under conditions of a twist number of 700 T / M and a draft = 3.5. A yarn was made.

  Next, warping and weaving were performed. 5100 warp yarns (1100 rough winding warp) were glued and warped, and woven with a 2/1 twill structure using a rapier loom.

  Next, dyeing was performed. The raw machine obtained by weaving is scoured according to conventional methods, intermediate set (185 ° C), alkali weight reduction (N treatment), embossing (190 ° C), dyeing (130 ° C), drying, finish treatment, finishing set (180 ° C., cloth speed 20 m / min, set zone 24 m) were sequentially performed.

When the obtained stretch fabric was evaluated visually, it was free from defects and excellent in appearance quality.
[Example 2]
As a polymer of a compound having a sulfonic acid group, a formaldehyde condensation polymer (b2) of phenolsulfonic acid represented by chemical formula (III) was used, and the DMAc fine dispersion was prepared.

  The DMAc fine dispersion was prepared in the same manner as in Example 1 to obtain a DMAc dispersion B2 (35% by weight) of a polymer having a sulfonic acid group. The polymer solution A1 prepared in Example 1, the polymer solution B2 of the compound having a sulfonic acid group as described above, and the other additive solution C1 prepared in Example 1 were 92% by weight, 5% by weight, and 3% by weight, respectively. % To obtain a spinning solution D2.

  This spinning solution was dry-spun at a spinning speed of 540 m / min with a speed ratio of 1.40 between the godet roller and the winder and wound up, and was polymerized with 20 dtex, monofilament, and a compound having a sulfonic acid group (having a sulfonic acid group) A polyurethane elastic yarn (200 g wound yarn) having a content of 5% by weight of a monomer having a molar concentration of 100 mol% was prepared.

  The composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1. Compound b2 had a number average molecular weight of about 40,000.

  Table 2 shows the elongation at break, breaking strength, setability, stress relaxation, alkali resistance 1, alkali resistance 2, chemical resistance, thermal softening point, and color tone of this polyurethane elastic yarn. The breaking strength increased as compared with Comparative Example 1 (described later), and the elongation remained the same. The set property was reduced as compared with Comparative Example 1, and the recoverability was improved. The color tone was also good. Alkali resistance 1, alkali resistance 2 and chemical resistance were significantly increased as compared with Comparative Example 1, showing 2.2 times, 4.3 times and 2.8 times, respectively. The thermal softening point, which is an index of heat resistance, was also improved by 4 ° C. from Comparative Example 1.

Moreover, when the stretch woven fabric was manufactured by the same method as Example 1 and the external appearance quality was evaluated visually, the obtained stretch fabric had no fault and was excellent in the external appearance quality.
[Example 3]
A DMAc solution (35% by weight) of polyurethane urea polymer (a2) composed of PTMG having a number average molecular weight of 1800, MDI, ethylenediamine, and diethylamine as a terminal blocking agent was polymerized by a conventional method to obtain a polymer solution A2. Next, the DMAc solution A2, the copolymer solution B1 of the compound having a sulfonic acid group prepared in Example 1, and the other additive solution C1 prepared in Example 1 were 92% by weight and 5.0%, respectively. The mixture was uniformly mixed at 3.0% by weight to obtain a spinning solution D3. This spinning solution D3 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, 20 decitex, 2-filament multifilament, co-weight of compound having sulfonic acid group A polyurethane elastic yarn (500 g wound yarn) having a combined content (a molar concentration of the monomer having a sulfonic acid group of 50 mol%) of 5% by weight was produced.

  The composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1. Compound b1 had a number average molecular weight of about 80,000.

Table 2 shows the elongation at break, breaking strength, setability, stress relaxation, alkali resistance 1, alkali resistance 2, chemical resistance, thermal softening point, and color tone of this polyurethane elastic yarn. Both the elongation at break and the strength at break increased compared to Comparative Example 2 (described later) in which the compound b1 of the compound having a sulfonic acid group was not blended. The set property was reduced as compared with Comparative Example 2, and the recoverability was improved. The color tone was also good.
Alkali resistance 1, alkali resistance 2 and chemical resistance were significantly increased as compared with Comparative Example 2, showing 2.7 times, 4.0 times and 3.2 times, respectively. The heat softening point, which is an index of heat resistance, was also improved by 10 ° C. from Comparative Example 2.

Moreover, when the stretch woven fabric was manufactured by the same method as Example 1 and the external appearance quality was evaluated visually, the obtained stretch fabric had no fault and was excellent in the external appearance quality.
[ Reference Example 1 ]
As a copolymer of a compound having a sulfonic acid group, an addition polymer of phenolsulfonic acid and divinylbenzene represented by the chemical formula (IV) (containing a molar concentration of a monomer having a sulfonic acid group of 50%, b3) is used. Adjusted.

  The DMAc solution was prepared in the same manner as in Example 1 to obtain a copolymer solution B3 (35% by weight) of a compound having a sulfonic acid group. 82% by weight, 15% by weight, 3% by weight of the polymer solution A2 prepared in Example 3, the copolymer solution B3 of a compound having a sulfonic acid group, and the other additive solution C1 prepared in Example 1, respectively. The mixture was uniformly mixed at 0% by weight to obtain a spinning solution D4. This spinning solution D4 was dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and winder of 1.30, wound up, 20 decitex, 2-filament multifilament, co-weight of compound having sulfonic acid group A polyurethane elastic yarn (500 g wound yarn) having a combined content (molar concentration of the monomer having a sulfonic acid group of 50 mol%) of 15% by weight was produced.

  The composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1. Compound b3 had a number average molecular weight of 120,000.

  Table 2 shows the elongation at break, breaking strength, setability, stress relaxation, alkali resistance 1, alkali resistance 2, chemical resistance, thermal softening point, and color tone of this polyurethane elastic yarn. The breaking strength increased as compared with Comparative Example 2 (described later) in which the copolymer b3 of the compound having a sulfonic acid group was not blended, and was particularly high. The elongation at break remained the same. The set property was reduced as compared with Comparative Example 2, and the recoverability was improved. The color tone was also good. Alkali resistance 1, alkali resistance 2 and chemical resistance were significantly improved as compared with Comparative Example 2, showing 3.0 times, 4.4 times and 3.1 times, respectively. The heat softening point, which is an index of heat resistance, was also improved by 13 ° C. from Comparative Example 2.

Moreover, when the stretch woven fabric was manufactured by the same method as Example 1 and the external appearance quality was evaluated visually, the obtained stretch fabric had no fault and was excellent in the external appearance quality.
[Comparative Example 1]
The polymer solution A1 prepared in Example 1 and the other additive solution 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. The spinning solution E1 was dry-spun at a spinning speed of 540 m / min with a speed ratio of the godet roller and the winder of 1.40, and wound to prepare a polyurethane elastic yarn of 20 dtex and monofilament.

  The composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1. Table 1 shows the elongation at break, breaking strength, setability, stress relaxation, chemical resistance, alkali resistance, thermal softening point, and color tone of this polyurethane elastic yarn. Alkali resistance 1, alkali resistance 2 and chemical resistance were significantly inferior to those of Examples 1 and 2 containing a polymer of a compound having a sulfonic acid group.

Furthermore, when a stretch woven fabric was produced in the same manner as in Example 1 and the appearance quality was visually evaluated, the appearance of the fabric was partially undesirably caused by polyurethane yarn sag due to various processing histories. It was something.
[Comparative Example 2]
The polymer solution A2 prepared in Example 3 and the other additive solution 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 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 winder of 1.20, wound up, 20 dtex, 2-filament multifilament polyurethane elastic yarn (500 g wound yarn) Was made.

The composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1. Table 1 shows the elongation at break, breaking strength, setability, stress relaxation, chemical resistance, alkali resistance, thermal softening point, and color tone of this polyurethane elastic yarn. Alkali resistance 1, alkali resistance 2 and chemical resistance were significantly inferior to those of Example 3 and Reference Example 1 containing a polymer of a compound having a sulfonic acid group.

Furthermore, when a stretch woven fabric was produced in the same manner as in Example 1 and the appearance quality was visually evaluated, the appearance of the fabric was partially undesirably caused by polyurethane yarn sag due to various processing histories. It was something.
[Comparative Example 3]
A DMAc solution F1 (35% by weight) of polyvinylidene fluoride (number average molecular weight 48,000, f1) manufactured by Kureha Chemical Industries, Ltd. was prepared. The DMAc solution was prepared in the same manner as described in Example 1. The polymer solution A2 prepared in Example 3, the above-mentioned polyvinylidene fluoride solution F1, and the other additive solution C1 prepared in Example 1 were uniformly mixed at 92% by weight, 5% by weight, and 3.0% by weight, respectively. Thus, the spinning solution E3 was obtained. 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 1.30, wound up, 20 dtex, 2-filament multifilament polyurethane elastic yarn (500 g wound yarn) Was made.

The composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1. Table 2 shows the elongation at break, breaking strength, setability, stress relaxation, alkali resistance 1, alkali resistance 2, chemical resistance, thermal softening point, and color tone of this polyurethane elastic yarn. The chemical resistance was inferior to that of Example 3, Reference Example 1 and the like improved to 1.5 times that of Comparative Example 2 in which no polyvinylidene fluoride was added. Furthermore, alkali resistance 1 and alkali resistance 2 were inferior to those of Example 3, Reference Example 1 and the like.

Furthermore, a stretch woven fabric was produced in the same manner as in Example 1, and the appearance quality was visually evaluated. As a result, the appearance of the stretch waving due to the sag, which seems to be due to the increased setting of the polyurethane yarn, occurred. Was unsatisfactory.
[Comparative Example 4]
A DMAc solution F2 (35% by weight) having a modified polyvinyl alcohol sulfonic acid modified by Nippon Synthetic Chemical Co., Ltd. (Goselan (R), the molar concentration of the monomer having a sulfonic acid group is 1.5%, f2) was prepared. The DMAc solution was prepared in the same manner as described in Example 1. The polymer solution A2 prepared in Example 3, the polyvinyl alcohol sulfonic acid modified product solution F2 described above, and the other additive solution C1 prepared in Example 1 were 82% by weight, 15% by weight, and 3.0% by weight, respectively. The mixture was uniformly mixed 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 winder of 1.30, wound up, 20 decitex, 2-filament multifilament polyurethane elastic yarn (500 g wound body) Was made.

The composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1. Table 2 shows the elongation at break, breaking strength, setability, stress relaxation, alkali resistance 1, alkali resistance 2, chemical resistance, thermal softening point, and color tone of this polyurethane elastic yarn. The heat softening point decreased by 9 ° C. as compared with Comparative Example 2, and the alkali resistance 1, alkali resistance 2, and chemical resistance were 1. those in Comparative Example 2 in which the polyvinyl alcohol sulfonic acid modified product was not added. It was significantly inferior to those improved to about 1 to 1.7 times, Example 3, Reference Example 1 and the like.

Furthermore, when a stretch woven fabric was produced in the same manner as in Example 1 and the appearance quality was visually evaluated, the appearance of the fabric was partially undesirably caused by polyurethane yarn sag due to various processing histories. It was something.
[Comparative Example 5]
A solid DMAc dispersion from which moisture has been removed from Hyfix GM (formerly Dainippon Pharmaceutical Co., Ltd., currently OG Co., Ltd., dihydroxydiphenylsulfone compound, 30% aqueous solution, dark brown), a synthetic tannin. F3 (35% by weight) was adjusted. The preparation of the DMAc dispersion was performed in the same manner as the preparation of the DMAc solution described in Example 1. F3 had a dark coffee-like dark brown color. The polymer solution A2 prepared in Example 3, the dihydroxydiphenylsulfone-based compound dispersion F2 described above, and the other additive solution C1 prepared in Example 1 were 96% by weight, 1.0% by weight, and 3.0%, respectively. The mixture was uniformly mixed by weight% to obtain a spinning solution E5. This spinning solution E5 was dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and winder of 1.30, wound up, 20 decitex, 2-filament multifilament polyurethane elastic yarn (500 g wound body) Was made.

The composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1. Table 2 shows the elongation at break, breaking strength, setability, stress relaxation, alkali resistance 1, alkali resistance 2, chemical resistance, thermal softening point, and color tone of this polyurethane elastic yarn. The heat softening point is the same as that of Comparative Example 2, and the alkali resistance 1, alkali resistance 2, and chemical resistance are the same or 1.2 times as those of Comparative Example 2 in which no dihydroxydiphenylsulfone compound was added. Compared with what was carried out, Example 3, Reference Example 1, etc., it was inferior.

  The resulting polyurethane elastic yarn had a strong reddish brown color, and a stretch fabric was produced in the same manner as in Example 1. However, the raw knitting was very unsatisfactory for providing the stretch fabric. It was. Moreover, when visually evaluated, the appearance of this was unsatisfactory because the occurrence of partial waviness due to polyurethane yarn sag due to various processing histories was observed.

  Since the polyurethane elastic yarn of the present invention has high strength, high recovery, alkali resistance, resistance to various drugs, and high heat resistance, clothes and the like using this elastic yarn have removable and fit properties. It is excellent in wear feeling, dyeability, discoloration resistance, appearance quality and the like.

  Because of these excellent properties, the polyurethane yarn of the present invention can be used not only alone but also in combination with various fibers to obtain an excellent stretch fabric, which is suitable for knitting, weaving and string processing. It is. Specific applications that can be used include socks, stockings, circular knitting, tricots, swimwear, ski pants, work clothes, smoke fire clothes, golf trousers, wet suits, bras, girdles, various textile products such as gloves, fastening materials, In addition, there are fastening materials for preventing sanitary products such as paper diapers, waterproofing materials, imitation baits, artificial flowers, electrical insulation materials, wiping cloths, copy cleaners, gaskets and the like.

Claims (13)

An elastic yarn of polyurethane main component is a polymeric diol and a diisocyanate, and contains a polymer containing a sulfonic acid group state, and are the molar concentration of monomer 5 mol% or more with a scrollable sulfonic acid group, and , polyurethane elastic yarn polymer comprising sulfonic acid groups and wherein the formaldehyde condensation polymers der Rukoto. The polyurethane elastic yarn according to claim 1, wherein the content of the polymer containing a sulfonic acid group is 0.5 wt% or more and less than 50 wt%. The polyurethane elastic yarn according to claim 1 or 2, wherein the polymer containing a sulfonic acid group has a number average molecular weight of 2,000 to 500,000. The polyurethane elastic yarn according to any one of claims 1 to 3, wherein the monomer having a sulfonic acid group is an aromatic sulfonic acid. The polyurethane elastic yarn according to claim 4, wherein the monomer having a sulfonic acid group is benzenesulfonic acid or phenolsulfonic acid. The polyurethane according to any one of claims 1 to 5 , wherein the polymer containing a sulfonic acid group is a copolymer of a monomer having a sulfonic acid group and a monomer having a sulfonyl group (excluding sulfonic acid). Elastic yarn. The polyurethane elastic yarn according to claim 6 , wherein the monomer having a sulfonyl group (excluding sulfonic acid) is an aromatic sulfone. The polyurethane elastic yarn according to claim 7 , wherein the monomer having a sulfonyl group (excluding sulfonic acid) is dihydroxydiphenyl sulfone. The copolymer of a monomer having a sulfonic acid group and a monomer having a sulfonyl group (excluding sulfonic acid) is a formaldehyde condensation polymer of benzenesulfonic acid or phenolsulfonic acid and 4,4′-dihydroxydiphenylsulfone. The polyurethane elastic yarn according to claim 6 , wherein The polyurethane elastic yarn according to any one of claims 1 to 9 , wherein a b value obtained by a hunter type color difference meter is less than 15. A method for producing a polyurethane elastic yarn containing a polymer containing a sulfonic acid group when producing an elastic yarn comprising a polyurethane whose main constituents are a polymer diol and a diisocyanate, wherein the polymer containing a sulfonic acid group is formaldehyde A method for producing a polyurethane elastic yarn, which is a condensed polymer . The method for producing a polyurethane elastic yarn according to claim 11 , wherein a polymer containing a sulfonic acid group is added to a polyurethane solution whose main constituent components are a polymer diol and a diisocyanate, and spinning is performed. The method for producing a polyurethane elastic yarn according to claim 11 or 12 , wherein the polymer containing a sulfonic acid group uses a monomer having a sulfonate.