KR0157684B1 - Manufacturing method of polyester ether elastic fiber - Google Patents

Abstract

The present invention relates to a method for producing a polyether-elastic elastic yarn is particularly excellent in elastic recovery rate, there is no change over time for elongation and adhesion does not occur.

The present invention is prepared by adding 1 to 5% by weight of carboxylic acid diester at the end of the polymerization when the polyetherester block polymer containing 1 to 5 mol% of aromatic dicarboxylic acid containing sulfonate group is synthesized. When melt spinning the polymer is a method for producing an elastic yarn characterized in that the spinning by adding 5 to 20 mol% of the liquid crystalline polymer on the basis of terephthalic acid.

Description

Manufacturing method of polyether elastomeric yarn

The present invention relates to a method for producing a thermoplastic polyether ester elastic yarn chemically modified polyether ester block copolymer.

More specifically, in the method of producing a polyether ester-based elastic yarn in which the crystalline segment is chemically modified, that is, the degree of crosslinking is improved to improve the elastic recovery rate, and the productivity is improved by improving the strength and solidification rate by increasing the orientation of the fiber during melt spinning. It is about.

Hard segments generally composed of monomeric diols such as dimethyl terephthalate and 1,3-propanediol, 1,4-butanediol and 1,5-propanediol, dimethyl terephthalate and polytetramethylene terephthalate ether glycol The elastic yarn of the polyether ester block copolymer composed of the soft segment constituted by the elastic yarn is an elastic yarn, and the elastic recovery characteristic of the fiber depends on the degree of crystallization of the hard segment.

Since the known elastic yarn has a disadvantage of low crystallinity and relatively high permanent strain, copolymerization of monomers having three or more functional groups causes chemical fineness to lower the permanent strain, but this method has low elongation at the expense of high initial tensile strength. There is a disadvantage that the heat setting property is reduced.

In addition, as in European Patent-366102, a sulfonate compound is added to improve elasticity by imparting ionomer properties or to impart cationic salting. However, this method tends to increase elongation recovery, but has a spinning speed. There is a disadvantage that is limited to the spinning speed of less than 1,000m / min.

In Japanese Patent Laid-Open No. 5-214087, there is a method in which a thermotropic liquid crystal compound is added to a hard segment to improve the strength and the drawing process is omitted, but this method tends to lower the elongation recovery rate of the yarn.

The present invention solves the shortcomings of the prior art as described above, while increasing the resilience and high intrinsic chlorine resistance and heat-setting properties of the polyester, while the high solidification speed of the polyester block copolymer elastomer The purpose is to provide a manufacturing method.

Hereinafter, the present invention will be described in detail.

The reason for the decrease in workability due to frequent trimming in manufacturing polyether elastomeric yarns is due to the adhesiveness and low strength of the polymer.

In order to eliminate the stickiness of the polymer, the solidification rate of the polymer must be increased, and trimming due to low strength can be overcome by increasing the chain length of the polymer.

The conventional method for speeding up the solidification rate is the inorganic particle addition method, which causes crystallization of the soft segment, which causes a problem that the mechanical properties due to aging decrease over time.

Therefore, in the present invention, a sulfonate compound of an aromatic dicarboxylic acid containing 5-20 mol% of the liquid crystal polymer of the hard segment and a sulfonate group imparting ionomer properties was selected as a result of the change over time due to the crystallization of the soft segment. .

The liquid crystalline polymer used in the present invention is a polymer of parahydroxy banjoic acid.

If the amount of the liquid crystalline polymer exceeds 20 mol%, the strength of the yarn is rather lowered, and if it is less than 5 mol%, the effect of increasing the speed of flux cannot be brought about.

In addition, the method of adding the liquid crystalline polymer is preferably a method of adding a liquid crystalline polymer having a low melt viscosity of 5 to 10% at the spinning temperature in the spinning step.

In the present invention, the content of the sulfonate compound may bring about a desired effect at 1 to 5 mol%. If it is less than 1 mol%, the elastic recovery rate is insignificant. If it is more than 5 mol%, the reaction does not occur and causes problems during spinning. When only one of the sulfonate compound and the liquid crystalline polymer is used alone, the effect is halved or the desired effect cannot be obtained.

The soft segment generally uses polytetramethylene ether glycol having an average molecular weight of 1500 to 3000, and may be used in an amount of 20 to 80% by weight based on the polymer.

The strength of the polymerization degree and the elastic yarn depends on the intrinsic viscosity and can be increased by the chain extension reaction in the solid phase polymerization or the melt synthesis process.

In the present invention, carboxylic acid diester having the following general formula was used.

(R is an alkyl or phenyl group having 1 to 3 carbon atoms)

Specific examples of the carboxylic acid diester include diphenyl carbonate.

In the addition of the carboxylic acid diester, it is effective to inject 1 to 5% by weight of the polymer at the end of the polymerization at the point of time when the molecular chain is the maximum growth in the molten state, and under reduced pressure to prevent depolymerization. It is good to carry out.

The viscosity of the polymer without adding carbonate was less than 2.0, and the viscosity of the polymer with carbonate was increased to 2.5 to 3.0 within a short time.

The polymer obtained by the above method was dried into pellets, melted at a melting temperature of 200 to 270 ° C, air cooled by passing through an extruder and a spinning nozzle, drawn at 2000 m / min, and drawn to a draw ratio of 1.5 to 2.0 in a high speed roller controlled at 60 ° C or below. After stretching, the elastic filament yarn is manufactured by spin-draw method, that is, direct spinning and stretching method, after the heat treatment is performed at a temperature of 20-40 ° C. lower than the melting point, followed by relaxation heat treatment at a relaxation rate of 20-40%. .

The elastic yarn prepared by the above method had excellent uniformity in terms of fineness, and had better elastic recovery rate than when the sulfonate compound was used alone.

In addition, in the case of the elastic yarn prepared by adding the inorganic nucleating agent to the spinning step or the polymerization step, the change in elongation and the strength tended to occur over time, and the adhesion to the roller occurred when it was taken at 1500 m / min or more. In this case, it is confirmed that the above-described process problems or problems with time change do not occur.

The polymer and elastic yarn physical properties used in Examples and Comparative Examples are as follows.

* Intrinsic viscosity (IV): The polymer was calculated from the solution viscosity at a concentration of 0.5% by using a mixture of tetrachloroethane and phenol 1: 1 by weight as a solvent at 35 ℃.

* Melt viscosity: Measured at room temperature with torsion of 100rad / sec.

* DSC Tm: Temperature rise rate 20 ℃ / min

* Instantaneous elongation recovery rate: 1% or 200% elongation by applying the load corresponding to 200% elongation on 10cm of sample, remove the load after 5 seconds and immediately read the length L and calculate it by the following equation.

Example 1

530 parts (2.7265 mol) of dimethyl terephthalate, 358 parts of tetramethylene glycol, 6.2 parts (0.05453 mol) of 5-sodium sulfoisophthalic acid dimethylate in a three-neck cylindrical flask with a condenser and a stirring motor. 400 parts of tetramethylene ether glycol, 300 parts of a polymer of titanium butoxide as titanium, and 0.5 parts of Iganox 1010 based on a polymer were subjected to a transesterification reaction and subjected to a transesterification reaction at a vacuum degree of 0.2 torr or less and a reaction temperature of 270 ° C. or less for 2 hours and 30 minutes. After reacting and replacing with nitrogen, 35 parts of diphenyl carbonate was added and reacted in a vacuum state for about 30 minutes while stirring to obtain pellets. The intrinsic viscosity of this polymer was 2.73 and the melt viscosity at 260 degreeC was 4500 poise.

The spinning polymer pellet and 37 parts (0.2763 mol as repeating units) of polymer pellets of parahydroxy benzoic acid having a melt viscosity of 4070 poises were simultaneously dried and charged into a test spinning machine hopper, and the spinning temperature was 260 ° C., and the number of spinnerets was odd. 8 holes, L / D = 2, discharged at 10g / min, extruded and cooled by air below 10 ° C, drawn at 2000m / min, drawn at 1st gourd roller at 60 ° C with a draw ratio of 1.5, and a second gourd roller. The physical properties of the elastic yarn obtained by heat treatment at 190 ° C. with a 30% relaxation rate at were 490% cutting elongation, 1.7g / d strength, and 95% elastic recovery rate at 200% elongation.

Comparative Examples 1 to 6

In Example 1, the amount of the sulfonate compound, the polymer of parahydroxy benzoic acid and the diphenyl carbonate was used in the same manner as in Table 1 except that the amount of the sulfonate compound was used.

Comparative Example 7

In Example 1, before adding 35 parts of diphenyl carbonate, 37 parts (0.2763 mole as a repeating unit) of parahydroxy benzoic acid were added thereto, followed by stirring for 1 hour and 30 minutes under vacuum while stirring, and 35 parts of diphenyl carbonate. The reaction was carried out in the same manner as in Comparative Example 1. The inherent viscosity of the polymer was 3,900 poise with a melt viscosity at 2.20,260 ° C.

Comparative Example 8

The same procedure as in Example 1 was conducted except that no polymer of parahydroxy benzoic acid was added.

Comparative Example 9

The same procedure was followed as in Example 1 except that no sulfonate compound was added.

Comparative Example 10

The same method as in Example 1 was conducted without adding diphenyl carbonate.

Comparative Example 11

The same procedure was followed as in Example 1 except that no sulfonate compound and a liquid crystalline polymer were added.

Comparative Example 12

The same procedure was followed as in Example 1, except that no sulfonate compound and diphenyl carbonate were added.

Table 1 shows the experimental results of Example 1 and Comparative Examples 1 to 12.

Claims (3)

Polyether esters were synthesized to contain 1 to 5 mol% of aromatic dicarboxylic acid containing selphonate groups, and 1 to 5 wt% of polycarbonate ester having the following general formula at the end of the polymerization was added to the polyether ester block. A polyether ester-based elastic yarn characterized in that a polymer is prepared, and the block polymer is spun and stretched in a spin-draw method, and when the melt spinning is performed, a liquid crystalline polymer is added in an amount of 5 to 20 mol% based on terephthalic acid. Manufacturing method. (R is a C1-3 alkyl group or a phenyl group) The method according to claim 1, wherein the liquid crystalline polymer is a polymer of para hydroxy benzoate liquid. The spinning temperature is 200 ° C to 270 ° C, the spinning speed is 1500m / min or more, and the relaxation rate is 20 to 40 ° C lower than the melting point of the crystal. Method for producing a polyether-elastic elastic yarn, characterized in that 40% of loose heat treatment.