Dyeable polyurethaneurea elastic yarn and manufacturing method therefor

Abstract

The present invention relates to a dyeable polyurethaneurea elastic yarn comprising: a mixed polyol composed of a polytetramethylene ether glycol (PTMG) and a polyethylene glycol having a number average molecular weight of 4,100-6,000; and an organic diisocyanate, wherein the polyethylene glycol is included in the amount of 3-15 mol% on the basis of the total amount of the mixed polyol. The polyurethaneurea elastic yarn of the present invention can be dyed using a reactive dye, can improve heat resistance when a blended product of a polyester or cellulose-based fiber and a polyurethane is dyed, and alleviates an elongation decrease due to the excessive use of a polyethylene glycol, and thus can solve the problem of thread breaks or holes occurring in a fabric.

Description

Flammable polyurethane urea elastic yarn and method for manufacturing the same

[0001] The present invention relates to a dyeable polyurethane urea elastic yarn and a method for producing the same, and more particularly, to a dyeable polyurethane urea elastic yarn and a method for producing the same, which enables dyeing with a reactive dye while improving heat resistance and enabling use with a counterpart yarn requiring high-temperature heat treatment, and which improves the problem of yarn breakage of the polyurethane urea elastic yarn in the raw material form by improving elongation.

[0002] Polyurethane urea elastic fibers are widely used in elastic clothing such as stockings, inner-wear and sportswear, as well as in sanitary products and various industrial materials due to their excellent elasticity and recovery properties.

[0003] In general, polyurethane urea is produced by reacting a polyol with an excess of a diisocyanate compound to obtain a prepolymer, and then an appropriate reaction is performed on this prepolymer to produce a spinning solution of polyurethane urea fibers, which is then spun to obtain elastic yarn.

[0004] Polyurethane urea elastic yarn is used in combination with various other counterparts such as cotton, acrylic, wool, and silk depending on the application, and in particular, in the case of sports or innerwear, it is often blended with cellulosic fibers such as cotton.

[0005] Polyurethane-urea elastic fibers are hydrophobic and have no dye sites within their molecular structure, making them difficult to dye. To improve the dyeability of polyurethane-urea elastic fibers, Korean Patent No. 10-0580326 discloses a method for producing polyurethane-urea elastic fibers with excellent dyeability and light resistance by adding a diester compound containing a triazine compound and a tertiary amine to a polymer solution during the production of polyurethane-urea elastic fibers. Korean Patent Publication No. 2015-0074111 discloses a dyeable thermoplastic polyurethane fiber produced from a composition comprising polyurethane, which comprises a polyol, at least one diisocyanate, at least one chain extender, and a reaction product of a functional modifier that is a reaction product of an aminodiol and a Brønsted acid. These technologies are intended to improve the dyeability of spandex, but it is difficult to expect improved dyeability for reactive dyes of polyurethane urea elastic fibers.

[0006] Thus, while existing technologies exist to improve the dyeability of spandex with acid dyes, no technology exists to enable dyeing with reactive dyes. To date, no spandex dyed with reactive dyes has been commercially produced, and the problem of improving the dyeability of polyurethane-urea elastomeric yarns with reactive dyes has persisted for decades without a satisfactory solution, resulting in the widespread perception that polyurethane fibers cannot be sufficiently dyed with reactive dyes. There is an urgent need for the development of polyurethane-urea elastomeric yarn products that can be dyed with reactive dyes. In particular, there is a pressing need for technologies that can improve the properties of the polyurethane polymer itself, rather than through covering or blending.

[0007] Meanwhile, in the case of polyurethane urea elastic yarn using polyethylene glycol, when a blend of polyester and cellulose fibers is used as a counter yarn, it goes through a high-temperature dyeing process twice, and during this process, the fabric power decreases due to insufficient heat resistance, making it difficult to apply. In addition, in the case of polyurethane urea elastic yarn using polyethylene glycol, the capping ratio is set to 1.8 or higher to prevent a decrease in heat resistance, but this lowers the elongation, and in the downstream process, the fabric is stretched and heat-set, which can cause yarn breakage or microscopic holes in the fabric, causing more serious problems than expected.

[0008] The present invention is intended to solve the problems of the prior art described above, and one object of the present invention is to provide a dyeable polyurethane urea elastic yarn and a method for producing the same, which improves the dyeability of polyurethane to a reactive dye, which is a problem in dyeing a blended product of polyurethane and other materials, and at the same time exhibits excellent heat resistance and high elongation.

[0009] Another object of the present invention is to provide a dyeable polyurethane urea elastic yarn and a method for producing the same, which can improve the problem of yarn breakage or hole formation of the original polyurethane urea elastic yarn by improving the heat resistance while making it dyeable with a reactive dye by mixing an excessive amount of polyethylene glycol into polytetramethylene ether glycol and thereby enabling use with a counterpart yarn such as polyester that requires high-temperature heat treatment.

[0010] The present inventors have discovered that when manufacturing a polymer for manufacturing polyurethane urea elastic yarn, dyeing with a reactive dye is possible by using polyethylene glycol in excess as one of two polyols, and that the decrease in heat resistance caused by the excess polyethylene glycol can be overcome by using high molecular weight polyethylene glycol, and thus completed the present invention. In general, polyurethane urea elastic yarn is difficult to dye with reactive dyes and tends to lose its inherent physical properties as an elastic yarn after exposure to high temperatures, such as when subjected to a high-temperature dyeing process, so the above discovery has very important technical significance.

[0011] One aspect of the present invention for achieving the above-described technical task relates to a polyurethane urea elastic yarn comprising a mixed polyol composed of polytetramethylene ether glycol (PTMG) and polyethylene glycol having a number average molecular weight of 4100 to 6000 and an organic diisocyanate, characterized in that the polyethylene glycol is contained in an amount of 3 to 15 mol% based on the total mixed polyol.

[0012] The heat resistance of the yarn, which is obtained by measuring the stress (P1) when the elastic yarn of the present invention is stretched to an elongation of 200% before heat treatment and the stress (P2) when the elastic yarn is stretched to an elongation of 200% after heat treatment, is characterized in that it exceeds 45% according to the following equation 1. At this time, the heat treatment conditions are as described in the examples.

[0013] [Formula 1]

[0014] Heat resistance (%) = P2 / P1 X 100

[0015]

[0016] In the present invention, the intrinsic viscosity (IV) of the polyurethane urea polymer constituting the polyurethane urea elastic yarn is 1.1 to 1.2, and the amine terminal of the polyurethane urea elastic yarn may be 3 to 20 meq / kg.

[0017] The polyurethane urea elastic yarn of the present invention can exhibit a dyeability of L* value of 25 or less when dyed with a reactive dye. Here, the dyeability refers to the L* value when dyeing with CI Reactive Black31 as a reactive dye in a dye solution having an owf concentration of 3% at 60°C for 60 minutes, and then measuring the reflectance of the yarn using a spectrophotometer and calculating it with the CIE lab color difference formula.

[0018] Another aspect of the present invention relates to a method for producing a polyurethane urea elastic yarn, comprising: polymerizing polytetramethylene ether glycol (PTMG) and polyethylene glycol having a number average molecular weight of 4100 to 6000 with a diisocyanate compound to produce a polyurethane prepolymer, dissolving the polyurethane prepolymer in a solvent to produce a prepolymer solution, subjecting the prepolymer solution to a chain extension reaction with an amine solution containing a diamine chain extender and an amine chain terminator to obtain a polyurethane urea spinning solution containing a polyurethane urea polymer, and spinning the obtained polyurethane urea spinning solution to produce a polyurethane urea elastic yarn, wherein the polyethylene glycol is used in an amount of 3 to 15 mol% based on the total polyol.

[0019] The intrinsic viscosity (IV) of the above polyurethane urea polymer is set to be 1.1 to 1.2, and the amine terminal of the polyurethane urea elastic fiber has a concentration of 3 to 20 meq / kg.

[0020] Another aspect of the present invention relates to an elastic fabric made by blending the above-described polyurethane urea elastic yarn with polyester or cellulose fibers.

[0021] The polyurethane urea elastic yarn of the present invention improves hydrophilicity by mixing 3 to 15 mol% of polyethylene glycol (PEG) having a molecular weight of 4100 to 6000 g / mol into polytetramethylene ether glycol (PTMG) during prepolymer polymerization of the polyurethane urea elastic yarn, thereby securing dyeability for reactive dyes and improving heat resistance, thereby providing the advantage of being applicable to fabrics that use PET and cellulose blended yarns as counterpart yarns, such as T / C or T / R spun yarns.

[0022] In addition, in the present invention, by limiting the intrinsic viscosity (IV) of the polyurethane polymer to 1.1 to 1.2, the elongation is improved, thereby solving the problem of polyurethane urea elastic yarn breaking and hole generation in the fabric during the downstream process.

[0023] In addition, according to the present invention, the inherent viscosity of the polymer and the number of amine terminals of the yarn are lowered, so that the polymerization operation conditions are milder than before during polymerization, thereby improving the stability of the polymerization operation.

[0024] The present invention is described in more detail below.

[0025] As used herein, the term "polyurethane-urea elastomeric yarn" refers to a synthetic fiber in which the fiber-forming material is a long-chain synthetic polymer composed of at least 85 wt% segmented polyurethane or polyurethane-urea. As used herein, the terms "polyurethane-urea elastomeric yarn" and spandex are used interchangeably.

[0026] “meq / kg” means the milligram equivalent of a specified component per kilogram of total component, i.e. polymer solids.

[0027] One aspect of the present invention relates to a polyurethane urea elastic yarn comprising a mixed polyol composed of polytetramethylene ether glycol (PTMG) and polyethylene glycol having a number average molecular weight of 4100 to 6000 and an organic diisocyanate, characterized in that the polyethylene glycol is contained in an amount of 3 to 15 mol% based on the total mixed polyol.

[0028] The present invention provides a polyurethane urea elastic yarn having excellent dyeability for reactive dyes, improved heat resistance, and improved elongation, and a method for producing the same. By mixing polyethylene glycol (PEG) with an increased molecular weight of 4100 to 6000 g / mol into polytetramethylene ether glycol (PTMG) during the polymerization of a polyurethane prepolymer, the heat resistance is improved, thereby enabling use with PET blended yarns requiring heat resistance, such as T / C or T / R spun yarns.

[0029] In order to increase the heat resistance of polyurethane urea elastic yarn, the molecular weight of polyethylene glycol (PEG) is preferably 4100 to 6000. If the molecular weight of polyethylene glycol is less than 4100, the heat resistance and elongation of the yarn are reduced, making it difficult to use when using a counterpart yarn that requires heat resistance, such as T / C or T / R spun yarn, due to a deterioration in physical properties during the heat setting and dyeing processes of the fabric. If the molecular weight of polyethylene glycol (PEG) exceeds 6000, the melting point of polyethylene glycol (PEG) is high, exceeding 60℃, making it difficult to apply in the process. In addition, the viscosity of the prepolymer is high, so the temperature of the prepolymer must be maintained above 60℃ to ensure fluidity. In a high-temperature environment, gels may be formed due to side reactions, which may deteriorate polymerization stability and spinning workability.

[0030] The high heat resistance of polyurethane-urea elastic yarn is a key characteristic for its use in blended fabrics, such as those combined with polyester or cotton. Heat resistance is particularly crucial during dyeing. Specifically, when used in blended fabrics with polyester or when dyed in intermediate colors, the dyeing temperature tends to be higher. Furthermore, to achieve good extensibility, dimensional stability, and surface finish, high-temperature dry heat treatment prior to dyeing is increasingly used. Therefore, elastic yarns must possess high heat resistance.

[0031] In the present invention, when using polyethylene glycol (PEG) having a molecular weight of 4100 to 6000 g / mol, the dyeability is improved at the same content (mol%) compared to when using polyethylene glycol (PEG) having a molecular weight of 2000 to 4000 g / mol. Therefore, when the molecular weight of polyethylene glycol (PEG) is 4100 to 6000, the PEG content is preferably 3 to 15 mol%. When the content of polyethylene glycol (PEG) is less than 3 mol%, the dyeability to reactive dyes is insufficient, and when it exceeds 15 mol%, the heat resistance of the yarn is lowered, making it difficult to use it with a counterpart yarn that requires heat resistance, such as T / C or T / R spun yarn.

[0032] The heat resistance of the yarn obtained by measuring the stress (P1) in the state of being elongated to 200% elongation before heat treatment and the stress (P2) in the state of being elongated to 200% elongation after heat treatment of the elastic yarn of the present invention is preferably greater than 45% according to the following equation 1.

[0033] [Formula 1]

[0034] Heat resistance (%) = P2 / P1 X 100

[0035] The heat treatment of the above yarn is carried out by elongating the yarn to 100% while exposed to the atmosphere, performing dry heat treatment at 190°C for 1 minute, cooling to room temperature, treating in a 0.9 g / L NaOH solution at 90°C for 30 minutes and washing in water three times, treating in a 0.4 g / L acetic acid solution at 130°C for 40 minutes and washing in water three times, dry heat treatment at 170°C for 1 minute, cooling to room temperature, and then relaxing.

[0036] In addition, in order to improve elongation, the intrinsic viscosity (IV) of the polyurethane urea polymer is maintained within the range of 1.1 to 1.2, and the number of amine terminals of the yarn is 3 to 20 meq / kg. When the intrinsic viscosity (IV) of the polyurethane urea polymer exceeds 1.2, the length of the polymer chain increases and the entanglement between chains increases, and the entanglement between chains interferes with the elongation of the polyurethane urea elastic yarn, which causes a problem of reduced elongation. In addition, when the intrinsic viscosity (IV) of the polyurethane urea polymer is less than 1.1, the molecular weight of the polymer chain is formed low, which causes a problem of reduced heat resistance of the yarn. Therefore, in order to improve elongation and maintain heat resistance, the intrinsic viscosity (IV) of the polyurethane urea polymer is preferably 1.1 to 1.2.

[0037] In addition, in the present invention, when the intrinsic viscosity (IV) of the polyurethane urea polymer is maintained at 1.2 or less, the penetration of the reactive dye into the molecular structure is easy, so that dyeability can be improved even at yarn ends less than 10, and thus post-polymerization by the ends that may occur during the storage process after yarn production can be suppressed, thereby preventing a decrease in elongation.

[0038] The polyurethane-urea elastic yarn of the present invention preferably has an amine terminal number of 3 to 20 meq / kg for the purpose of improving elongation. The amine terminals of the yarn serve as dyeing sites capable of binding to dyes. However, if the amine terminal number of the yarn is less than 3 meq / kg, sufficient dyeability effect for reactive dyes cannot be expected due to insufficient dyeing sites. Furthermore, if the amine terminal number of the yarn exceeds 20 meq / kg, the elongation may decrease due to post-polymerization during storage.

[0039] The polyurethane urea elastic yarn of the present invention is easy to access by a reactive dye by using an excessive amount of polyethylene glycol, and at the same time, the number of amine terminals is adjusted to a sufficient amount to secure a dyeing site, so that there are abundant reactive groups that can bind with a reactive dye, thereby enabling the polyurethane urea elastic yarn to implement dyeability for a reactive dye.

[0040] The dyeable polyurethane urea elastic yarn of the present invention is dyed with CI Reactive Black31 as a reactive dye in a dye solution having an owf concentration of 3% for 60 to 60 minutes, and then the reflectance of the yarn is measured using a spectrophotometer and, when calculated using the CIE lab color difference formula, the L* value is preferably less than 25. More preferably, it is less than 22, and most preferably, it is less than 20.

[0041] Another aspect of the present invention relates to a method for producing a flammable polyurethane urea elastic yarn. In the method of the present invention, polytetramethylene ether glycol (PTMG) and polyethylene glycol having a number average molecular weight of 4100 to 6000 are polymerized with a diisocyanate compound to produce a polyurethane prepolymer, which is then dissolved in a solvent to produce a prepolymer solution. Subsequently, the prepolymer solution and an amine solution containing a diamine chain extender and an amine chain terminator are subjected to a chain extension reaction to obtain a polyurethane urea spinning solution containing a polyurethane urea polymer, and the obtained polyurethane urea spinning solution is spun to produce a polyurethane urea elastic yarn. At this time, the polyethylene glycol is used in an amount of 3 to 15 mol% based on the total polyol.

[0042] In the present invention, it is preferable to mix polyethylene glycol in an amount of 3.0 to 15.0 mol% relative to the total polyol. If polyethylene glycol is used in an amount less than 3.0 mol%, dyeing with a reactive dye becomes difficult, and if it is used in an amount exceeding 15.0 mol%, problems may arise in process application due to poor spinning workability and deterioration of yarn properties caused by reduced heat resistance.

[0043] Specific examples of organic diisocyanates used in the production of polyurethane urea elastic yarns used in the present invention include 4.4'-diphenylmethane diisocyanate, 1,5'-naphthalene diisocyanate, 1,4'-phenylene diisocyanate, hexamethylene diisocyanate, 1,4'-cyclohexane diisocyanate, 4,4'-dicyclohexyl methane diisocyanate, isophorone diisocyanate, and the like. One type of these organic diisocyanates or a mixture of two or more types thereof may be used, but the present invention is not necessarily limited thereto.

[0044] Diamines can be used as chain extenders used to chain extend prepolymers, and examples of such diamine chain extenders include hydrazine, ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,2-butanediamine (1,2-diaminobutane), 1,3-butanediamine (1,3-diaminobutane), 1,4-butanediamine (1,4-diaminobutane), 1,3-diamino2,2-dimethylbutane, 4,4'-methylene-bis-cyclohexylamine, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, 1,6-hexanediamine, 2,2-dimethyl-1,3-diaminopropane, 2,4-diamino1-methylcyclohexane, N-methylaminobis(3-propylamine), 2-methyl-1,5-pentanediamine, Examples thereof include, but are not limited to, 1,5-diaminopentane, 1,4-cyclohexanediamine, 1,3-diamino4-methylcyclohexane, 1,3-cyclohexane-diamine, 1,1-methylenebis(4,4'-diaminohexane), 3-aminomethyl-3,5,5-trimethylcyclohexane, 1,3-pentanediamine (1,3-diaminopentane), m-xylenediamine, and mixtures thereof.

[0045] In the present invention, a chain terminator is generally used in a chain extension reaction to control the molecular weight of the polyurethane. Any chain terminator known in the art may be used. Examples of chain terminators include, but are not limited to, diethylamine (DEA), cyclohexylamine, butylamine, hexanol, butanol, and mixtures of two or more thereof.

[0046] Solvents that improve radioactivity by adjusting the concentration of the solid content of the polymer include compounds such as diethylacetamide, dimethylformamide, hexamethylphosphoramide, dimethylnitrosamine, dimethylpropionamide, methoxydimethylacetamide, N-methylpyrrolidine, dimethylsulfoxide, and tetramethylenesulfone. Dimethylformamide or dimethylacetamide is advantageous in terms of compatibility with the polymer, radioactivity, and solvent recovery. It is recommended to adjust the amount of solvent used so that the solid content of the polymer is 15-45%, and if it is less than 15% or more than 45%, it may have a negative effect on radioactivity.

[0047] In the spinning and winding stages, the spinning raw material is defoamed, dry-spinning is performed at a spinning temperature of 230 to 300°C, and then winding is performed at a winding speed of 500 to 1500 m / min.

[0048] Another aspect of the present invention relates to an elastic fabric comprising a polyurethane urea elastic yarn and polyester or cellulose fibers. The polyurethane urea elastic yarn of the present invention may be used alone, freely combined with other fibers, or covered.

[0049] The polyurethane urea elastic yarn of the present invention can be knitted with a nylon fiber, a polyester fiber, a cellulose fiber such as cotton, or rayon as a counter yarn to manufacture a fabric, and in particular, when a polyester and cellulose fiber blended yarn, such as a polyester and cotton blended yarn or a polyester and rayon blended yarn, is used as a counter yarn to knit a fabric, the dyeability for reactive dyes can be improved by making it easier for dyes to approach due to the improvement in hydrophilicity of the polyurethane urea elastic yarn, and the properties of the yarn can be maintained even during the dyeing process due to the improvement in heat resistance and elongation, thereby preventing a deterioration in the properties of the fabric or yarn breakage.

[0050] The present invention is described in more detail below with reference to examples; however, these examples are only intended to illustrate the implementation of the present invention, and the present invention is not limited to these examples.

[0051] Example

[0052] Example 1

[0053] 90.1 kg of polytetramethylene ether glycol (PTMG) was mixed with 10.0 mol% of polyethylene glycol (molecular weight 4300), and 26.4 kg of 4,4'-diphenylmethane diisocyanate was added. The mixture was stirred at 90°C for 120 minutes in a nitrogen gas stream to produce a polyurethane prepolymer having isocyanate at both ends. After cooling the prepolymer to room temperature, 229 kg of dimethylacetamide was added as a solvent to obtain a polyurethane prepolymer solution. Next, 3.2 kg of ethylenediamine as a chain extender and 0.4 kg of diethylamine as a chain terminator were dissolved in 50 kg of dimethylacetamide and added to the prepolymer solution at 10°C or lower to obtain a polyurethaneurea solution having an IV of 1.15. Additionally, 1.5 wt% of triethylene glycol-bis-3-(3-tertiary butyl-4-hydroxyphenyl) propionate as an antioxidant and hydrotalcite (Mg4Al2(OH)) as an inorganic chlorine antagonist were added to the polyurethane urea solution. 12 A polyurethane urea spinning solution was prepared by mixing 4 wt% of CO3·3H2O) and 0.5 wt% of titanium dioxide as a light-resistant agent. The spinning solution obtained as above was spun at a speed of 900 m / min by dry spinning to produce a polyurethane urea elastic yarn having 40 denier 3 filaments and an amine terminal number of 10 meq / kg.

[0054]

[0055] Example 2

[0056] During the process of preparing the prepolymer of Example 1, a polyurethane urea elastic yarn was manufactured in the same manner as Example 1, except that polyethylene glycol having a molecular weight of 5500 was used.

[0057]

[0058] Example 3

[0059] During the process of preparing the prepolymer of Example 1, a polyurethane urea elastic yarn was manufactured in the same manner as Example 1, except that 5 mol% of polyethylene glycol was mixed.

[0060]

[0061] Example 4

[0062] During the process of preparing the prepolymer of Example 1, a polyurethane urea elastic yarn was manufactured in the same manner as Example 1, except that 5 mol% of polyethylene glycol having a molecular weight of 5500 was mixed.

[0063]

[0064] Examples 5-8

[0065] Polyurethane urea elastic yarn was manufactured in the same manner as in Examples 1 to 4, except that the intrinsic viscosity (IV) of the polyurethane polymer was changed as shown in Table 1 below.

[0066]

[0067] Examples 9-14

[0068] Polyurethane urea elastic yarn was manufactured in the same manner as in Example 1, except that polyethylene glycol having a molecular weight of 5500 was used, and the content of polyethylene glycol, the intrinsic viscosity of the polymer, and the number of amine terminals of the yarn were changed as shown in Table 1 below.

[0069]

[0070] Comparative Examples 1-4

[0071] Polyurethane urea elastic yarn was manufactured in the same manner as in Example 1, except that the molecular weight of polyethylene glycol (PEG) was changed as shown in Table 1 below during the process of manufacturing the prepolymer.

[0072]

[0073] Comparative examples 5-8

[0074] Polyurethane urea elastic yarn was manufactured in the same manner as in Example 1, except that the content of polyethylene glycol was changed as described in Table 1 below.

[0075]

[0076] Comparative examples 9-16

[0077] Polyurethane urea elastic yarn was manufactured in the same manner as in Example 1, except that polyethylene glycol having a molecular weight of 5500 was used, and the content of polyethylene glycol, the intrinsic viscosity of the polymer, and the number of amine terminals of the yarn were changed as shown in Table 1 below.

[0078]

[0079] Exam example

[0080] The properties of the polyurethane urea elastic yarn manufactured in the examples and comparative examples were evaluated by the method below, and the results are shown in Table 1 below.

[0081] (1) Heat resistance (power retention before / after heat treatment): The heat resistance of the yarn is calculated by using an automatic elongation measuring device to repeat elongation and relaxation between 0 and 300% 5 times, and then the stress value at 200% elongation after the 5th elongation and relaxation is calculated. The stress value (P1) of the yarn before heat treatment and the stress (P2) after heat treatment are measured, and the heat resistance of the yarn is evaluated according to Equation 1 below. At this time, the yarn is heat treated by exposing the yarn to the atmosphere to 100% elongation, dry heat treatment at 190℃ for 1 minute, cooling to room temperature, treating in a 0.9 g / L NaOH solution at 90℃ for 30 minutes, washing in water 3 times, treating in a 0.4 g / L acetic acid solution at 130℃ for 40 minutes, washing in water 3 times, dry heat treatment at 170℃ for 1 minute, cooling to room temperature, and then relaxing.

[0082] [Formula 1]

[0083] Heat resistance (%) = P2 / P1 X 100

[0084] (2) L* value: The L* value, which indicates the degree of dyeing, was calculated by measuring the reflectance of the yarn using a spectrophotometer and then using the CIE Lab color difference formula. The L* value is a value that indicates brightness, and when dyed with the same dye, the darker the dye, the lower the L* value.

[0085] (Dyeing method)

[0086] CI Reactive Black31 was used as a reactive dye, with an owf of 3% and a bath ratio of 1:20. The dye and sample were added to a dye bath prepared with 60 g / L of Na2SO4, and the temperature was raised to 60°C at a rate of 2°C / min. Once the temperature reached 60°C, 20 g / L of Na2CO3 was added, maintained for 60 minutes, cooled to room temperature, and washed with water. Washing and draining were repeated until no color appeared in the drained water.

[0087] (3) Storage stability of polymer: When the prepared urethane urea solution is sampled without bubbles in a transparent glass vial and the turbidity is measured using a turbidity colorimeter, if the turbidity is 0.4 or higher, the polymer's viscosity aging rate is 200 P / hr or higher, and the polymer's storage stability is judged to be poor.

[0088] (4) Radiation workability: When the full bobbin ratio (%) calculated by Equation 2 below is less than 90% during radiation work, the radiation workability is judged to be poor.

[0089] [Formula 2]

[0090] Full Bobbin Rate (%) = (Full bobbin production / total production) X 100

[0091] Classification PEG molecular weight PEG content (mol%) Polymer IV Yarn Amine terminal (meq / kg) Process applicability L* value Heat resistance (%) Fabric Number of holes Storage stability Radiation workability Example 1 4300 101 1510 Good Good 16.6 45.70 Example 2 5500 101 1510 Good Good 10.5 47.70 Example 3 4300 51 1510 Good Good 19.1 53.20 Example 4 5500 51 1510 Good Good 16.7 55.70 Example 5 4300 101 1310 Good Good 17.1 45.40 Example 6 5500 101 1310 Good Good 9.9 46.80 Example 7 4300 101 1710 Good Good 17.6 46.90 Example 85500101.1710 Good Good 12.149.20 Example 95500101.155 Good Good 13.846.30 Example 10550051.155 Good Good 21.653.60 Example 115500101.1513 Good Good 8.749.40 Example 12550051.1513 Good Good 18.456.40 Example 135500101.1520 Good Good 7.751.70 Example 14550051.1520 Good Good 16.356.80 Comparative Example 12000101.1510 Good Good 20.230.30Comparative Example 23500101.1510Good Good 13.636.30Comparative Example 37000101.1510Poor Bad---Comparative Example 4700051.1510Poor Bad---Comparative Example 5430021.1510Good Good 56.555.40Comparative Example 6550021.1510Good Good 41.957.90Comparative Example 74300201.1510Good Good 3.126.41Comparative Example 85500201.1510Good Good 2.728.31Comparative Example 95500101.0520Good Good No. 15.437.70Comparative Example 10550051.0513Good Good 11.938.50Comparative Example 115500101.2520Good Good 14.360.17Comparative Example 12550051.2513Good Good 10.555.46Comparative Example 135500101.151Good Good 48.854.90Comparative Example 145500151.151Good Good 37.542.20Comparative Example 155500101.1523Good Good 12.357.36Comparative Example 165500101.1323Good Good 10.044.65

[0092]

[0093] Referring to the results in Table 1 above, in the case of Comparative Examples 1 and 2, the PEG molecular weight is less than 4100, so the heat resistance is low, making it difficult to use with PET blended yarns that require heat resistance, such as T / C or T / R spun yarns. In the case of Comparative Examples 3 and 4, the PEG molecular weight is more than 6000, so the melting point of PEG is high at 60°C or higher, and storage stability and spinnability are poor, making it difficult to apply to the process.

[0094] In Comparative Examples 5 to 6, the PEG content was less than 3 mol%, resulting in poor dyeability. In Comparative Examples 7 to 8, the PEG content was more than 15 mol%, resulting in low heat resistance, making it difficult to use with PET blended yarns that require heat resistance, such as T / C or T / R spun yarns.

[0095] Comparative Examples 9 to 10 have a polyurethane urea polymer with an intrinsic viscosity (IV) of less than 1.1, and the polymer chain length is short, so heat resistance is low, and spinning workability is poor, making it difficult to apply to the process. Comparative Examples 11 to 12 have a polyurethane urea polymer with an intrinsic viscosity (IV) of more than 1.2, and as the polymer chain length increases, chain entanglement increases, reducing yarn elongation, and causing holes in the fabric to occur, making them difficult to use.

[0096] Comparative examples 13 to 14 have an amine terminal of less than 3 meq / kg, and thus have insufficient dyeing sites within the yarn, resulting in poor dyeability. Comparative examples 15 to 16 have an amine terminal of more than 15 meq / kg, and thus have a reduced elongation due to post-polymerization during the yarn storage process, resulting in holes on the fabric, making them difficult to use.

[0097]

[0098] The present invention described above is not limited to the above-described embodiments, and it will be apparent to a person skilled in the art to which the present invention pertains that various substitutions, modifications, and changes are possible within a scope that does not depart from the technical spirit of the present invention.

Claims

1. A polyurethane urea elastic yarn comprising a mixed polyol composed of polytetramethylene ether glycol (PTMG) and polyethylene glycol having a number average molecular weight of 4,100 to 6,000 and an organic diisocyanate, characterized in that the polyethylene glycol is contained in an amount of 3 to 15 mol% based on the total mixed polyol.

2. A flame-retardant polyurethane urea elastic yarn, characterized in that the heat resistance of the yarn exceeds 45%, as determined by measuring the stress at an elongation of 200% of the elastic yarn before (P1) and after (P2) heat treatment, according to the following mathematical formula 1. [Formula 1] Heat resistance (%) = P2 / P1 X 100 3. A flammable polyurethane urea elastic yarn, characterized in that the inherent viscosity (IV) of the polyurethane urea polymer constituting the polyurethane urea elastic yarn in the first paragraph is 1.1 to 1.

2.

4. A flammable polyurethane urea elastic yarn, characterized in that the amine terminal of the polyurethane urea elastic yarn in the first paragraph is 3 to 20 meq / kg.

5. A dyeable polyurethane urea elastic yarn according to claim 1, characterized in that the polyurethane urea elastic yarn exhibits a dyeability of L* value of 30 or less when dyed with a reactive dye.

6. A method for producing a saltable polyurethane urea elastic yarn, comprising: polymerizing polytetramethylene ether glycol (PTMG) and polyethylene glycol having a number average molecular weight of 4,100 to 6,000 with a diisocyanate compound to produce a polyurethane prepolymer, then dissolving the polyurethane prepolymer in a solvent to produce a prepolymer solution, subjecting the prepolymer solution to a chain extension reaction with an amine solution containing a diamine chain extender and an amine chain terminator to obtain a polyurethane urea spinning stock containing a polyurethane urea polymer, and spinning the obtained polyurethane urea spinning stock to produce a polyurethane urea elastic yarn, wherein the polyethylene glycol is used in an amount of 3 to 15 mol% based on the total polyol.

7. A method for producing a flammable polyurethane urea elastic yarn, characterized in that in paragraph 6, the intrinsic viscosity (IV) of the polyurethane urea polymer is 1.1 to 1.2, and the amine terminal of the polyurethane urea elastic yarn is 3 to 20 meq / kg.

8. An elastic fabric made by blending the flammable polyurethane urea elastic yarn described in any one of clauses 1 to 5 with other fibers.

9. An elastic fabric according to claim 8, characterized in that the other fiber is a polyester fiber, a cellulose fiber, or a blend of polyester fiber and cellulose fiber.