JP2010150720A - Elastic fabric - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide elastic fabric having excellent high heat resistance in dying (high heat resistance when an unsaturated fatty acid or a heavy metal adheres thereto, in particular). <P>SOLUTION: The elastic fabric includes polyurethane elastic fiber which is formed by copolymerizing polytrimethylene ether glycol having crystallization energy of 10J/g or more and crystallization temperature of -60 to -40°C diisocyanate and diamine chain extender, which has DSC melting point falling in a range of 120-150°C, and in which enthalpy in a range of 120-150°C is 5.5J/g or more. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an elastic fabric. More specifically, the present invention relates to an elastic fabric that is superior in heat resistance during dyeing (particularly heat resistance when unsaturated fatty acids or heavy metals are attached) as compared with conventional elastic fabrics including polyurethane elastic yarns.

  Elastic fibers are widely used in stretch clothing and industrial materials such as leg wear, inner wear, and sports wear because of their excellent stretch properties.

  Polyurethane elastic yarns that are widely used as such elastic fibers are required to have high tensile elongation, high elastic recovery, high heat resistance, and heat setting properties. Especially, high heat resistance is strongly requested | required in the use used with the mixed fabric combined with the polyester thread | yarn, and especially the heat resistance at the time of a dyeing process is important.

  That is, when used in combination with polyester yarns or when intermediate colors are developed, the dyeing temperature itself during dyeing tends to be high. In addition, in order to obtain good stretch properties, dimensional stability, and surface quality, there are increasing cases of performing dry heat treatment at a high temperature before dyeing. For this reason, the elastic yarn needs to have high heat resistance.

  However, in the mixed elastic fabric of polyester yarn and polyurethane elastic yarn, the oil agent moves from the mixed yarn such as polyester yarn to the elastic yarn, and the mixed yarn adhering oil agent adheres to the elastic yarn. In general, unsaturated fatty acids are used in oils. On the other hand, an oil containing a thermal embrittlement promoting substance of unsaturated fatty acid is applied to the elastic yarn that is mixed with the polyester yarn, nylon yarn, or the like to constitute the mixed elastic fabric. Furthermore, metal components derived from machinery are mixed in these oil agents although they are in a trace amount. Therefore, the unsaturated fatty acid in the oil that has been transferred from the mixed yarn and the thermal embrittlement promoting substance and the trace metal component of the unsaturated fatty acid in the oil given to the polyurethane elastic yarn react with each other by heat during dyeing, Deterioration of polyurethane elastic yarn is promoted, and yarn breakage and partial strength reduction are likely to occur. In some cases, fine perforations of the fabric may be generated, which may cause more serious problems than expected.

  Therefore, even when an unsaturated fatty acid or a metal component is attached to the elastic yarn together with the oil agent, it is strongly required to have excellent heat resistance. Moreover, although it is contrary to high heat resistance, it is also required that heat setting can be performed at a conventional temperature, preferably at a lower temperature than conventional.

  For example, in order to prevent yellowing in a polyurethane elastic yarn containing a benzotriazole-based ultraviolet absorber for enhancing the light embrittlement prevention property, a metal deactivator is contained in the elastic yarn, and a benzotriazole-based ultraviolet ray is added. A technique for preventing a complex from forming between the absorbent and copper has been proposed (see Patent Document 1). However, it is difficult to increase the heat resistance of a polyurethane elastic yarn during dry heat treatment or high temperature dyeing even when a metal deactivator is added. When a mixed fabric is dyed at a high temperature, the heat resistance is still unsatisfactory and its use may be limited.

  In addition, a technique relating to a polyurethane elastic yarn containing a necessary amount of a triazine absorber and an N, N-dialkylsemicarbazide group has been proposed for protection against atmospheric haze and light fading (see Patent Document 2). However, excessive addition of a light-absorbing agent tends to inhibit the heat resistance of the polyurethane elastic yarn during dry heat treatment or high temperature dyeing. Therefore, heat resistance is still unsatisfactory when using a dry heat treatment at a high temperature before dyeing, or dyeing at a high temperature using a mixed fabric with a polyester yarn, which may limit use.

  Furthermore, Patent Document 3 describes that polyurethane using polytrimethylene ethylene ether glycol can be used for fibers, fabrics and the like. However, the method described in this document performs the polyurethane-forming reaction without a solvent, the reaction between isocyanate and amine cannot be controlled, the disproportionation reaction occurs, and the polymer is easily gelled locally. Such a polymer cannot be easily obtained. For this reason, gel (foreign matter) is easily contained in the polymer, and if it is spun, it can be said that the spinnability is poor. Moreover, even if it can be spun, since the orientation of the polymer chain is disturbed, it tends to be inferior in heat resistance as a fabric. For this reason, no specific method has been suggested regarding the actual spinning of fibers to form a fabric.

Patent Document 4 describes that a polyurethane is produced by polymerization using a solvent, and that polytrimethylene ether glycol or the like can be used as a polymer diol as a main constituent component of the polyurethane. Has been. However, this document does not describe an embodiment in which a polyurethane elastic yarn is actually spun using polytrimethylene ether glycol, and the actually described embodiment has a purity of 1,3-propanediol units. Since it is an embodiment using a polyether polyol which is considered to be not so high, it cannot be said that the melting point of the resulting polyurethane is lowered, and the heat resistance of the raw yarn and the fabric is not sufficiently met.
JP 2000-169700 A Japanese Patent No. 3028237 JP 2005-535744 A JP 2008-248137 A

  An object of the present invention is to solve the above-described problems of the prior art and to provide an elastic fabric excellent in heat resistance during dyeing (particularly heat resistance when unsaturated fatty acids and heavy metals are attached). .

In order to achieve the above object, the present invention employs any of the following means.
(1) An elastic fabric comprising a polyurethane elastic yarn polymerized from polytrimethylene ether glycol having a crystallization point, a diisocyanate, and a diamine chain extender.
(2) The elastic fabric according to (1), wherein the polytrimethylene ether glycol has a crystallization energy of 10 J / g or more.
(3) The elastic fabric according to (1) or (2), wherein the polytrimethylene ether glycol has a crystallization temperature of −60 to −40 ° C.
(4) The polyurethane elastic yarn has a DSC melting point in the range of 120 ° C. to 150 ° C., and the enthalpy in the range of 120 ° C. to 150 ° C. is 5.5 J / g or more. 3) The elastic fabric according to any one of the above.
(5) The polyurethane elastic yarn according to any one of (1) to (4), wherein the heat setting efficiency HSE is 25 or more.
(6) The elastic fabric according to any one of (1) to (5), wherein the polyurethane elastic yarn has a resistance to repetitive dyeing at 130 ° C. of 65% or more. (7) The polytrimethylene ether glycol has a hydroxyl value. The elastic fabric according to any one of (1) to (6), wherein is 25 to 120.
(8) The elastic fabric according to any one of (1) to (7), wherein a reaction equivalent ratio (molar ratio) between the polytrimethylene ether glycol and the diisocyanate is 1: 1 to 1: 5.
(9) The elastic fabric according to any one of (1) to (8), wherein the polyurethane elastic yarn has a terminal group concentration derived from a diamine compound of 5 to 50 meq / kg.
(10) The elastic fabric according to any one of (1) to (9), wherein the polyurethane elastic yarn is polymerized by a prepolymer method.
(11) The elastic fabric according to any one of (1) to (10), wherein the polyurethane elastic yarn is spun by a dry method.

  The elastic fabric of the present invention can exhibit excellent heat resistance (particularly heat aging resistance) even when unsaturated fatty acids or heavy metals adhere to the yarn when dyeing at high temperatures, and is manufactured using this elastic fabric. Apparel and the like have excellent detachability, fit, wearing feeling, dyeing color, discoloration resistance, appearance quality and the like.

  The elastic fabric of the present invention includes a polyurethane urea elastic yarn (hereinafter referred to as polyurethane elastic yarn) polymerized from polytrimethylene ether glycol, diisocyanate and a diamine chain extender as a main constituent.

  The polyurethane elastic yarn is polymerized from polytrimethylene ether glycol, diisocyanate, and diamine chain extender. In the present invention, it is important to use polytrimethylene ether glycol having a crystallization point. By polymerizing polyurethane from polytrimethylene ether glycol having a crystallization point, the crystallinity of the soft segment in the polyurethane is increased, and the heat resistance of the resulting polyurethane elastic yarn is improved. In order to further enhance the effect, the polytrimethylene ether glycol preferably has a crystallization energy of 10 J / g or more.

  The hydroxyl value of polytrimethylene ether glycol is preferably in the range of 25-120. More preferably, it is 30-100, More preferably, it is between 35-70. By using polytrimethylene ether glycol having a hydroxyl value in this range, it is possible to obtain an elastic yarn suitable for use in a warp knitted elastic fabric excellent in stretch performance. The hydroxyl value is measured by the method described in JIS K1557-1: 2007.

  The polytrimethylene ether glycol may be mixed or copolymerized with other glycols to such an extent that the properties are not impaired. Such other glycols are not particularly required to be polyether-based, and can be used alone or in combination of two or more from polyester-based and polycarbonate-based.

  The reaction equivalent ratio (molar ratio) of polytrimethylene ether glycol and diisocyanate is preferably in the range of 1: 1 to 1: 5. More preferably, it is 1: 1.2-1: 3.5, More preferably, it is between 1: 1.3-1: 2.2. Within this range, a polyurethane elastic yarn having an appropriate elongation and excellent workability can be obtained.

  As the diisocyanate, one or more compounds selected from aromatic diisocyanate, alicyclic diisocyanate, and aliphatic diisocyanate compounds can be used. Examples of the aromatic diisocyanate compound include 5-isocyanate-1- (isocyanatemethyl) -1,3,3-trimethylcyclohexane, 1-isocyanate-4-[(4-isocyanatephenyl) methyl] benzene, and 1-isocyanate-2. -[(4-isocyanate-phenyl) methyl] benzene, 1,1′-methylenebis (4-isocyanatecyclohexane), 4-methyl-1,3-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate (hereinafter abbreviated as MDI) And 2,4-tolylene diisocyanate, 1,4-diisocyanate benzene, xylylene diisocyanate, 2,6-naphthalene diisocyanate, and the like. Such an aromatic diisocyanate is particularly preferable for synthesizing polyurethane urea having high heat resistance and high strength.

  Examples of the alicyclic and alicyclic diisocyanate compounds include methylene bis (cyclohexyl isocyanate), isophorone diisocyanate, methylcyclohexane 2,4-diisocyanate, methylcyclohexane 2,6-diisocyanate, cyclohexane 1,4-diisocyanate, hexahydroxylylene diisocyanate, Examples include hexahydrotolylene diisocyanate and octahydro 1,5-naphthalene diisocyanate. Aliphatic and alicyclic diisocyanate compounds are particularly preferred in order to suppress yellowing of the polyurethane yarn.

  Among the diisocyanate compounds as described above, an aromatic diisocyanate compound is preferable because it exhibits excellent heat resistance of the resulting yarn, and MDI, or MDI and one or more aromatics. More preferably, it is a mixture with a diisocyanate compound.

  Examples of the diamine chain extender include low molecular weight diamine compounds such as hydrazine, ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 2-methyl-1,5-pentanediamine, 1,2-diaminobutane, 1, 3-diaminobutane, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, 2,2-dimethyl-1,3-diaminopropane, 1,3-diamino-2,2-dimethylbutane, 2 , 4-Diamino-1-methylcyclohexane, 1,3-pentanediamine, 1,3-cyclohexanediamine, bis (4-aminophenyl) phosphine oxide, hexamethylenediamine, 1,3-cyclohexyldiamine, hexahydrometaphenylenediamine 2-methylpentamethylenediamine, bis (4-amino Phenyl) phosphine oxide and the like. It is possible to use one or a mixture of two or more of these. Moreover, you may use together low molecular weight diol compounds, such as ethylene glycol, to such an extent that a characteristic is not impaired.

  Among the diamine compounds, diamine compounds having 2 to 5 carbon atoms are preferred, and ethylenediamine is particularly preferred from the viewpoint of producing an elastic yarn excellent in elongation, elastic recovery and the like. In addition to these chain extenders, a triamine compound (such as diethylenetriamine) capable of forming a crosslinked structure may be used in combination as long as the effects of the present invention are not lost.

  In order to control the molecular weight of the resulting polyurethane, it is preferable to use a chain terminator in the chain extension reaction. It is preferable that the molar ratio of the chain extender to the chain terminator is between 5 and 15 because the yarn characteristics after spinning are stable. More preferably, it is between 8-12.

  As such chain terminators, monoalcohol compounds such as n-butanol and monoamine compounds such as dimethylamine, diethylamine, cyclohexylamine, and n-hexylamine can be used. A monoamine compound is preferred, and diethylamine is more preferred. Chain end terminators are usually used in admixture with chain extenders.

  The polymerization method of the polyurethane elastic yarn polymerized from the above polytrimethylene ether glycol, diisocyanate and diamine chain extender is not particularly limited, and any of melt polymerization method and solution polymerization method may be used. The method may be used. However, the solution polymerization method is more preferable. In the case of the solution polymerization method, there is an advantage that the generation of foreign matters such as gels in polyurethane is small.

  In the case of the solution polymerization method, for example, raw materials such as diol compounds such as polytrimethylene ether glycol, diisocyanate compounds, and diamine compounds are used in solvents such as DMAC, DMF, DMSO, and NMP. A polyurethane solution can be obtained by polymerization. The reaction method is not particularly limited. For example, the one-shot method in which each raw material is charged and dissolved in a solvent and heated to an appropriate temperature to react, and then the diol compound and the diisocyanate compound are first used without a solvent. A prepolymer method may be mentioned, in which the prepolymer is dissolved in a solvent and then subjected to a chain extension reaction with a diamine compound to synthesize polyurethane, and the prepolymer method is preferred.

  The spinning method for forming polyurethane elastic yarn by spinning polyurethane obtained by the solution polymerization method is not particularly specified, and publicly known methods can be applied. From the viewpoint of properties, the dry spinning method is preferred. The concentration of polyurethane in the spinning solution is not particularly limited, but is preferably between 20 and 60% by weight from the molecular weight and solution viscosity of polyurethane and the elastic properties of the resulting elastic yarn. More preferably, it is between 30-50 weight%, More preferably, it is between 35-45 weight%.

  In dry spinning, for example, the following conditions may be employed. A polyurethane urea solution flow discharged from the spinneret is introduced into a spinning cylinder provided with at least two gas supply parts and a gas suction part provided between the gas supply parts, and is passed through the spinning cylinder. . The temperature of the gas supplied from the gas supply unit provided at the lower part of the spinning cylinder is preferably 60 ° C. or less from the viewpoint of eliminating yarn unevenness. The speed ratio between the godet roller and the winder after passing through the spinning cylinder may be determined according to the purpose of use of the yarn. Generally, the speed ratio of the winder to the godet roller is 1.1 to 1. Is preferably in the range of .8. The spinning speed is preferably 300 to 800 m / min.

  In the present invention, the fineness, cross-sectional shape and the like of the polyurethane elastic yarn are not particularly limited, and may be determined according to the purpose of use. For example, the cross section may be circular or flat.

  In addition, the polyurethane elastic yarn includes a hindered phenolic agent such as a UV absorber, an antioxidant, and a gas-resistant stabilizer, so-called BHT and “Smizer” GA-80 manufactured by Sumitomo Chemical Co., Ltd. Benzotriazole drugs such as various "Tinuvin", phosphorus drugs such as "Sumilyzer" P-16 manufactured by Sumitomo Chemical Co., Ltd., hindered amine drugs including various "Tinubin", and oxidation Inorganic pigments such as titanium, zinc oxide and carbon black, metal soaps such as magnesium stearate, bactericides and deodorants containing silver and zinc and their compounds, silicone and mineral oil Contains various antistatic agents including lubricants, barium sulfate, cerium oxide, betaine and phosphoric acid. It may be. In order to further enhance the durability to light and various nitric oxides in particular, a nitric oxide supplement, for example, HN-150 manufactured by Nippon Hydrazine Co., Ltd., a thermal oxidation stabilizer, for example, Sumitomo Chemical Co., Ltd. It is preferable to use “Sumilyzer” GA-80 manufactured by Sumitomo Chemical Co., Ltd., and “Sumisorb” 300 # 622 manufactured by Sumitomo Chemical Co., Ltd.

  These agents may be added to the polyurethane solution before dry spinning, and any method can be adopted as an addition / mixing method. As typical methods, it is preferable to employ a method of adding to a spinning solution and mixing with a static mixer, a method of stirring, or the like. Here, the additive is preferably added as a solution. When it is a solution, it can be uniformly added to the polyurethaneurea solution.

  The polyurethane elastic yarn as described above has a DSC melting point in the range of 120 to 150 ° C. in DSC, and the enthalpy in the range of 120 to 150 ° C. is 5.5 J / g or more. By using such an elastic yarn, the heat resistance at the dyeing processing temperature is remarkably improved, and an elastic fabric having excellent stretch properties can be obtained.

  The polyurethane elastic yarn preferably has a heat setting efficiency HSE calculated by the method described later of 25 or more. If this value is less than 25, there will be a problem that the end of the warp knitted fabric is curled during high-order processing.

  The heat setting HSE is measured as follows. That is, the elastic yarn constituting the fabric is treated free with 100 ° C. steam for 10 minutes, then free treated with 100 ° C. boiling water for 2 hours, and then dried at room temperature for one day. Thereafter, the sample yarn (length = (L5)) is stretched 150% (= 2.5 × (L5)) and treated with steam at 115 ° C. for 1 minute, and dry heat treatment at the same length at 120 ° C. for 1 minute. And leave at room temperature for 1 day at the same length. Thereafter, the length (L6) is measured, and the heat setting property HSE is calculated from the following formula.

HSE = 100 × ((L6) − (L5)) / (L5)
In order to obtain an elastic yarn having a heat-setting HSE of 25 or more as described above, for example, it is preferable that the purity of 1,3-propanediol, which is a raw material of polytrimethylene ether glycol, is 98% or more.

  The polyurethane elastic yarn of the present invention preferably has a resistance of 50% or more at repeated dyeing at 130 ° C. More preferably, it is 60% or more, More preferably, it is 65% or more. The term “resistance” as used herein refers to the retention ratio of the resilience when the treatment for 60 minutes in a high-temperature liquid at 130 ° C. is repeated three times. Specifically, it is described in the section of “Heat resistance during dyeing 4” described later. What is evaluated by the method described. If this resistance is low, the elastic fabric will be in a so-called “no stiffness” state, and the stretch performance will be extremely deteriorated.

  In order to set the resistance of the polyurethane elastic yarn to 130 ° C. repetitive dyeing to 65% or more, for example, the purity of 1,3-propanediol, which is a raw material of polytrimethylene ether glycol, is preferably 98% or more.

  The polyurethane elastic yarn in the present invention preferably has a terminal group concentration derived from a diamine compound of 5 to 50 meq / kg. More preferably, it is between 10 and 45 meq / kg. When the terminal group concentration is higher than 50 meq / kg, the polymer has a short molecular weight, and there is a problem that the recovery power and heat resistance are inferior. In other words, it becomes a yarn with low strength and elongation.

In addition, in order to measure the terminal group density | concentration derived from the diamine compound of a polyurethane elastic yarn, it carries out as follows. That is, the polyurethane elastic fiber is cut and dissolved with DMAc to obtain a solution having a polyurethane urea concentration of 1.77% by weight. And using Hiratuma Co., Ltd. automatic titrator (COM-900), potentiometric titration with p-toluenesulfonic acid (0.01N), total content of primary amine and secondary amine (A) Ask for. Subsequently, salicylaldehyde (20% isopropyl alcohol solution) was added to this solution and reacted with a primary amine, and then the secondary amine was subjected to potentiometric titration with p-toluenesulfonic acid (0.01 N), The secondary amine content (B) is determined. The end group concentration derived from the diamine compound is calculated from the following formula.
Effective terminal amine value (meq / kg) = (A)-(B)
In the present invention, the fabric is formed using the polyurethane elastic yarn as described above. Such a fabric may be composed only of the polyurethane elastic yarn. For example, the effect of the present invention can be manifested in a mixed elastic fabric in which, for example, polyester yarn or nylon yarn is mixed.

  That is, when a polyurethane elastic yarn is mixed with a polyester yarn, a nylon yarn or the like to make a fabric, the oil agent of the mixed yarn such as a polyester yarn is transferred to the polyurethane elastic yarn, and the unsaturated fatty acid or the metal component is the polyurethane elastic yarn. Adhere to. When used in combination with polyester yarn or nylon yarn, or when neutral colors are developed, the dyeing temperature itself during dyeing tends to increase, and good stretchability, dimensional stability, surface quality Therefore, the polyurethane elastic yarn has high crystallinity of the soft segment in the polyurethane and has high heat resistance. No deterioration, no thread breakage, partial strength reduction, or perforation.

  The fabric may be a knitted fabric or a woven fabric. In the case of knitted fabrics, warp knitting or weft knitting may be used, and in the case of woven fabrics, any woven structure such as plain weave or oblique weave may be used.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

[DSC melting point and enthalpy of polyurethane elastic yarn]
The DSC melting point measurement using a differential scanning calorimeter was performed using a differential scanning calorimeter (manufactured by TA Instruments Japan Co., Ltd., 2920MDSC). Samples 10 to 10 mg obtained by cutting the polyurethane elastic yarn were heated at a heating rate of 10 ° C./min, and a peak observed from 120 ° C. to 150 ° C. was obtained as the melting point. Moreover, the enthalpy (J / g) shown over 120 to 150 degreeC was measured. In addition, when evaluating the polyurethane yarn to which the oil agent is adhered, it is evaluated after washing it off with an organic solvent such as a refining agent or petroleum ether.

[Heat setting property of polyurethane elastic yarn (HSE)]
The elastic yarn constituting the fabric was treated with free steam at 100 ° C. for 10 minutes, then treated free with boiling water at 100 ° C. for 2 hours and dried at room temperature for one day. Next, the sample yarn (length = (L5)) was stretched 150%. This length (= 2.5 × (L5)) was treated with 115 ° C. steam for 1 minute. Furthermore, the same length was subjected to a dry heat treatment at 120 ° C. for 1 minute, and further left at room temperature for 1 day at the same length. Next, the elongation state of the sample yarn was removed, and the length (L6) was measured. The value of heat setting property is calculated by the following formula.
Heat setting property (%) = 100 × ((L6) − (L5)) / (L5)
In addition, the measurement was performed 5 times and the average value of each value of the heat setting property calculated from the measurement of 5 times was adopted.

[Breaking strength]
The breaking strength was measured by subjecting the polyurethane elastic yarn to a tensile test using an Instron 4502 type tensile tester.

Extending a sample having a test length of 5 cm by 300% at a tensile speed of 50 cm / min was repeated five times. Furthermore, it extended until the sample cut | disconnected 6th time. The stress at the time of this break was defined as (G3).
Breaking strength (cN) = (G3)
In addition, the measurement was performed 5 times and the average value of each value of the breaking strength obtained from the measurement of 5 times was employ | adopted.

[Heat resistance at the time of dyeing 1 (resistance in a state where unsaturated fatty acid and heavy metal are adhered to a nylon-mixed fabric having a relatively low dyeing temperature)]
Number of machine wells consisting of 85% by weight nylon filament (24 dtex, 7 filaments) manufactured by Toray Industries, Inc. and 15% by weight polyurethane elastic yarn (20 dtex), number of courses on machine A 25 / inch (25 / 2.54 cm) two-way half tricot was produced by a normal knitting method to obtain a raw knitted fabric.

  The obtained raw knitted fabric was preset at 170 ° C. for 60 seconds under the condition of 3% elongation, and 0.1 ml of drug 1 was applied, followed by (within approximately 1 to 1 minute) 0.1 ml of After applying medicine 2, dry heat treatment (175 ° C, after 60 seconds of dry heat treatment, once taken out and dissipated to room temperature, then 180 ° C, 60 seconds of dry heat treatment), then up to 20% alternately in both vertical and horizontal directions Elongation, subjected to a bending tester of 2 times / second. In addition, as the medicine 1, a spinning oil for mineral oil based nylon containing 1% oleic acid was used. Moreover, the chemical | medical agent 2 used the copper acetate aqueous solution (copper concentration of 100 ppm). The raw knitted fabric to which the drug 1 and the drug 2 are attached in this way has a small amount of machine oil (mixed with metal) and nylon spinning oil for knitting adhered to the nylon stretch raw knitted fabric before dyeing. The amount of drug 1 attached to 0.9 g of raw knitted fabric was 3.0 mg, and the amount of drug 2 attached was 3.0 mg.

  The obtained stretch fabric was dyed by a conventional method. That is, Kayanol Milling Blue 2RW (manufactured by Nippon Kayaku Co., Ltd.) 1.0 owf staining solution, dyed by liquid flow staining at 98 ° C.

The degree of damage of the polyurethane structure in the obtained dyed stretch fabric was observed visually or enlarged, and judged according to the following criteria. The determination was performed by five people, and the mode value (the determination that appeared most frequently) was used. When the determination was divided into two, two, and one, the determination was “Δ”.
○: No damage.
Δ: Sag or depression was observed in the fabric, and the polyurethane elastic yarn became brittle when enlarged.
X: The fabric has a hole.

[Heat resistance at dyeing 2 (resistance to repeated dyeing in nylon-mixed fabric with relatively low dyeing temperature)]
In order to evaluate the heat aging resistance at the time of dyeing polyurethane yarn at high temperature, the polyurethane yarn was subjected to a high temperature liquid treatment by the following method, the breaking strength of the polyurethane yarn before and after that was measured, and the retention rate was calculated. . In addition, when evaluating the polyurethane yarn to which the oil agent is adhered, it is evaluated after washing it off with an organic solvent such as a refining agent or petroleum ether.

  The polyurethane yarn was fixed in a 100% stretched state, pre-set (170 ° C., 60 seconds), then left unstrained for 24 hours at room temperature, and the breaking strength (G3) was measured. In addition, after pre-setting, it is sealed in a pressure vessel containing high-temperature water at 98 ° C., and the treatment at 98 ° C. for 60 minutes is set as one set, and the treatment in the high-temperature liquid is performed three times. went. At this time, after the first high-temperature liquid treatment, after the second high-temperature liquid treatment, the sample was once taken out from the pressure vessel and radiated to room temperature, and then subjected to the next high-temperature liquid treatment. The polyurethane yarn after the third high-temperature liquid treatment was taken out of the pressure vessel, brought into an unstrained state, allowed to stand at room temperature for 24 hours, and the breaking strength (G5) was measured by the same method as described above. The ratio (breaking strength retention) of the breaking strength (G5) of the yarn after the third high-temperature liquid treatment to the breaking strength (G3) of the yarn that was only pre-set was calculated and used as an index of heat resistance 2 .

Breaking strength retention rate (%) = 100 × (G5) / (G3)
[Heat resistance at the time of dyeing 3 (resistance in a state where unsaturated fatty acid and heavy metal are adhered to a polyester mixed fabric having a relatively high dyeing temperature)]
On-machine course consisting of 82% by weight polyethylene terephthalate filament (33 dtex, 48 filaments) manufactured by Toray Industries, Inc. and 18% by weight polyurethane elastic yarn (22 dtex), 13 / inch (13 / 2.54 cm) A two-way half tricot of several 30 / inch (30 / 2.54 cm) was produced by a normal knitting method to obtain a raw knitted fabric.
The obtained raw knitted fabric was preset at 190 ° C. for 60 seconds under the condition of 3% elongation, and 0.1 ml of drug 1 was applied, followed by (within approximately 1 to 1 minute) 0.1 ml of After the chemical 2 is applied, dry heat treatment (195 ° C, after 60 seconds of dry heat treatment, once taken out and dissipated to room temperature, then 200 ° C, 60 seconds of dry heat treatment) is performed, and then up to 20% alternately in both vertical and horizontal directions Elongation, subjected to a bending tester of 2 times / second. In addition, a spinning oil for mineral oil-based polyester containing 1% oleic acid was used as the medicine 1. Moreover, the chemical | medical agent 2 used the copper acetate aqueous solution (copper concentration of 100 ppm). In the raw knitted fabric to which the drug 1 and the drug 2 are attached in this way, a small amount of machine oil (mixed with metal) and polyester spinning oil during knitting adhere to the polyester stretch raw knitted fabric before dyeing. The amount of drug 1 attached to 1.0 g of raw knitted fabric was 3.0 mg, and the amount of drug 2 attached was 3.0 mg.

  The obtained stretch fabric was dyed by a conventional method. That is, high energy type disperse dye "Dianix" Black HG-FS conc (Dystar Co., Ltd.) 4% owf and POE alkylamine ether sulfate "New Bon WS" (Nikka Chemical Co., Ltd. leveling agent) 1 It dye | stained at 125 degreeC for 60 minute (s) with the dyeing bath which adjusted to pH5 with the buffer solution of acetic acid and sodium acetate.

  Next, in a treatment bath containing 2 g / l hydrosulfite, 2 g / l special anionic surfactant “Senkanol CW” (manufactured by Senka), and 1 g / l sodium hydroxide at 70 ° C. for 20 minutes, Reduction cleaning was performed.

The degree of damage of the polyurethane structure in the obtained dyed stretch fabric was observed visually or enlarged, and judged according to the following criteria. The determination was performed by five people, and the mode value (the determination that appeared most frequently) was used. When the determination was divided into two, two, and one, the determination was “Δ”.
○: No damage.
Δ: Sag or depression was observed in the fabric, and the polyurethane elastic yarn became brittle when enlarged.
X: The fabric has a hole.

[Heat resistance at the time of dyeing 4 (resistance to repeated dyeing in a polyester mixed fabric having a relatively high dyeing temperature)]
In order to evaluate the heat aging resistance at the time of dyeing a polyurethane yarn at a high temperature, the polyurethane yarn was subjected to a high-temperature liquid treatment by the following method, the breaking strength of the polyurethane yarn before and after that was measured, and the retention rate was calculated. In addition, when evaluating the polyurethane yarn to which the oil agent is adhered, it is evaluated after washing it off with an organic solvent such as a refining agent or petroleum ether.

  The polyurethane yarn was fixed in a stretched state of 100%, pre-set (190 ° C., 60 seconds), then left unstrained for 24 hours at room temperature, and the breaking strength (G3) was measured. In addition, after pre-setting, it is sealed in a pressure vessel containing high-temperature water at 130 ° C., and the treatment at 130 ° C. for 60 minutes is set as one set, and the treatment in the high-temperature liquid is performed three times. went. At this time, after the first high-temperature liquid treatment, after the second high-temperature liquid treatment, the sample was once taken out from the pressure vessel and radiated to room temperature, and then subjected to the next high-temperature liquid treatment. The polyurethane yarn after the third high-temperature liquid treatment was taken out of the pressure vessel, brought into an unstrained state, allowed to stand at room temperature for 24 hours, and the breaking strength (G5) was measured by the same method as described above. The ratio of the breaking strength (G5) of the yarn after the third high-temperature liquid treatment (breaking strength retention) to the breaking strength (G3) of the yarn that was only pre-set was calculated and used as an index of heat resistance 4 .

Breaking strength retention rate (%) = 100 × (G5) / (G3)
[Appearance quality]
A dyed stretch fabric was produced in the same manner except that the application of the drug 1 and the drug 2 and the bending test were not performed in the heat resistance 1 test at the time of dyeing or the heat resistance 3 test at the time of dyeing. That is, after forming a raw knitted fabric, a dyed stretch fabric was prepared by presetting, dry heat treatment, and dyeing. About the obtained dyed stretch fabric (a fabric having a width of 1.8 m and a length of about 20 m), the appearance of the fabric was visually inspected, the polyurethane structure was enlarged and observed, and the determination was made according to the following criteria. The determination was performed by five people, and the mode value (the determination that appeared most frequently) was used. When the determination was divided into two, two, and one, the determination was “Δ”.
○: There are no wavy or streak-like defects, and the structure is homogeneous.
(Triangle | delta): There are a partial wavy and a stripe defect, and it is 1 or less per 20m.
X: There are wavy and streak-like defects, and there are one or more places per 20 m.

[Crystallizing energy and crystallization temperature of polytrimethylene ether glycol]
Using a differential scanning calorimeter (manufactured by TA Instruments Japan Co., Ltd., 2920MDSC), 7-10 mg of polytrimethylene ether glycol was increased from −100 ° C. to 100 ° C. at a heating rate of 3 ° C./min. The crystallization temperature (° C.) and crystallization energy (J / g) were measured by heating.

[Preparation of polytrimethylene ether glycol 1, 2]
The polytrimethylene ether glycols 1 and 2 used in the following examples were prepared using 1,3-propanediol having a purity of 99.8% as a raw material, as disclosed in JP-T-2003-517082, JP-T-2005-511835, JP-A-2004-352713. The polymer was prepared by a known method described in JP-A-2008-248137, and polymerized so that the number average molecular weight was 3100 (polytrimethylene ether glycol 1) and 1550 (polytrimethylene ether glycol 2). These obtained polytrimethylene ether glycols showed an endothermic peak of crystallization at −48 ° C. in the melting point measurement by DSC. The crystallization enthalpies were 35 J / g for polytrimethylene ether glycol 1 and polytrimethylene ether glycol, respectively. 2 was 60 J / g. Polytrimethylene ether glycol 1 showed a melting peak at 15 ° C. Polytrimethylene ether glycol 2 exhibited melting peaks at 12 ° C and 17 ° C.

[Preparation of polytrimethylene ether glycol 3]
The polytrimethylene ether glycol 3 used in the following comparative examples was prepared by using 1,3-propanediol having a purity of 95.0% as a raw material, as disclosed in JP-T-2003-517082, JP-T-2005-511834, JP-A-2004-352713, It was prepared by a known method described in Kai 2008-248137 and polymerized so that the number average molecular weight was 1550. The obtained polytrimethylene ether glycol 3 had no melting endothermic peak at -60 ° C to -40 ° C and a melting peak at 8 ° C in the melting point measurement by DSC.

[Example 1]
Polytrimethylene ether glycol 1 (number average molecular weight 3100) and 4,4′-diphenylmethane diisocyanate (MDI) at a molar ratio of 1: 2.20 in a nitrogen stream at 90 ° C. under no solvent for 3 hours Reacted. The residual isocyanate group after the reaction was 2.76% by weight.

  353.28 g of the resulting isocyanate-terminated urethane prepolymer was dissolved in 655.36 g of dimethylacetamide (DMAc), and then 17.43 g of 40 wt% ethylenediamine / DMAc solution and 5.66 g of 15 wt% diethylamine / DMAc solution. A viscous polymer solution was prepared by adding and stirring the mixed chain extender solution at 40 ° C. The solution viscosity of the resulting polymer solution (polyurethane urea concentration: 35% by weight) was measured with a falling ball viscometer and found to be 1900 poise at 40 ° C.

  A DMAc 35% by weight solution of this polymer solution and an addition polymer of divinylbenzene and p-cresol (“METACROL” (registered trademark) 2390 manufactured by DuPont) was added to 98.5% and 1.5% by weight. The mixture was uniformly mixed to obtain a spinning solution.

  Next, this spinning solution was dry-spun by a normal method, taken up by a godet roller, and wound around a normal cardboard tube to produce a 20 dtex monofilament elastic yarn. At this time, the winding speed was 540 m / min, and the speed ratio between the godet roller and the winder was 1.40.

  The obtained polyurethane elastic yarn had a DSC melting point in the range of 120 ° C to 150 ° C. Table 1 shows the enthalpy (J / g) in the range of 120 ° C to 150 ° C. Table 1 shows the heat setting properties (HSE) of the obtained polyurethane elastic yarn.

  Next, from the obtained polyurethane elastic yarn (20 dtex) and nylon filament (24 dtex, 7 filament) manufactured by Toray Industries, Inc., the number of wells on the machine consisting of 85 wt% nylon filament and 15 wt% polyurethane elastic yarn A two-way half tricot having 11 / inch and an on-machine course number of 25 / inch was produced by a normal knitting method to obtain a raw knitted fabric (nylon-based stretch fabric). This raw knitted fabric was tested for heat resistance 1 at the time of dyeing, and the heat resistance at the time of dyeing at the time of adhesion of unsaturated fatty acid and heavy metal was evaluated. Further, the appearance quality was evaluated after dyeing the raw knitted fabric.

  Furthermore, the heat resistance at the time of repeated dyeing of the obtained polyurethane elastic yarn was evaluated by a heat resistance 2 test at the time of dyeing.

The heat resistance during dyeing of nylon stretch fabrics is higher than that of Comparative Example 1 in both heat resistance 1 during dyeing (resistance to unsaturated fatty acids and heavy metals) and heat resistance 2 during dyeing (resistance due to repeated dyeing). Shows significant improvement.
The stretch fabric obtained by dyeing had no defects and was excellent in appearance quality.

[Example 2]
Polytrimethylene ether glycol 1 (number average molecular weight 3100) and 4,4′-diphenylmethane diisocyanate (MDI) at a molar ratio of 1: 2.00 in a nitrogen stream at 90 ° C. under no solvent for 3 hours Reacted. The residual isocyanate group after the reaction was 2.33% by weight.

  348.44 g of the obtained isocyanate-terminated urethane prepolymer was dissolved in 646.48 g of dimethylacetamide (DMAc), and then 14.52 g of 40 wt% ethylenediamine / DMAc solution and 4.71 g of 15 wt% diethylamine / DMAc solution. A viscous polymer solution was prepared by adding and stirring the mixed chain extender solution at 40 ° C. The solution viscosity of the obtained polymer solution (polyurethane urea concentration: 35% by weight) was measured with a falling ball viscometer and found to be 1800 poise at 40 ° C.

  A DMAc 35% by weight solution of this polymer solution and an addition polymer of divinylbenzene and p-cresol (“METACROL” (registered trademark) 2390 manufactured by DuPont) was added to 98.5% and 1.5% by weight. The mixture was uniformly mixed to obtain a spinning solution.

  Next, this spinning solution was dry-spun by a normal method, taken up by a godet roller, and wound around a normal cardboard tube to produce a 20 dtex monofilament elastic yarn. At this time, the winding speed was 540 m / min, and the speed ratio between the godet roller and the winder was 1.40.

  The obtained polyurethane elastic yarn had a DSC melting point in the range of 120 ° C to 150 ° C. Table 1 shows the enthalpy (J / g) in the range of 120 ° C to 150 ° C. Table 1 shows the heat setting properties (HSE) of the obtained polyurethane elastic yarn.

  Next, from the obtained polyurethane elastic yarn (20 dtex) and nylon filament (24 dtex, 7 filament) manufactured by Toray Industries, Inc., the number of wells on the machine consisting of 85 wt% nylon filament and 15 wt% polyurethane elastic yarn A two-way half tricot having 11 / inch and an on-machine course number of 25 / inch was produced by a normal knitting method to obtain a raw knitted fabric (nylon-based stretch fabric). This raw knitted fabric was tested for heat resistance 1 at the time of dyeing, and the heat resistance at the time of dyeing at the time of adhesion of unsaturated fatty acid and heavy metal was evaluated. Further, the appearance quality was evaluated after dyeing the raw knitted fabric.

  Furthermore, the heat resistance at the time of repeated dyeing of the obtained polyurethane elastic yarn was evaluated by a heat resistance 2 test at the time of dyeing.

The heat resistance at the time of dyeing of nylon stretch fabrics is higher than that of Comparative Example 1 in both heat resistance 1 (resistance to unsaturated fatty acids and heavy metals) during dyeing and heat resistance 2 (resistance to repeated dyeing) during dyeing. Shows significant improvement.
The stretch fabric obtained by dyeing had no defects and was excellent in appearance quality.

[Example 3]
Polytrimethylene ether glycol 2 (number average molecular weight 1550) and 4,4′-diphenylmethane diisocyanate (MDI) at a molar ratio of 1: 1.60 in a nitrogen stream at 90 ° C. under no solvent for 3 hours Reacted. The residual isocyanate group after the reaction was 2.59% by weight.

  377.50 g of the resulting isocyanate-terminated urethane prepolymer was dissolved in 700.33 g of dimethylacetamide (DMAc), and then 17.48 g of a 40 wt% ethylenediamine / DMAc solution and 5.67 g of a 15 wt% diethylamine / DMAc solution. A viscous polymer solution was prepared by adding and stirring the mixed chain extender solution at 40 ° C. The solution viscosity of the obtained polymer solution (polyurethane urea concentration: 35% by weight) was measured with a falling ball viscometer and found to be 2100 poise at 40 ° C.

  A DMAc 35% by weight solution of this polymer solution and an addition polymer of divinylbenzene and p-cresol (“METACROL” (registered trademark) 2390 manufactured by DuPont) was added to 98.5% and 1.5% by weight. The mixture was uniformly mixed to obtain a spinning solution.

  Next, the spinning solution was dry-spun by a normal method, taken up by a godet roller, and then wound on a normal cardboard tube to produce a 22 dtex, 2-filament elastic yarn. At this time, the winding speed was 600 m / min, and the speed ratio between the godet roller and the winder was 1.20.

  The obtained polyurethane elastic yarn had a DSC melting point in the range of 120 ° C to 150 ° C. Table 1 shows the enthalpy (J / g) in the range of 120 ° C to 150 ° C. Table 1 shows the heat setting properties (HSE) of the obtained polyurethane elastic yarn.

  Next, on-machine comprising 82% by weight of polyethylene terephthalate filament and 18% by weight of polyurethane elastic yarn from the obtained polyurethane elastic yarn (22 dtex) and polyethylene terephthalate filament (33 dtex, 48 filament) manufactured by Toray Industries, Inc. A two-way half tricot having a number of wells of 13 / inch and an on-machine course number of 30 / inch was produced by a normal knitting method to obtain a raw knitted fabric (polyester stretch fabric). This raw knitted fabric was tested for heat resistance 3 at the time of dyeing, and the heat resistance at the time of dyeing at the time of adhesion of unsaturated fatty acid and heavy metal was evaluated. Further, the appearance quality was evaluated after dyeing the raw knitted fabric.

  Furthermore, the heat resistance at the time of repeated dyeing of the obtained polyurethane elastic yarn was evaluated by a test of heat resistance 4 at the time of dyeing.

  The heat resistance during dyeing of polyester stretch fabrics is significantly greater than that of Comparative Example 2 in both heat resistance 3 (resistance to unsaturated fatty acids and heavy metals) during dyeing and heat resistance 4 (resistance due to repeated dyeing) during dyeing. Showed a significant improvement. Furthermore, the stretch fabric obtained by dyeing had no defects and was excellent in appearance quality.

[Example 4]
Polytrimethylene ether glycol 2 (reacts number average molecular weight 1550 and 4,4′-diphenylmethane diisocyanate (MDI) at a molar ratio of 1: 1.45 in a nitrogen stream at 90 ° C. for 3 hours without solvent. The residual isocyanate group after the reaction was 1.98% by weight.

  370.24 g of the resulting isocyanate-terminated urethane prepolymer was dissolved in 687.03 g of dimethylacetamide (DMAc), and then 13.11 g of 40 wt% ethylenediamine / DMAc solution and 4.25 g of 15 wt% diethylamine / DMAc solution. A viscous polymer solution was prepared by adding and stirring the mixed chain extender solution at 40 ° C. The solution viscosity of the obtained polymer solution (polyurethane urea concentration: 35% by weight) was measured with a falling ball viscometer and found to be 2000 poise at 40 ° C.

  A DMAc 35% by weight solution of this polymer solution and an addition polymer of divinylbenzene and p-cresol (“METACROL” (registered trademark) 2390 manufactured by DuPont) was added to 98.5% and 1.5% by weight. The mixture was uniformly mixed to obtain a spinning solution.

  Next, the spinning solution was dry-spun by a normal method, taken up by a godet roller, and then wound on a normal cardboard tube to produce a 22 dtex, 2-filament elastic yarn. At this time, the winding speed was 600 m / min, and the speed ratio between the godet roller and the winder was 1.20.

  The obtained polyurethane elastic yarn had a DSC melting point in the range of 120 ° C to 150 ° C. Table 1 shows the enthalpy (J / g) in the range of 120 ° C to 150 ° C. Table 1 shows the heat setting properties (HSE) of the obtained polyurethane elastic yarn.

  Next, on-machine comprising 82% by weight of polyethylene terephthalate filament and 18% by weight of polyurethane elastic yarn from the obtained polyurethane elastic yarn (22 dtex) and polyethylene terephthalate filament (33 dtex, 48 filament) manufactured by Toray Industries, Inc. A two-way half tricot having a number of wells of 13 / inch and an on-machine course number of 30 / inch was produced by a normal knitting method to obtain a raw knitted fabric (polyester stretch fabric). This raw knitted fabric was tested for heat resistance 3 at the time of dyeing, and the heat resistance at the time of dyeing at the time of adhesion of unsaturated fatty acid and heavy metal was evaluated. Further, the appearance quality was evaluated after dyeing the raw knitted fabric.

  Furthermore, the heat resistance at the time of repeated dyeing of the obtained polyurethane elastic yarn was evaluated by a test of heat resistance 4 at the time of dyeing.

The heat resistance during dyeing of polyester stretch fabrics is significantly greater than that of Comparative Example 2 in both heat resistance 3 (resistance to unsaturated fatty acids and heavy metals) during dyeing and heat resistance 4 (resistance due to repeated dyeing) during dyeing. Showed a significant improvement. Furthermore, the stretch fabric obtained by dyeing had no defects and was excellent in appearance quality.
[Example 5]
Polytrimethylene ether glycol 2 (number average molecular weight 1550) and PTMG (manufactured by BASF Japan Ltd., number average molecular weight 1800) in a weight ratio of 7: 3 and 4,4′-diphenylmethane diisocyanate (MDI) Were reacted at a molar ratio of 1: 1.60 under a nitrogen stream at 90 ° C. under no solvent for 3 hours. The residual isocyanate group after the reaction was 2.50% by weight.

  374.27 g of the resulting isocyanate-terminated urethane prepolymer was dissolved in 694.36 g of dimethylacetamide (DMAc), and then 16.73 g of 40 wt% ethylenediamine / DMAc solution and 5.43 g of 15 wt% diethylamine / DMAc solution. A viscous polymer solution was prepared by adding and stirring the mixed chain extender solution at 40 ° C. The solution viscosity of the resulting polymer solution (polyurethane urea concentration: 35% by weight) was measured with a falling ball viscometer and found to be 2200 poise at 40 ° C.

  A DMAc 35% by weight solution of this polymer solution and an addition polymer of divinylbenzene and p-cresol (“METACROL” (registered trademark) 2390 manufactured by DuPont) was added to 98.5% and 1.5% by weight. The mixture was uniformly mixed to obtain a spinning solution.

  Next, the spinning solution was dry-spun by a normal method, taken up by a godet roller, and then wound on a normal cardboard tube to produce a 22 dtex, 2-filament elastic yarn. At this time, the winding speed was 600 m / min, and the speed ratio between the godet roller and the winder was 1.20.

  The obtained polyurethane elastic yarn had a DSC melting point in the range of 120 ° C to 150 ° C. Table 1 shows the enthalpy (J / g) in the range of 120 ° C to 150 ° C. Table 1 shows the heat setting property (HSE) of the obtained polyurethane elastic yarn.

  Next, on-machine comprising 82% by weight of polyethylene terephthalate filament and 18% by weight of polyurethane elastic yarn from the obtained polyurethane elastic yarn (22 dtex) and polyethylene terephthalate filament (33 dtex, 48 filament) manufactured by Toray Industries, Inc. A two-way half tricot having a number of wells of 13 / inch and an on-machine course number of 30 / inch was produced by a normal knitting method to obtain a raw knitted fabric (polyester stretch fabric). This raw knitted fabric was tested for heat resistance 3 at the time of dyeing, and the heat resistance at the time of dyeing at the time of adhesion of unsaturated fatty acid and heavy metal was evaluated. Further, the appearance quality was evaluated after dyeing the raw knitted fabric.

  Furthermore, the heat resistance at the time of repeated dyeing of the obtained polyurethane elastic yarn was evaluated by a test of heat resistance 4 at the time of dyeing.

  The heat resistance during dyeing of polyester stretch fabrics is significantly greater than that of Comparative Example 2 in both heat resistance 3 (resistance to unsaturated fatty acids and heavy metals) during dyeing and heat resistance 4 (resistance due to repeated dyeing) during dyeing. Showed a significant improvement. Furthermore, the stretch fabric obtained by dyeing had no defects and was excellent in appearance quality.

[Comparative Example 1]
PTMG (manufactured by BASF Japan Ltd., number average molecular weight 2900) and 4,4′-diphenylmethane diisocyanate (MDI) at a molar ratio of 1: 2.10 under a nitrogen stream at 90 ° C. under no solvent condition. The reaction was performed for 3 hours. The residual isocyanate group after the reaction was 2.70% by weight.

  354.37 g of the resulting isocyanate-terminated urethane prepolymer was dissolved in 657.39 g of dimethylacetamide (DMAc), and then 17.11 g of 40 wt% ethylenediamine / DMAc solution and 5.55 g of 15 wt% diethylamine / DMAc solution. A viscous polymer solution was prepared by adding and stirring the mixed chain extender solution at 40 ° C. The solution viscosity of the obtained polymer solution (polyurethane urea concentration: 35% by weight) was measured with a falling ball viscometer and found to be 1800 poise at 40 ° C.

  A DMAc 35% by weight solution of this polymer solution and an addition polymer of divinylbenzene and p-cresol (“METACROL” (registered trademark) 2390 manufactured by DuPont) was added to 98.5% and 1.5% by weight. The mixture was uniformly mixed to obtain a spinning solution.

  Next, this spinning solution was dry-spun by a normal method, taken up by a godet roller, and wound around a normal cardboard tube to produce a 20 dtex monofilament elastic yarn. At this time, the winding speed was 540 m / min, and the speed ratio between the godet roller and the winder was 1.40.

  The obtained polyurethane elastic yarn did not have a DSC melting point in the range of 120 ° C to 150 ° C. Table 1 shows the enthalpy (J / g) in the range of 120 ° C to 150 ° C. Table 1 shows the heat setting properties (HSE) of the obtained polyurethane elastic yarn.

  Next, from the obtained polyurethane elastic yarn (20 dtex) and nylon filament (24 dtex, 7 filament) manufactured by Toray Industries, Inc., the number of wells on the machine consisting of 85 wt% nylon filament and 15 wt% polyurethane elastic yarn A two-way half tricot having 11 / inch and an on-machine course number of 25 / inch was produced by a normal knitting method to obtain a raw knitted fabric (nylon-based stretch fabric). This raw knitted fabric was tested for heat resistance 1 at the time of dyeing, and the heat resistance at the time of dyeing at the time of adhesion of unsaturated fatty acid and heavy metal was evaluated. Further, the appearance quality was evaluated after dyeing the raw knitted fabric.

Furthermore, the heat resistance at the time of repeated dyeing of the obtained polyurethane elastic yarn was evaluated by a heat resistance 2 test at the time of dyeing.
The result was significantly inferior to Examples 1 and 2.

  Further, when the raw knitted fabric was dyed and the appearance quality was evaluated, 200 or more partial waviness due to polyurethane yarn sag due to various processing histories occurred and was unsatisfactory. .

[Comparative Example 2]
PTMG (manufactured by BASF Japan Ltd., number average molecular weight 1800) and 4,4′-diphenylmethane diisocyanate (MDI) at a molar ratio of 1: 1.6 in a nitrogen stream at 90 ° C. under no solvent condition. The reaction was performed for 3 hours. The residual isocyanate group after the reaction was 2.29% by weight.

  366.74 g of the obtained isocyanate-terminated urethane prepolymer was dissolved in 680.45 g of dimethylacetamide (DMAc), and then 15.02 g of 40 wt% ethylenediamine / DMAc solution and 4.87 g of 15 wt% diethylamine / DMAc solution. A viscous polymer solution was prepared by adding and stirring the mixed chain extender solution at 40 ° C. The solution viscosity of the resulting polymer solution (polyurethane urea concentration: 35% by weight) was measured with a falling ball viscometer and found to be 1900 poise at 40 ° C.

  A DMAc 35% by weight solution of this polymer solution and an addition polymer of divinylbenzene and p-cresol (“METACROL” (registered trademark) 2390 manufactured by DuPont) was added to 98.5% and 1.5% by weight. The mixture was uniformly mixed to obtain a spinning solution.

  Next, the spinning solution was dry-spun by a normal method, taken up by a godet roller, and then wound on a normal cardboard tube to produce a 22 dtex, 2-filament elastic yarn. At this time, the winding speed was 600 m / min, and the speed ratio between the godet roller and the winder was 1.20.

  The obtained polyurethane elastic yarn did not have a DSC melting point in the range of 120 ° C to 150 ° C. Table 1 shows the enthalpy (J / g) in the range of 120 to 150 ° C. Table 1 shows the heat setting properties (HSE) of the obtained polyurethane elastic yarn.

  Next, on-machine comprising 82% by weight of polyethylene terephthalate filament and 18% by weight of polyurethane elastic yarn from the obtained polyurethane elastic yarn (22 dtex) and polyethylene terephthalate filament (33 dtex, 48 filament) manufactured by Toray Industries, Inc. A two-way half tricot having a number of wells of 13 / inch and an on-machine course number of 30 / inch was produced by a normal knitting method to obtain a raw knitted fabric (polyester stretch fabric). This raw knitted fabric was tested for heat resistance 3 at the time of dyeing, and the heat resistance at the time of dyeing at the time of adhesion of unsaturated fatty acid and heavy metal was evaluated. Further, the appearance quality was evaluated after dyeing the raw knitted fabric.

  Furthermore, the heat resistance at the time of repeated dyeing of the obtained polyurethane elastic yarn was evaluated by a test of heat resistance 4 at the time of dyeing.

  The result was significantly inferior compared to Examples 3 and 4.

  Further, when the raw knitted fabric was dyed and the appearance quality was evaluated, 66 portions of waving caused by polyurethane yarn sag due to various processing histories occurred per 20 m, which was unsatisfactory.

[Comparative Example 3]
Polytrimethylene ether glycol 3 (number average molecular weight 1550) and 4,4′-diphenylmethane diisocyanate (MDI) at a molar ratio of 1: 1.60 in a nitrogen stream at 90 ° C. under no solvent for 3 hours Reacted. The residual isocyanate group after the reaction was 2.59% by weight.

  377.50 g of the resulting isocyanate-terminated urethane prepolymer was dissolved in 700.33 g of dimethylacetamide (DMAc), and then 17.48 g of a 40 wt% ethylenediamine / DMAc solution and 5.67 g of a 15 wt% diethylamine / DMAc solution. A viscous polymer solution was prepared by adding and stirring the mixed chain extender solution at 40 ° C. The solution viscosity of the obtained polymer solution (polyurethane urea concentration: 35% by weight) was measured with a falling ball viscometer and found to be 2100 poise at 40 ° C.

  A DMAc 35% by weight solution of this polymer solution and an addition polymer of divinylbenzene and p-cresol (“METACROL” (registered trademark) 2390 manufactured by DuPont) was added to 98.5% and 1.5% by weight. The mixture was uniformly mixed to obtain a spinning solution.

  Next, the spinning solution was dry-spun by a normal method, taken up by a godet roller, and then wound on a normal cardboard tube to produce a 22 dtex, 2-filament elastic yarn. At this time, the winding speed was 600 m / min, and the speed ratio between the godet roller and the winder was 1.20.

  The obtained polyurethane elastic yarn did not have a DSC melting point in the range of 120 ° C to 150 ° C. Table 1 shows the enthalpy (J / g) in the range of 120 ° C to 150 ° C. Table 1 shows the heat setting properties (HSE) of the obtained polyurethane elastic yarn.

  Next, on-machine comprising 82% by weight of polyethylene terephthalate filament and 18% by weight of polyurethane elastic yarn from the obtained polyurethane elastic yarn (22 dtex) and polyethylene terephthalate filament (33 dtex, 48 filament) manufactured by Toray Industries, Inc. A two-way half tricot having a number of wells of 13 / inch and an on-machine course number of 30 / inch was produced by a normal knitting method to obtain a raw knitted fabric (polyester stretch fabric). This raw knitted fabric was tested for heat resistance 3 at the time of dyeing, and the heat resistance at the time of dyeing at the time of adhesion of unsaturated fatty acid and heavy metal was evaluated. Further, the appearance quality was evaluated after dyeing the raw knitted fabric.

  Furthermore, the heat resistance at the time of repeated dyeing of the obtained polyurethane elastic yarn was evaluated by a test of heat resistance 4 at the time of dyeing.

  The result was significantly inferior compared to Examples 3 and 4.

  Further, when the raw knitted fabric was dyed and the appearance quality was evaluated, 66 portions of waving caused by polyurethane yarn sag due to various processing histories occurred per 20 m, which was unsatisfactory.

  The elastic fabric according to the present invention can exhibit excellent heat resistance (particularly heat aging resistance) even when unsaturated fatty acids or heavy metals adhere to the yarn when dyeing at high temperature, and is manufactured using this elastic fabric. Apparel and the like have excellent detachability, fit, wearing feeling, dyeing color, discoloration resistance, appearance quality and the like.

  Specific applications that can be used include socks, stockings, circular knitting, tricots, swimwear, ski trousers, work clothes, smoke fire clothes, golf trousers, wet suits, bras, girdles, gloves, various textile products, and fastening materials. In addition, there are examples of fastening materials for preventing leakage of sanitary products such as paper diapers, fastening materials for waterproofing materials, imitating baits, artificial flowers, electrical insulation materials, wiping cloths, copy cleaners, gaskets, and the like.

Claims (11)

  An elastic fabric comprising a polyurethane elastic yarn polymerized from polytrimethylene ether glycol having a crystallization point, a diisocyanate, and a diamine chain extender.   The elastic fabric according to claim 1, wherein the polytrimethylene ether glycol has a crystallization energy of 10 J / g or more.   The elastic fabric according to claim 1 or 2, wherein the polytrimethylene ether glycol has a crystallization temperature of -60 to -40 ° C.   The polyurethane elastic yarn has a DSC melting point in a range of 120 ° C to 150 ° C, and an enthalpy in a range of 120 ° C to 150 ° C is 5.5 J / g or more. Elastic fabric.   The elastic fabric according to any one of claims 1 to 4, wherein the polyurethane elastic yarn has a heat setting efficiency HSE of 25 or more.   The elastic fabric according to any one of claims 1 to 5, wherein the polyurethane elastic yarn has a resistance to repetitive dyeing at 130 ° C of 65% or more.   The elastic fabric according to any one of claims 1 to 6, wherein the polytrimethylene ether glycol has a hydroxyl value of 25 to 120.   The elastic fabric according to any one of claims 1 to 7, wherein a reaction equivalent ratio (molar ratio) between the polytrimethylene ether glycol and the diisocyanate is 1: 1 to 1: 5.   The elastic fabric according to any one of claims 1 to 8, wherein the polyurethane elastic yarn has a terminal group concentration derived from a diamine compound of 5 to 50 meq / kg.   The elastic fabric according to any one of claims 1 to 9, wherein the polyurethane elastic yarn is polymerized by a prepolymer method.   The elastic fabric according to any one of claims 1 to 10, wherein the polyurethane elastic yarn is spun by a dry method.