JPS63219620A - Production of polyurethane elastomeric fiber - Google Patents

Abstract

PURPOSE:To obtain the titled elastomeric fiber outstanding in dyeability and chemical resistance, free from fiber breakage in the cold winter season, by reaction in an organic polar solvent between a specific linear hydroxyl compound component, an excess of organic diisocyanate and chain extender having two active hydrogen groups followed by spinning. CONSTITUTION:A polymer solution prepared by reaction in an organic polar solvent between (I) a linear polyhydroxyl compound component having hydroxyl groups at the both ends made up of a mixture of (A) a component carrying hydroxyl groups at the both ends derived from (i) isophthalic acid and (ii) at least one kind of glycol selected from polytetramethylene ether glycol, 1,6- hexanediol and polypropylene ether glycol, and (B) polytetramethylene ether glycol (PTMEG), (II) an excess of organic diisocyanate and (III) a chain extender having two active hydrogen groups is brought to spinning to obtain the objective fiber.

Description

[Detailed description of the invention]

[Industrial Application Field 1] The present invention relates to a method for producing polyurethane elastic fibers containing a specific linear polyhydroxy compound and polytetramethylene ether glycol as the 41-acid components. By improving the elastic properties at low temperatures, which are disadvantageous, without impairing the excellent mechanical strength and hydrolysis resistance of polyurethane elastic 4I fibers containing glycol as a constituent component, it can be used in the winter and cold seasons. Polyurethane elasticity in 41! The present invention relates to a method for producing polyurethane elastic fibers that reduces yarn breakage during use of fiberglass and improves productivity. [Prior Art] Conventionally, a prepolymer is synthesized from a linear polyhydroxy compound having hydroxyl groups as both end groups and an excess of a specific diisocyanate, and a prepolymer is synthesized in a polar organic solvent to form a prepolymer of substantially 21 [! ]
A substantially linear small aggregate consisting of a soft segment and a hard segment that has been formed by reacting with a chain extender having an active hydrogen group is spun by a dry or wet spinning method to form a polyurethane elastic fiber. It is well known to obtain. The polyurethane elastic fiber thus obtained can be made into core yarn or twisted yarn, or can be finished into elastic products through a warping process, but the polyurethane elastic fiber cannot be used during the winter and cold seasons. When the room temperature in the workplace where products are manufactured drops to about 5°C, polyurethane elastic fibers often break at the start of work even if heating is started. The reason for this is that many of the polyurethane elastic fibers obtained by conventional methods exhibit a phenomenon in which the elastic recovery rate is significantly reduced at low temperatures. In particular, the soft segment
Polyurethane elastic fibers made of polytetramethylene ether glycol have excellent mechanical strength and elastic recovery, as well as good hydrolysis and chemical resistance, and are characterized by high elongation, but elastic recovery is poor at low temperatures. It has the fatal drawback of significantly decreasing the Until now, as a method to improve this drawback, it has been proposed to mix polypropylene ether glycol with Japanese Patent Publication No. 40-12389, and Japanese Patent Publication No. 46-22101 and Japanese Patent Publication No. 49-37438.
Mixing polylactone with the number, and Special Publication No. 47-1
No. 5710 and Japanese Patent Publication No. 48-15206q disclose a method of mixing polyester glycol. However, although the method of mixing polypropylene ether glycol improves the elastic recovery properties at low temperatures, in addition to lowering mechanical strength, polypropylene ether glycol easily absorbs moisture, so the prepolymer tends to foam, resulting in a constant quality. The method of mixing polylactone has disadvantages such as difficulty in obtaining polyurethane elastic fibers, and although the elastic recovery properties at low temperatures are improved, it is difficult to obtain polyurethane elastic ljA fibers consisting only of Volite 1 to ramethylene ether glycol as the polyol component. It has the disadvantage that chemical resistance, especially hydrolysis resistance, is significantly lower than that of . Also, the method of mixing polyester glycol significantly improves the elastic recovery at low temperatures, but the polyurethane elasticity obtained from only polytetramethylene ether glycol as the polyol component! Compared to fibers, it has the drawbacks of insufficient chemical resistance, especially hydrolysis resistance, and low mechanical strength. In any of the above methods, even if an attempt is made to better improve the elastic recovery properties at low temperatures, there are drawbacks such as a decrease in mechanical strength or a decrease in hydrolysis resistance, resulting in unsatisfactory polyurethane elasticity. A fiber was not obtained. Problems to be Solved by the Invention The present invention aims to improve the mechanical strength and hydrolysis resistance of polyurethane elastic fibers containing polytetramethylene ether glycol as a main component as a linear polyhydroxy compound having hydroxyl groups at both ends. The purpose is to improve elastic recovery at low temperatures without degrading the elasticity, and to reduce the number of yarn breakages during the winter and cold seasons. Means for Solving Problem K] As a result of intensive research to solve the above problems, the present inventors have found that
This has led to the present invention. That is, the present invention provides a polymer obtained by reacting a linear polyhydroxy compound having hydroxyl groups at both ends with an excess of organic diisocyanate-1 and a chain extender having substantially two active hydrogen groups. In the method for obtaining polyurethane elastic fibers from a solution, a compound having hydroxyl groups at both ends and consisting of isophthalic acid and glycols represented by the following general formula (A) is used as the linear polyhydroxy compound, and polytetramethylene ether glycol is used as the linear polyhydroxy compound. This is a method for producing polyurethane elastic fibers having a substantially linear structure, which comprises mixing and using a polyurethane elastic fiber with a substantially linear structure. However, m is a positive number, and G represents a group obtained by removing the hydroxyl groups at both ends of the glycol. The glycol of the compound represented by the general formula (A) is polytetramethylene ether glycol. 1,6-hexanediol, polypropylene ether glycol, or a mixture of two or more thereof. In addition, when polypropylene ether glycol is used as the glycol, if the polypropylene ether glycol exceeds 70% (weight ff1) of the glycol, there will be no change in the low temperature properties, but the mechanical strength of the polyurethane elastic S fiber will decrease. shows a tendency to decrease, and when 1,6-hexanediol is used, if 1,6-hexanediol exceeds 50% (weight) of the glycols, the compound represented by the general formula (A) This is undesirable as it produces undissolved components at 60°C, causing problems in liquid feeding, etc. The compound represented by the general formula (A) having hydroxyl groups at both ends used in the present invention has a number average molecular weight of 200 to 2,500, preferably 300 to 1,500. Then, isophthalic acid dimethyl ester is added and a transesterification reaction is performed to obtain a compound having hydroxyl groups at both ends. The number average molecular weight of the compound is 500 to 5000,
Preferably it is 1000-3500. The present invention

[Among the linear polyhydroxy compounds, the mixing ratio of the compound represented by general formula (A) and polytetramethylene ether glycol is 1:99 to 80:20.
(Weight ratio) Preferably it is 5:95 to 70:30 (weight ratio). As a specific method for obtaining the polyurethane elastic fiber of the present invention, the compound (A) having hydroxyl groups at both ends obtained by the above method and polytetramethylene ether glycol may be mixed together or separately in an excess molar amount. A diisocyanate, preferably 1.7 mol or more of organic diisocyanate-1. is reacted with 1 mol of hydroxyl group to obtain a prepolymer having an isocyanate group at the terminal. A small amount of low molecular weight glycol or water can be added to the prepolymer prepared in this manner during or after synthesis of the prepolymer to cause the reaction to occur. This prepolymer is (1) extended with a chain extender having substantially two active hydrogen atoms. The general formula used in the present invention has water Fi groups at both ends (
The compound represented by A) and polytetramethylene ether glycol may be mixed together in the following manner to form a polyurethane polymer. (1) After mixing both polyhydroxy compounds, a prepolymer is synthesized, and the polymer is quenched using a chain extender. (2) Prepolymers of both polyhydroxy compounds are synthesized separately, mixed and then added during polymerization, or each prepolymer is added simultaneously during polymerization to obtain a polymer. (3) After synthesizing a prepolymer using both polyhydroxy compounds separately and polymerizing each with a chain extender,
Mix both types of union. The polymer can also be obtained by completing the polymerization using various other methods. In such a method, the polar solvent may be present from the beginning of the polymer or may be added during the polymerization process, but it must be substantially inert to various reactants; for example, dimethylformamide, dimethyl Acetamide, dimethyl sulfoxide and the like are preferred. The polymer solution thus obtained is passed through a spinneret into a coagulation bath, such as water, a water-dimethylformamide mixed bath, a water-dimethylacetamide mixed bath,
Polyurethane elastic fibers are obtained by spinning in a bath of ethylene glycol or the like or dry spinning in a hot air stream at about 170 to 350°C through a spinneret. Examples of the organic diisocyanate used in the present invention include 4,4'-diphenylmethane diisocyanate, 3,3'-dichloro-4,4'-diphenylmethane diisocyanate, m-xylylene diisocyanate, 2.4-1-lylene diisocyanate, 2.6- One type or a combination of two or more types of tolylene diisocyanate and the like can be mentioned. Further, as the chain extender having substantially two active hydrogen groups used in the present invention, ethylenediamine, 1,2-
Propylene diamine, m-xylylene diamine, p-xylylene diamine, cyclohexylene diamine, 1-lylene diamine, piperazine, ethylene glycol, 1
．． Examples include one or a combination of two or more of 4-butanediol and the like. The polyurethane elastic 41i fiber according to the present invention contains therein a light stabilizer, an ultraviolet absorber, a gas discoloration inhibitor, and a dye. It may contain pigments, activators, matting agents, etc. as appropriate. K Examples] Examples are shown below, where all parts indicate small hanging parts, strength and elongation are the strength (duram/denier) and elongation (%) of the fiber at break, and the 300χ modulus is , 300%
This is the tensile strength (grams/denier) of 41 when stretched. Further, the elastic recovery rate was determined using the following formula under the conditions of 20° C. and 65% relative humidity. Elastic recovery rate (%) = λ1/λo x 100 However, l
: Fiber length 40111#I at a speed of 1000%/min 30
Fiber length when elongated to 0% (α)i: 4fi fiber length 40 uttn is elongated to 300% at a speed of 1000%/min, immediately returned at circumferential speed, and the fiber length when the stress becomes 0 ( α) Low-temperature properties are expressed as elastic recovery rate (%) at 5°C. Hydrolysis resistance was determined by immersing the sample in 2% and 5% concentration caustic soda solutions and heat-treating at 100°C for 60 minutes (bath ratio 50:1), then comparing the strength of the sample taken out from the bath with that of the untreated sample. It is expressed as a ratio (%) to the strength. Example 1 914 parts of dimethyl isophthalate was added with a number average molecular weight of 845.
polytetramethylene ether glycol (hereinafter referred to as P
Add 1019 parts of THEG (845), 683 parts of 1,6-hexanediol, and 0.9 parts of zinc acetate, heat at 195°C for 8 hours under nitrogen flow and normal pressure to remove generated methanol, and , under reduced pressure at 280°C (13 sll (
+) A transesterification reaction was carried out by heating for 9 hours to produce polyether ester glycol (with a number average molecular weight of 11930).
A compound (hereinafter referred to as compound (A-1)) was obtained. To 120 parts of the compound (A-1), number average molecule fi 19
70 polytetramethylene ether glycol (hereinafter referred to as
PTHEG (1970)) 120 copies; 4.
Add 55.4 parts of 4'-diphenylmethane diisocyanate to a reaction vessel and react at 80°C for 60 minutes with stirring.
A prepolymer was prepared. Separately, dimethylformamide (hereinafter referred to as DHF) 68
5 parts, 0.54 parts of 1,2-propylenediamine, 3.96 parts of ethylenediamine, and 0.5 parts of jetanolamine.
31 parts were added thereto, and while stirring, the prepolymer was gradually added dropwise while diluting the prepolymer to 60% with OMF to obtain a uniform viscous polymer solution of 1200 voices. The polymer solution obtained in this way was extruded into water through a spinneret with six holes having a diameter of 0.10 sφ, and
It was passed through a heat treatment machine at 45° C. and wound up at a speed of 150 Tl/1 lin to obtain a 40 d polyurethane elastic thread (experiment number 1-1). The physical properties are shown in Table 1. Similarly, the above compound (A-1) and PT)4EG(
(1970) by changing the mixing ratio, and the physical properties are shown in Table 1 as Experiment No. 1-2.The mixing ratio was further changed to compare the low-temperature properties of each polyurethane yarn at 5°C. The elastic recovery rate of the elastic yarn was measured, and its change is shown in Figure 1. In addition, for comparison of hydrolysis resistance, the strength retention rate of each polyurethane elastic yarn when treated with 5% NaOH was measured. The changes are shown graphically in Figure 2. In this example, compared to the case of Comparative Example 1 below in which PTMEG (1970) alone was used as the linear polyhydroxy compound, the low-temperature characteristics were significantly improved by using compound (A-1) in combination. Moreover, the hydrolysis resistance is the same as that of PT14EG 41. The results were good, and no decrease in mechanical strength was observed. Example 2 PTHEG (845 parts) was added to 238 parts of dimethyl isophthalate.
), 0.24 part of zinc acetate was added, and the generated methanol was removed by heating at 195°C for 3 hours under normal pressure in a nitrogen stream, and further heated at 280°C under reduced pressure (13 mInHg) 1
By heating for 6 hours, a polyether ester glycol with a number average molecular ffi of 1980 (hereinafter referred to as compound (A-2)
) is a helmet. To 120 parts of the compound (A-2), PT
Add 120 parts of HEG (1970) and 54.7 parts of 484゛-diphenylmethane diisocyanate to the reaction vessel,
A prepolymer was produced by reacting at 80° C. for 60 minutes with stirring. Separately, 0.54 parts of 1,2-propylenediamine, 3.96 parts of ethylenediamine, and 0.15 parts of jetanolamine were added to 793 parts of DHF, and while stirring, the prepolymer was diluted to 60% with DHF. While gradually dripping,
A uniform viscous polymer solution of 500 voids was poured into the armpit. The thus obtained polymer solution was extruded into water through a spinneret having 6 holes with a diameter of 0.10 mm, and
It was passed through a heat treatment machine at 5°C and wound at a speed of 150n+/min to obtain a 40d polyurethane elastic yarn (Experiment No. 2).
-1). The physical properties are shown in Table 1. Similarly, the above compound (A-2) and PTHEG (1
Polyurethane elastic threads were prepared by changing the mixing ratio of 970) and their physical properties are shown in Table 1 as Experiment No. 2-2. Hydrolyzability was measured and shown in FIGS. 1 and 2. In this example, compared to the case of Comparative Example 1 below in which PT14EG (1970) alone was used as the linear polyhuman Oxy compound, the low temperature properties were significantly improved by using compound fA-2) in combination. Furthermore, the hydrolysis resistance was equivalent to that using PTHEG alone, and no decrease in mechanical strength was observed. Example 3 PTHEG (84 parts) was added to 420 parts of dimethyl isophthalate.
5) Add 883 parts of polypropylene ether glycol with a number average molecular weight of 425 and 0.41 parts of zinc acetate, heat at 195°C for 3 hours in a nitrogen stream under normal pressure to remove the generated methanol, and further add 280 parts of polypropylene ether glycol with a number average molecular weight of 425. °C under reduced pressure (1
0utl! II) By heating for 16 hours, a polyether ester glycol (hereinafter referred to as compound (A-3)) having a number average molecular weight of 1930 was obtained. PTHEG (19 parts) was added to 120 parts of the compound (A-3).
70) Add 120 parts and 1-55.4 parts of 4.4'-diphenylmethane diisocyanate to a reaction vessel, and heat at 80°C for 60 minutes.
A prepolymer was produced by reacting with stirring for a minute. Next, 0.54 parts of 1,2-propylenediamine, 3.96 parts of ethylenediamine, and 0.15 parts of jetanolamine were added to 793 parts of DHF, and the prepolymer was diluted to 60% with DHF while stirring. The mixture was gradually added dropwise to obtain a uniform viscous polymer solution with 560 voids. The polymer solution obtained in this way was
The hole diameter is 61 holes! ! ] extruded into water from a spinneret with
Experiment No. 3-1). The physical properties are shown in Table 1. Similarly, the above compound (A-3) and PTHEG (1
Polyurethane elastic yarns were prepared by changing the mixing ratio of 970), and their physical properties are shown in Table 1 as Experiment No. 3-2. Furthermore, by changing the mixing ratio, their low-temperature properties and Hydrolysis resistance was measured and shown in FIGS. 1 and 2. In this example, compared to the case of Comparative Example 1 below in which PTHEG (1970) alone was used as the linear polyhydroxy compound, the combination use of compound (A-3) only improved the low-temperature properties. However, the hydrolysis resistance was also good like PTHEG, and the mechanical strength was also good. Example 4 PTHEG (8 parts) was added to 1059 parts of dimethyl isophthalate.
45) 569 parts, 763 parts of 1,6-hexanediol,
Polypropylene ether glycol with a number average molecular weight of 425. 286 parts and 1.05 parts of zinc acetate were added, and in a nitrogen stream,
The produced methanol was removed by heating at 195°C for 8 hours under normal pressure, and then heated at 280°C under reduced pressure (11 MHU) for 14 hours to form a polyether ester glycol with a number average molecular fi of 1980 (hereinafter referred to as compound (A- 4) was obtained. To 72 parts of the compound (A-4), PT1
4EG (1970) and 54.7 parts of 4,4'-diphenylmethane diisocyanate were added to the reaction vessel.
A prepolymer was produced by reacting at 80° C. for 60 minutes with stirring. Separately, 0.54 parts of 1,2-propylenediamine, 3.96 parts of ethylenediamine, and 0.15 parts of jetanolamine were added to 793 parts of DHF, and the prepolymer was diluted to 60% with DHF while stirring. While gradually dripping,
A uniform viscous polymer solution with 480 voids was obtained. The polymer solution thus obtained was extruded into water through a spinneret having 6 holes with a diameter of 0.10 m + φ.
It was passed through a heat treatment machine at 45°C and wound up at a speed of 1501 parts min to obtain a 40 d polyurethane elastic yarn (Experiment No. 4-1). This physical property is shown first. In this example, compared to the case of Comparative Example 1 below in which PTHEG (1970) alone was used as the linear polyhydroxy compound, the low-temperature characteristics were improved by using compound (A-4) in combination. Moreover, the hydrolysis resistance was as good as that of PTHEG, and almost no decrease in mechanical strength was observed. Example 5 935 parts of 1.6-hexanediol, 561 parts of polypropylene ether glycol having a number average molecular weight of 425, and 1.27 parts of zinc acetate were added to 1283 parts of dimethyl isophthalate, and the mixture was heated to 8.5 parts at 197°C under normal pressure in a nitrogen stream. After removing the generated methanol by heating for an hour, the temperature was further heated to 280℃ under reduced pressure for <13 hours.
A transesterification reaction was carried out by heating at mH(]) 114 hours to obtain a polyether ester glycol having a number average molecular weight of 11940 (hereinafter referred to as compound (A-5')). PTHEG (1970
) and 55.1 parts of 4,4°-diphenylmethane diisocyanate were added to a reaction vessel and reacted at 80° C. for 60 minutes with stirring to produce a prepolymer. Next, 0.54 parts of 1,2-propylenediamine, 3.96 parts of ethylenediamine, and 0.10 parts of jetanolamine were added to 793 parts of DHF, and the prepolymer was diluted to 60% with DI4F while stirring. The mixture was gradually added dropwise to obtain a uniform viscous polymer solution with 530 voids. The polymer solution thus obtained was made into a diameter of 0.10II #I
It was extruded into water through a spinneret having 6 holes with a hole diameter of φ, passed through a heat treatment machine at 245° C., and wound at a speed of 150 n/iin to obtain a polyurethane elastic yarn of 40 d (Experiment No. 5-1). The physical properties are shown in Table 1. In this example, compared to the case of Comparative Example 1 below in which PTHEG (1970) alone was used as the linear polyhydroxy compound, the low-temperature characteristics were only improved by using compound (A-5) in combination. However, the hydrolysis resistance was also good like PTHEG, and the mechanical strength was also good. Example 6 578 parts of dimethyl isophthalate was added with a number average molecular weight of 425.
1813 parts of polypropylene ether glycol. Add 0.57 parts of zinc acetate, and under normal pressure in a nitrogen stream. The generated methanol was removed by heating at 195°C for 3 hours, and further heated at 280°C under reduced pressure (10MH(+) for 20 hours to form a polyether ester glycol with an acid average molecular weight of 11970 (hereinafter referred to as compound (A-6)). ) was obtained. To 48 parts of the compound (A-6), PTHEG (1970
) and 54.8 parts of 4゜4゛-diphenylmethane diisocyanate were added to a reaction vessel, and the mixture was heated at 80°C for 60 minutes.
A prepolymer was produced by vertically reacting Wll. Separately, 0.54 parts of 1,2-propylenediamine, 3.96 parts of ethylenediamine, and 0.31 parts of jetanolamine were added to 793 parts of DHF, and while stirring, the prepolymer was diluted to 60% with DHF. , was gradually added dropwise to obtain a uniform viscous polymer solution with 460 voids. The polymer solution thus obtained was heated to a diameter of 0.10 m#lφ.
extruded into water from a spinneret with a pore size of 6 holes,
It was passed through a heat treatment machine at 241° C. and wound at a speed of 150 n/n+in to obtain a 40 d polyurethane elastic yarn (experiment number @ ei). The physical properties are shown in Table 1. In this example, compared to the case of Comparative Example 1 below in which PTHEG (1970) 10 was used as the linear polyhydroxy compound, the strength of mechanical properties was improved by using compound (A-6) in combination. is slightly lowered, but the low-temperature properties are significantly improved, and the hydrolysis resistance is lower than that of PTH.
It was found that it was equivalent to that using EG alone. Reference Example 1,354 parts of 1,6-hexanediol and 1.6 parts of zinc acetate were added to 1,599 parts of dimethyl isophthalate, and the resulting methanol was removed by heating at 195°C for 8 hours under normal pressure in a nitrogen stream. ℃ under reduced pressure (10 mmH (+>
By heating for 10 hours, a polyester glycol having a number average molecular weight of 1930 (hereinafter referred to as compound (A-7)) was obtained. This compound (A-7) has a high melting point of about 80° C., which is too high for a polyol component for polyurethane elastic fibers, so it could not be used, so it was used in Experiment No. 7-1 in Table 1). Comparative Example 1 240 parts of PTHEG (1970) and 54.8 parts of 4,4°-diphenylmethane diisocyanate were added to a reaction vessel and reacted at 80°C for 60 minutes with stirring to produce a prepolymer. Polyurethane elastic yarn was obtained from a uniform viscous polymer solution with 530 voids by the same polymerization operation as in Example 2.
Experiment number 8-1). The physical properties are shown in Table 1. Compared to Comparative Example 1, which uses only PTHEG, the polyurethane elastic yarns prepared by Examples 1 to 6 according to the present invention not only have significantly improved low-temperature properties, but also have excellent hydrolysis resistance. The properties were also good. Comparative Example 2 PTHEG (1970) 168 parts to polypropylene ether glycol 72 with a number average molecular weight of 1980
54.7 parts of 4,4'-diphenylmethane diisocyanate was added to the reaction vessel, and the mixture was heated at 80°C for 60 minutes.
A prepolymer was produced by reacting for a minute with stirring. Hereinafter, a polyurethane elastic thread was obtained from a uniform viscous polymer solution of 480 poise by the same polymerization operation as in Example 2 (
Experiment number 8-2). The physical properties are shown in Table 1. A polyurethane elastic thread using a mixture of PTHEG and polypropylene ether glycol has improved low-temperature properties, but has the drawback of reduced mechanical strength. Comparative Example 3 Number average molecule f for 120 parts of PTHEG (1970)
i 2010 poly-ε-caprolactone glycol 1
20 parts of 4,4-diphenylmethane diisocyanate was added to the reaction vessel, and the mixture was heated at 80°C.
for 60 minutes. The mixture was reacted with stirring to produce a prepolymer. Thereafter, a polyurethane elastic thread was obtained from a uniform viscous polymer solution of 510 voids by the same polymerization operation as in Example 2 (Experiment No. 8-3). The physical properties are shown in Table 1. A polyurethane elastic yarn using poly-ε-caprolactone glycol as PTHEG had good low-temperature properties, but extremely poor alkali resistance. Comparative Example 4 2.2-dimethylpropane-1,3-diol and 1,
Polyester glycol 160 with number average molecular fi 1530 made by combining 11 q of mixed diol with 6-hexane diol at a mixing ratio of 30:70 and adipic acid.
and 160 parts of PTHEG (hereinafter referred to as PTHEG (1510)) having a number average molecule of fj11510 were mixed, 102.6 parts of 4.4'-diphenylmethane diisocyanate was added to the reaction vessel, and the mixture was heated at 80°C for 60 minutes. The mixture was reacted with stirring to produce a prepolymer. Separately, 0.66 parts of 1,2-propylenediamine, 4.84 parts of ethylenediamine, and 0.19 parts of jetanolamine were added to 803 parts of DI4F, and while stirring, the prepolymer was diluted to 60% with DI4F. It was gradually added dropwise to obtain a uniform viscous polymer solution with 250 voids. The thus obtained polymer solution was spun in the same manner as in Example 2 to obtain a polyurethane elastic thread (Experiment No. 8-4). The physical properties are shown in Table 1. This polyurethane elastic yarn has good low-temperature properties, but
Although the alkali resistance was better than that of the polyurethane elastic yarn of Comparative Example 3 (Experiment No. 8-3), it was significantly inferior compared to the polyurethane elastic yarn of Examples 1 to 6 based on the present invention. . Below is a blank space Example 7 240 parts of the compound (A-1) prepared in Example 1 was dissolved by heating, and 1-55.1 part of 4.4'-diphenylmethane diisocyanate was added to the reaction vessel. , 60 minutes at 90°C. A prepolymer is produced by reacting with stirring, and DH is added to this prepolymer.
126 parts of F was added to obtain a diluted prepolymer (hereinafter referred to as
A-1 (D-PP)). Also, PT14EG (19
70) Add 54.8 parts of 4,4°-diphenylmethane diisocyanate to 240 parts, and heat at 80°C for 60 minutes.
The reaction was carried out under stirring for 1 minute to prepare a prepolymer, and 126 parts of DHF was added to this to obtain a diluted prepolymer (
Hereinafter referred to as PTHEG (D-PP)). Separately, 0.54 parts of 1,2-propylenediamine, 0.31 parts of jetanolamine, and 3.96 parts of ethylenediamine were added to 848 parts of DHF, and A-1 (D-
PP) and PTHEG (CI-PP) were gradually added dropwise at a ratio of 3 to obtain a uniform viscous polymer solution with 510 voids. The thus obtained polymer solution was extruded into water through a spinneret having 6 holes with a diameter of 0.10 maφ, and
It was passed through a heat treatment machine at 5° C. and wound at a speed of 15011/l1 inch to obtain a 40 d polyurethane elastic yarn (Experiment No. 9). The physical properties are shown in Table 2. Compared to experiment number 1-2, in which a prepolymer was synthesized by mixing compound (A-1) and PTMEG (1970),
Respective prepolymers of compound (A-1) and PTMEG (1970). In this example (Experiment No. 9), which synthesized - and used a mixture of them during polymerization, the same excellent low-temperature properties and hydrolysis resistance were obtained. Similarly, in place of compound (A-1), (A-2) to
Experiment Nos. 10, 11, 12, 13, and 14) were used to synthesize and polymerize a prepolymer using (A-6), and to obtain polyurethane elastic threads from the polymer solution. These physical properties are also shown in Table 2. Compared to polyurethane elastic yarns obtained by mixing compounds (A-2) to (A-6) and synthesizing prepolymers, they have almost the same excellent low-temperature properties, hydrolysis resistance, and It showed mechanical strength. Note to Table 2) P, G (D-PP) is a polyol (P, G
) shows the diluted prepolymer obtained from Example 8 240 parts of the compound (A-1) obtained in Example 1 was dissolved by heating, 55.1 parts of 4,4°-diphenylmethane diisocyanate was added to the reaction vessel, and the mixture was heated at 90°C for 60 minutes. The mixture was reacted with stirring to produce a prepolymer. Next, 0.54 parts of 1,2-propylenediamine, 3.96 parts of ethylenediamine, and 0.15 parts of jetanolamine were added to 793 parts of DHF, and the prepolymer was diluted to 60% with DHF while stirring. A uniform viscous polymer solution with 550 voids was obtained (hereinafter referred to as
Separately, under the conditions shown in Comparative Example 1, a uniform and viscous polymer solution with 540 voids containing PTHEG alone as a polyol component was obtained (hereinafter referred to as PTHEG(P)). ). The thus treated polymer solution ^-1 (P) and PTHEG
(P) was warmed and stirred at a ratio of 3 nia to make a homogeneous solution,
It was extruded into water from a spinneret with 6 holes with a diameter of 0.10a + φ, passed through a heat treatment machine at 245 ° C.
The yarn was wound at a speed of 1/iin to obtain a 40 d polyurethane elastic yarn (Experiment No. 15). Hereinafter, instead of A-1, A-2, ^-3. ^
-4. Table 3 shows the physical properties of the polyurethane elastic yarn (experiment number IG, 17.18.19.20) obtained using 8-5 and A-6. The polyurethane elastic yarn obtained by mixing the polymer solution obtained from PTI4EG is
Polyurethane elastic threads were prepared by mixing compound (A) and PTHEG to synthesize a prepolymer (Examples 1 to 6).
(described in 1999), both exhibited nearly identical excellent low-temperature properties, hydrolysis resistance, and mechanical strength. Notes in Table 3 below) P, G (P) indicates a polyurethane polymer solution obtained from the polyol (P, G).

【Effect of the invention】

The polyurethane elastic fiber of the present invention has a high strength. The present invention exhibits excellent properties in physical properties such as modulus and elastic recovery rate, and chemical properties such as dyeability, oil resistance, and hydrolysis resistance. As is clear from the physical properties of polyurethane elastic fibers, they exhibit superior elastic recovery even at low temperatures of 10° C. or lower, compared to polyurethane elastic fibers containing only polytetramethylene ether glycol as a polyol component. In addition, the polyurethane elastic fiber according to the present invention is much more resistant to hydrolysis by acids and alkalis than when polyester glycol obtained from dicarboxylic acid adipic acid and diol is used as the linear polyhydroxy compound. In addition to exhibiting excellent resistance, it is possible to avoid the decrease in breaking strength that occurs when polypropylene ether glycol is simply mixed with polytetramethylene ether glycol as a linear polyhydroxy compound.

[Brief explanation of the drawing]

FIG. 1 is a graph showing the low-temperature characteristics, that is, the change in elastic recovery rate at 5°C, when the blending ratio of the polyurethane elastic yarn component according to the present invention is changed, and FIG. 2 is a graph showing the change in the elastic recovery rate at 5° C. As for hydrolysis resistance when changing the ratio,
It is a graph showing changes in strength retention when treated with 5% NaOH.

Claims (1)

[Claims] Obtained by reacting a linear polyhydroxy compound having hydroxyl groups at both ends with an excess organic diisocyanate and a chain extender having substantially two active hydrogen groups in a polar organic solvent. When obtaining polyurethane elastic fibers from a polymer solution, the linear polyhydroxy compound (a) has a hydroxyl group at both ends and is composed of isophthalic acid and glycols (A), and polytetramethylene ether glycol (B). ) consisting of a mixture of (b) component (A
1. A method for producing polyurethane elastic fibers, characterized in that the glycols constituting () are one or a mixture of two or more of polytetramethylene ether glycol, 1,6-hexanediol, and polypropylene ether glycol.