KR101253420B1 - Polyurethaneurea Elastic Fiber having high Power and Process for Preparing it - Google Patents

Abstract

The present invention relates to a method for preparing a polyurethane urea elastic yarn, 1) to prepare a prepolymer using an ether glycol and diisocyanate having a number average molecular weight of about 600 to 1300 Dalton, 2) a chain extender in the prepolymer After the addition to obtain a polyurethane urea polymerized product, the present invention relates to a method for producing a high-power elastic yarn, characterized in that by aging and spinning the obtained polyurethaneurea spinning stock solution. Polyurethane urea elastic yarn prepared by the above method has a high power of yarn, the interwoven fabric using the elastic yarn expresses excellent power.

Description

Polyurethaneurea Elastic Fiber having high Power and Process for Preparing it

The present invention relates to a method for producing a polyurethane urea and to an elastic yarn produced using the same, and more particularly to preparing a prepolymer using ether-based glycol having a low number average molecular weight of about 600 to 1300 Dalton and diisocyanate Polyurethane urea and a high-power elastic yarn prepared using the same, characterized in that the polyurethane urea obtained by adding a chain extender to the prepolymer to obtain a polyurethane urea polymer, and then stirred by spinning to obtain a polyurethane urea spinning stock solution It is about.

More specifically, the present invention relates to a technology that enables high power and light weight of interwoven fabrics by producing a polyurethane urea elastic yarn having excellent yarn power.

Polyurethane urea is a primary polymerization reaction product which generally reacts a polyol which is a high molecular weight diol compound with an excess diisocyanate compound to obtain a prepolymer having an isocyanate group at both ends of the polyol, and the prepolymer in an appropriate solvent. After dissolving, a diamine-based or diol-based chain extender is added to the solution, and a chain terminator such as monoalcohol or monoamine is reacted to form a spinning solution of polyurethaneurea fibers, and then subjected to dry and wet spinning. The polyurethaneurea elastic fiber is obtained by this.

Polyurethane urea elastic fibers are used in various applications because of their inherent properties with excellent elasticity and elastic recovery ability, and as the range of applications thereof is expanded, new additional properties are continuously required for existing fibers.

In general, polyurethaneurea elastic fiber is used as a fabric by interlacing with other yarns (nylon, cotton, silk, wool, etc.). It is made of high power elastic yarn of denier (denier) to make the fabric light weight while high power. The demand for expressing is increasing gradually. In addition, thermal embrittlement occurs due to high heat in post-processing after knitting, which causes problems such as deterioration of the power of the fabric. Polyurethane urea elastic fiber having high power and heat resistance to solve such problems The demand for is increasing.

In response to the above problems, efforts have been made to improve the power and heat resistance of polyurethane-based elastic fibers. The most common method used by elastic yarn manufacturers has been to increase the power by increasing the capping ratio in the preparation of polymers for elastic yarn production, and to improve heat resistance by using a chain extension agent having high bonding strength and no side chain. will be. However, in the case of improving power and heat resistance in the above manner, problems such as rapid rise in viscosity and lower solubility due to gel formation of the polymer may occur, which may limit process control. That is, a method for improving the power and heat resistance of the polyurethane-based elastic fiber while securing yarn elongation and maintaining a stable polymer has not been established.

In order to solve the above problems, according to a preferred embodiment of the present invention, in the method for producing a polyurethane urea elastic yarn consisting of a polyol and a diisocyanate polymer, 1) ether glycol having a low number average molecular weight of 600 to 1300 Dalton and A prepolymer is prepared using diisocyanate, and 2) a chain extender is added to the prepolymer to obtain a polyurethane urea polymer, and then the polyurethane urea spinning solution obtained by stirring is aged to spin. Provided are methods for producing a power elastic yarn. The fabric interwoven with the high power elastic yarn manufactured as described above exhibits excellent power.

The present invention is to produce a polyurethane urea elastic yarn having excellent power, by using the polyurethane urea elastic yarn to enable high power and light weight of the interwoven fabric, and when the heat setting it to a technology that is not embrittled by heat It is about.

Hereinafter, the method of manufacturing the polyurethaneurea elastic yarn of this invention is demonstrated in detail. The polyurethaneurea used in the preparation of the elastic yarn of the present invention is prepared by reacting an organic diisocyanate with a polymer diol to prepare a prepolymer, and then dissolving it in an organic solvent and then reacting with a diamine and a monoamine.

Specific examples of the diisocyanate used in the production of the polyurethaneurea elastic yarn used in the present invention include 4,4'-diphenylmethane diisocyanate, 1,5'-naphthalene diisocyanate, 1,4'-phenylenedi isocyanate, hexa Methylene diisocyanate, 1,4'-cyclohexane diisocyanate, 4,4'-dicyclohexyl methane diisocyanate, isophorone diisocyanate, and the like.

The polyols used in the present invention are also limited to polytetramethylene ether glycol, polypropylene glycol, and the like ether system. The number average molecular weight of the polyol used in the present invention is 600 to 1300 Daltons.

When an ether polyol having a number average molecular weight of about 600 to 1300 is added, the length of the soft segment is shorter than that of the polyol having a molecular weight higher than that of the polyol, thereby exhibiting substantially the same effect as that of increasing the capping ratio. Elastic fibers can be obtained. Specifically, if the number average molecular weight is less than 600 Daltons, the solubility of the polymer is lowered and cannot be applied. If the number average molecular weight exceeds 1300 Daltons, there is a problem that the yarn power improving effect is lowered.

Diamines are used as the chain extender, and examples thereof include ethylenediamine, 1, 2-diaminopropane, 1, 3-diaminopropane, 1,4-diaminobutane, 2,3-diaminobutane, 1, One kind or a mixture of two or more kinds thereof, such as 5-diaminopentane, 1, 6-hexamethylenediamine and 1,4-cyclohexanediamine, can be exemplified.

As the chain terminator of the polyurethane urea, an amine having a monofunctional group, for example, diethylamine, monoethanolamine, dimethylamine and the like can be used.

In addition, in the present invention, in order to prevent discoloration of the polyurethane urea and deterioration of physical properties due to ultraviolet rays, atmospheric smog, and heat treatment associated with spandex processing, a steric hindrance phenol compound, a benzofuran-one compound, and a semicarbazide Type compound, a benzo triazole type compound, a polymeric tertiary amine stabilizer, etc. can be added combining them suitably.

Furthermore, the polyurethaneurea elastic yarn of the present invention may include additives such as titanium dioxide, magnesium stearate, and the like in addition to the above components.

The elastic yarn produced by the present invention has a high power, specifically, the power (5th Unload at 200% [g / d]) of the yarn immediately after production is 0.0380 g / d to 0.0550 g / d. If the yarn's power is less than 0.0380g / d, it has a power level similar to that of ordinary spandex, so it cannot be regarded as a high power yarn. If it exceeds 0.0550g / d, the power is not a problem by itself but other properties such as elongation It is expected that this will be degraded.

Hereinafter, the present invention will be described in detail with reference to specific examples and comparative examples, but these examples are merely to illustrate the present invention and should not be construed as limiting the scope of the present invention.

NCO% of the polymers mentioned in Examples and Comparative Examples to be described later, physical properties of the polyurethane urea elastic yarn, and the power of the fabric were measured as follows.

* NCO% measurement

NCO% = [100 * 2 * NCO chemical formula * (capping ratio-1)] / {(diisocyanate molecular weight * capping ratio) + polyol molecular weight}

Where the capping ratio is the diisocyanate molar ratio / polyol molar ratio.

* Denia of yarn

Measure the weight of 90cm * 10 strands of sample length and calculate Denia according to the following formula.

Denier = weight of 10 strands of sample g / 9m * 9000m / 1g

* Elongation of yarn

Measurement is made at a sample length of 10 cm and a tensile speed of 100 cm / min using an automatic power measuring device (MEL, Textechno). In this case, the strength and elongation at break are measured, and the load (200% modulus) applied to the yarn at 200% elongation is also measured.

* The power of yarn

Using an automatic elongation measuring device (MEL machine, Textechno Co., Ltd.), the sample is measured by repeating 300% 5 times with a sample length of 10cm * 20 strands and a tensile speed of 100cm / min.

* Heat resistance of yarn

After repeating the elongation between 0-300% five times by using the automatic strength measuring device, measure the stress (P1) at 200% and the stress (P2) after heat treatment at the fifth elongation. It is represented by the heat resistance of.

The heat treatment of the yarn is 100% elongated while being exposed to the air, followed by dry heat treatment at 190 ° C. for 1 minute, cooling to room temperature, followed by wet heat treatment at 100 ° C. for 30 minutes in a relaxed state, and drying at room temperature.

Heat Resistance (%) = P2 / P1 X 100

* Power of fabric

Circular knitted fabrics were fabricated using elastic yarn and Nylon yarn using a circular knitting machine having a diameter of 32 inches, 28 gauge, and 96 feeders. The circular knitted fabric was knitted using 70 denier of nylon yarn and 40 denier of elastic yarn prepared above, and the content of the elastic yarn was 8% of the total knit weight.

After pre-setting, dyeing, and final-setting the circular knitting fabric made of interwoven nylon / polyurethane urea elastic yarn, the sample is processed using an automatic elongation measuring device (MEL machine, Textechno). 2.5 cm in width * Sample length 20 cm, tensile rate 100 cm / min 100% repeated five times elongation is measured.

<Example 1>

As a capping ratio (CR) of 1.55 and polyol, polytetramethylene ether glycol (molecular weight 1000) was used, and 4,4'-diphenylmethane diisocyanate was mixed. Ethylenediamine and 1,2-diamino propane were used as the chain extender at a ratio of 80 mol% and 20 mol%, and diethylamine was used as the chain terminator. The ratio of the chain extender to the chain terminator was 10: 1, and the amine used was prepared at a total concentration of 7 mol%, and dimethylacetamide was used as the solvent. As a solid preparation of the additive polymer of ethylene bis (oxyethylene) bis - (3- (5- t-butyl-4-hydroxy-m-weekends) -propionate), 1.5% by weight, 5,7-di-t 0.5% by weight of 1,1,1 ', 1'-tetramethyl-4,4' - (methylene-di- p -tert-butylphenyl) 1% by weight of poly (N, N-diethyl-2-aminoethyl methacrylate) and 0.1% by weight of titanium dioxide were added and mixed to obtain a polyurethane urea spinning stock solution.

That is, 329.72 g of 4,4'-diphenylmethane diisocyanate and 850.0 g of polytetramethylene ether glycol (molecular weight 1000) are reacted with stirring at 90 ° C. for 150 minutes in a nitrogen gas stream for a polyurethaneurea having an isocyanate at the sock end. Was prepared. After cooling the prepolymer to room temperature, 1815.73 g of dimethylacetamide was added to obtain a polyurethaneurea prepolymer solution. Then 22.48 g (0.56 mole) of ethylenediamine, 6.93 g (0.14 mole) of 1,2-diopropane and 3.42 g of diethylamine were dissolved in 436.14 g of dimethylacetamide and added to the prepolymer solution at 10 ° C. or lower. It added and obtained the polyurethaneurea solution.

The spinning stock solution obtained as described above was spun at a speed of 900 m / min by dry spinning (spinning temperature: 270 ^o C) to prepare two polyurethaneurea elastic yarns of 20 denia 1 filament and 40 denia 3 filament, and evaluated for their physical properties. It is shown in Tables 1 and 2.

<Example 2>

It is the same as Example 1 except preparing with capping ratio (CR) 1.65, 350.99g of 4,4'- diphenylmethane diisocyanate, and 850.0g of polytetramethylene ether glycol (molecular weight 1000). The obtained spinning stock solution was spun at a speed of 900 m / min by dry spinning (spinning temperature: 270 ^° C.) to prepare two polyurethane urea elastic yarns of 20 denia 1 filament and 40 denia 3 filament, and evaluated for their physical properties. 1 and 2 are shown.

<Example 3>

It is the same as Example 1 except preparing with capping ratio (CR) 1.75, 372.26g of 4,4'- diphenylmethane diisocyanate, and 850.0g of polytetramethylene ether glycol (molecular weight 1000). The obtained spinning stock solution was spun at a speed of 900 m / min by dry spinning (spinning temperature: 270 ^° C.) to prepare two polyurethane urea elastic yarns of 20 denia 1 filament and 40 denia 3 filament, and evaluated for their physical properties. 1 and 2 are shown.

<Comparative Example 1>

The polyol is the same as in Example 2 except that polytetramethylene ether glycol (molecular weight 1800) was used. The obtained spinning stock solution was spun at a speed of 900 m / min by dry spinning (spinning temperature: 270 ^° C.) to prepare two polyurethane urea elastic yarns of 20 denia 1 filament and 40 denia 3 filament, and evaluated for their physical properties. 1 and 2 are shown.

PTMG
Molecular Weight NCO% Denier burglar
[g / d] Shindo
[%] 200%
Modulus
[g] 5th
Unload at
200% [g / d] Heat resistance
[%] Example 1 1000 3.330 20.1 1.38 456 5.11 0.0402 55 39.8 1.66 453 12.29 0.0383 56 Example 2 1000 3.866 19.6 1.32 438 5.83 0.0432 58 40.3 1.62 429 13.92 0.0401 60 Example 3 1000 4.383 19.8 1.24 420 6.40 0.0475 63 39.5 1.55 414 15.40 0.0429 64 Comparative Example 1 1800 2.468 19.4 0.96 475 3.60 0.0294 53 40.5 1.03 465 8.80 0.0308 59

As shown in Table 1, it was confirmed that the polyurethaneurea elastic yarn manufactured using polytetramethylene ether glycol (molecular weight 1000) showed high yarn power.

Table 2 below shows the processing conditions and power of the fabric after the circular knitted fabric prepared by the fabric evaluation method.

Yarn
Denier Presetting temperature (℃) Final setting temperature (℃) Fabric weight [g / m2] Fabric power
5th unload at 50%
[g / m2] Example 2 20 190 180 113 136.7 40 195 185 192 283.6 Comparative Example 1 20 190 180 117 95.6 40 195 185 198 225.2

As shown in Table 2, the fabric produced in Example 2 when the nylon circular knitted fabric was prepared was confirmed to have superior fabric power compared to the fabric produced in Comparative Example 1.

Claims (5)

In the production method of polyurethane urea elastic yarn composed of a polyol and a diisocyanate polymer,
1) preparing a prepolymer using an ether glycol and diisocyanate mixture having a number average molecular weight of 600 to 1300 Dalton, 2) adding a chain extender to the prepolymer to obtain a polyurethaneurea polymer, and then stirring the mixture. The obtained polyurethaneurea spinning stock solution is aged and then spun to prepare a yarn, and the power of the prepared yarn (5th Unload at 200% [g / d]) is 0.0380 g / d to 0.0550 g / d. Method of manufacturing elastic yarn with excellent power to. The diisocyanate of claim 1, wherein the diisocyanate is 4,4'-diphenylmethane diisocyanate, 1,5'-naphthalene diisocyanate, 1,4'-phenylene diisocyanate, hexamethylene diisocyanate, 1,4'-cyclohexane A method for producing an elastic yarn having excellent power, characterized in that one or more selected from the group consisting of diisocyanate, 4,4'-dicyclohexyl methane diisocyanate, or isophorone diisocyanate is used. The method of claim 1, wherein the ether glycol is polytetramethylene ether glycol or polypropylene glycol. The chain extender of claim 1 wherein the chain extender is ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 2,3-diaminobutane, 1,5-di A method for producing an elastic yarn having excellent power, characterized in that one or two or more selected from the group consisting of aminopentane, 1,6-hexamethylenediamine and 1,4-cyclohexanediamine. delete