KR101157327B1 - A Process for Preparing Polyurethaneurea Elastic Fiber having high Power and Heat-resistance and fiber using it - Google Patents

Abstract

The present invention relates to a method for producing a polyurethane urea elastic yarn, and more particularly, 1) to prepare a prepolymer by mixing a reaction molar ratio of diisocyanate to 1.45 to 2.15 glycol and diisocyanate, and 2) to the prepolymer After adding a chain extender to obtain a polyurethaneurea polymer, 3) adding triethylenetetraamine (TETA) to the polyurethaneurea polymer at 0.01 to 15% by weight relative to the final polymer solid to prepare a polyurethaneurea spinning stock solution, It is characterized in that the spinning, according to the present invention, it is possible to easily produce an elastic yarn having a high power and heat resistance without sharply changing the polymer production conditions. Polyurethane urea elastic yarn prepared by the above method has a high power and excellent heat resistance, the cross-woven fabric using the elastic yarn can improve the thermal embrittlement by post-processing is performed after the high power of the fabric.

Polyurethane urea elastic yarn, triethylene tetraamine, high power, heat resistance, fabric power

Description

A process for preparing polyurethaneurea elastic fiber having high power and heat-resistance and fiber using it}

The present invention relates to a method for producing a polyurethane urea and to an elastic yarn produced by using the same, and more specifically, to prepare a prepolymer by mixing a glycol and diisocyanate with a reaction molar ratio of diisocyanate to 1.45 to 2.15 Polyurethane characterized by adding a chain extender to the polymer to obtain a polyurethaneurea polymer, and then adding and spinning triethylenetetraamine (TETA) to the final polyurethaneurea polymer at 0.01 to 15% by weight relative to the final polymer solids. Urea and high-power elastic yarn produced using the same.

More specifically, by manufacturing a polyurethane urea elastic yarn excellent in power and heat resistance, the polyurethane urea elastic yarn is used to enable high power and light weight of the woven fabric, so that it is not embrittled by heat when heat setting it It is about technology to do.

Polyurethane urea is a primary polymerization product that generally reacts a polyol, which is a high molecular weight diol compound, with an excess of diisocyanate compound to obtain a prepolymer having isocyanate groups at both ends of the polyol, and the prepolymer is a suitable solvent. After dissolving in a solution, 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 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, polyurethane urea elastic fibers are thermally embrittled by high heat in the post-processing after knitting with the other company (nylon, cotton, silk, wool, etc.), which causes problems such as lowering the power of the fabric. . In order to solve this problem, there is an increasing demand for high power and heat resistant polyurethane urea elastic fibers, and in particular, the demand to improve the power while reducing the weight of fabric when knitting using denier elastic yarn. Is gradually increasing.

In response to the above problems, efforts have been made to improve the heat resistance and yarn power of polyurethane-based elastic fibers. The most common method used by elastic yarn manufacturers has been to improve the power by increasing the content of hard segments in the production 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. It is to let. However, in the case of improving the power and heat resistance in the above manner, problems such as rapid viscosity increase and solubility deterioration due to gel formation of the polymer may occur, and thus process control may not be easy. That is, there is no way to establish a method capable of improving the power and heat resistance of the polyurethane-based elastic fiber while maintaining a stable polymer.

Polyurethane urea elastic yarn production method comprising a polyol and diisocyanate polymer according to the present invention is 1) to prepare a prepolymer by mixing a reaction molar ratio of diisocyanate to 1.45 to 2.15 glycol and diisocyanate, 2) prepolymer 3) Polyurethaneurea polymer was obtained by adding a chain extender to the polymer. 3) Polyethyleneurea polymer was prepared by adding 0.01 to 15% by weight of triethylenetetraamine (TETA) to the final polymer solid. , It is characterized by radiating it.

Polyurethane urea elastic yarn excellent in heat resistance according to the present invention is manufactured by the method described above, characterized in that the load on the yarn at 200% elongation during recovery after 300% 5 repeated elongation is characterized in that more than 1.4g.

Fabrics knitted using the high-power and high heat-resistant elastic yarn prepared in this way can improve the thermal embrittlement by post-processing after the high power of the fabric and knitting.

The present invention is to produce a polyurethane urea elastic yarn having a high power and heat resistance, to enable high power of the woven fabric using the polyurethane urea elastic yarn, it is not embrittled by heat when heat setting.

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.

In the present invention, the reaction molar ratio of the diisocyanate to the glycol of the prepolymer is preferably 1.45 to 2.15 for the physical properties of the polyurethane urea elastic yarn. If the reaction molar ratio is less than 1.45 or greater than 2.15, the physical properties of the elastic yarn are reduced.

The polymer diols used in the present invention include polytetramethylene ether glycol, polypropylene glycol, polycarbonate diol, copolymers of alkylene oxide and lactone monomers, copolymers of poly (tetramethylene ether) glycol, 3-methyl-tetrahydrofuran and It may be exemplified as one or a mixture of two or more thereof in a copolymer of tetrahydrofuran and the like, but is not necessarily limited thereto.

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.

Triethylenetetraamine (TETA) is used to improve modulus and heat resistance, with a content of 0.01 to 15% by weight relative to the final polyurethaneurea solids. When the additive is added to the polyurethaneurea polymer as a crosslinking agent, it forms an intermolecular hydrogen bond in a hard segment to densify the overall molecular structure to obtain an elastic yarn having high modulus and excellent heat resistance. can do. When the content of the additive is less than 0.01% by weight compared to the final polyurethane urea polymer, the power improvement effect is insufficient, and when more than 15% by weight may cause a problem that the elongation of the yarn is greatly reduced.

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 polyurethaneurea elastic yarn produced by the present invention has high power and heat resistance. Preferably, the load on the yarn at 200% elongation during recovery after 300% 5 repeated elongation is 1.4g or more, and the power retention after heat treatment is 50% or more. Polyurethane urea elastic yarn that satisfies these conditions is capable of high power of the knitted fabric and can be prevented from being embrittled by heat when heat setting it.

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.

* Yarn Denia

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

Using an automatic elongation measuring device (MEL machine, Textechno Co., Ltd.), measure the sample length as 10cm and tensile speed 100cm / min. At this time, the strength and elongation at break are measured, and the load on the yarn (200% modulus) 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.

* Power retention rate after heat treatment of yarn

Measure the initial yarn power (5'th unload at 200%, P0). After 100% elongation of the yarn exposed to the atmosphere, dry heat treatment for 1 minute at 190 ℃ and cooled to room temperature. Dry heat-treated yarn was moist-heated at 100 ° C. for 30 minutes in a relaxed state and dried at room temperature to measure the power of the yarn (5'th unload at 200%, P1). Calculate

 Power retention after heat treatment (%) = P1 / P0 X 100

* Power of fabric

The elastic knitted fabric and nylon yarn were manufactured using a circular knitting machine having a diameter of 32 inches, a 28 gauge, and a 96 feeder. The circular knitted fabric was knitted using 70 denier of nylon yarn and 40 denier of elastic yarn prepared above, and the content of elastic yarn was 8% of the total weight of the knitted fabric. to be.

After pre-setting, dyeing, and final-setting the circular knitting fabric made of interwoven nylon / polyurethane urea elastic yarn, the sample is measured by 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>

Glycol and diisocyanate were mixed at a capping ratio (CR) of 1.75, and ethylenediamine and 1,2-diamino propane were used at a ratio of 80 mol% and 20 mol%, and diethylamine was used as a 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.

That is, 468.6 g of 4,4'-diphenylmethane diisocyanate and 1926.0 g of polytetramethylene ether glycol (molecular weight 1800) are reacted with stirring at 90 ° C. for 180 minutes in a nitrogen gas stream, and a polyurethane urea having an isocyanate in the sock end. Was prepared. After cooling the prepolymer to room temperature, 3350.7 g of dimethylacetamide was added to obtain a polyurethaneurea prepolymer solution. Subsequently, 33.6 g (0.56 mole) of ethylenediamine, 10.3 g (0.14 mole) of 1,2-diopropane, and 5.1 g of diethylamine were dissolved in 651 g of dimethylacetamide and added to the prepolymer solution at 10 ° C. or lower. To obtain a polyurethaneurea solution.

As an additive to the solid content of this polymer, 0.5 weight% of triethylene tetraamines (TETA), 0.5 weight% of 5,7-di- t- butyl- 3- (3, 4- dimethylphenyl) -3H-benzofuran-2-one , 1,1,1 ', 1'-tetramethyl-4,4'-(methylene-di- p -phenylene) dicemicarbazide 1 wt%, poly (N, N-diethyl-2-aminoethyl 1 weight% of methacrylate) and 0.1 weight% of titanium dioxide were added and mixed to obtain a polyurethane urea spinning stock solution.

The spinning stock solution obtained as described above was spun at a speed of 900 m / min by dry spinning (spinning temperature: 260 ^° C.) to prepare a polyurethane urea elastic yarn of 40 denia 3 filaments, and the physical properties thereof were shown in Tables 1 and 2. It was.

< Example  2>

Polyurethane urea elastic yarn was prepared in the same manner as in Example 1, except that 5 wt% of triethylenetetraamine (TETA) was added to the solid content of the final polyurethaneurea polymer, and the physical properties thereof were evaluated in Tables 1 and 2 Shown in

< Example  3>

Polyurethane urea elastic yarn was prepared in the same manner as in Example 1 except that 10 wt% of triethylenetetraamine (TETA) was added to the solid content of the final polyurethaneurea polymer, and the physical properties thereof were evaluated in Tables 1 and 2 Shown in

< Example  4>

Polyurethane urea elastic yarn was prepared in the same manner as in Example 1 except that 15 wt% of triethylenetetraamine (TETA) was added to the solid content of the final polyurethaneurea polymer, and the physical properties thereof were evaluated in Tables 1 and 2 Shown in

< Comparative example  1>

It was prepared under the same conditions as in Example 1 except that triethylenetetraamine (TETA) was not added. That is, 468.6 g of 4,4'-diphenylmethane diisocyanate and 1926.0 g of polytetramethylene ether glycol (molecular weight 1800) are reacted with stirring at 90 ° C. for 180 minutes in a nitrogen gas stream, and a polyurethane urea having an isocyanate in the sock end. Was prepared. After cooling the prepolymer to room temperature, 3350.7 g of dimethylacetamide was added to obtain a polyurethaneurea prepolymer solution. Subsequently, 33.6 g (0.56 mole) of ethylenediamine, 10.3 g (0.14 mole) of 1,2-diopropane, and 5.1 g of diethylamine were dissolved in 651 g of dimethylacetamide and added to the prepolymer solution at 10 ° C. or lower. To obtain a polyurethaneurea solution.

As an additive with respect to the solid content of this polymer, 1.5 weight% of ethylene bis (oxyethylene) bis- (3- (5- t -butyl-4-hydroxy m -toyl) propionate), 5,7-di- t -Butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one 0.5% by weight, 1,1,1 ', 1'-tetramethyl-4,4'-(methylene-di- p 1 weight% of -phenylene) dicicacarbide, 1 weight% of poly (N, N-diethyl-2-aminoethyl methacrylate), and 0.1 weight% of titanium dioxide were added and mixed to obtain a polyurethaneurea spinning stock solution.

The spinning stock solution obtained as described above was spun at a speed of 900 m / min by dry spinning (spinning temperature: 260 ^° C.) to prepare a polyurethane urea elastic yarn of 40 denia 3 filaments, and the physical properties thereof were shown in Tables 1 and 2. It was.

Table 1

NCO% additive
(TETA)
content
[weight%] De burglar
[g / d] Shindo
[%] 200%
Modulus
[g] 5'th
Unload
at 200%
[g] After heat treatment
5'th
unload
at 200%
[g] Heat resistance
(Power
Retention rate)
[%] Example 1 2.82 0.5% 39.2 1.36 458 12.11 1.42 0.74 52 Example 2 2.82 5% 40.1 1.60 453 14.46 1.57 0.91 58 Example 3 2.82 10% 39.8 1.94 442 19.37 1.82 1.13 62 Example 4 2.82 15% 39.5 2.07 411 23.51 1.95 1.23 63 Comparative Example 1 2.82 0% 40.3 1.24 463 8.82 1.37 0.59 43

* TETA: Triethylenetetraamine

When 0.5 to 15% by weight of triethylenetetraamine (TETA) was added as shown in [Table 1], it was confirmed that yarn power and heat resistance were improved.

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

[Table 2]

Presetting temperature (℃) Final setting temperature (℃) Fabric weight [g / m2] Fabric power
5'th unload at
50%
[g / m2] Example 2 190 180 255 126.3 Comparative Example 1 190 180 249 96.2

As shown in Table 2, the fabric produced in Example 2 when the nylon circular knitted fabric was manufactured was confirmed to have superior fabric power compared to the fabric produced in Comparative Example 1 even when pre-set at 190 ° C. In other words, when triethylenetetramine is not used as an additive, power improvement of the fabric was confirmed to be difficult.

Claims (6)

In the production method of polyurethane urea elastic yarn composed of a polyol and a diisocyanate polymer, 1) a prepolymer is prepared by mixing glycol and diisocyanate with a reaction molar ratio of diisocyanate to glycol at 1.45 to 2.15, 2) adding a chain extender to the prepolymer to obtain a polyurethaneurea polymer, 3) Polyurethane urea elastic yarn manufacturing method characterized in that to produce a polyurethane urea spinning stock solution by adding triethylene tetraamine (TETA) to 0.01 to 15% by weight relative to the final polymer solids to the polyurethane urea polymer . 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 a polyurethaneurea elastic yarn, characterized in that one or two or more selected from the group consisting of diisocyanate, 4,4'-dicyclohexyl methane diisocyanate, or isophorone diisocyanate is used.   The polyol according to claim 1, wherein the polyol used in the prepolymer is polytetramethylene ether glycol, polypropylene glycol, polycarbonate diol, copolymer of a mixture of alkylene oxide and lactone monomer and poly (tetramethylene ether) glycol, or 3 -A method for producing a polyurethaneurea elastic yarn, characterized in that one or two or more selected from the group consisting of a copolymer of methyl-tetrahydrofuran and tetrahydrofuran. 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 a polyurethaneurea elastic yarn, characterized in that one or two or more selected from the group consisting of aminopentane, 1,6-hexamethylenediamine and 1,4-cyclochlorodiamine. The method of claim 1, wherein the isocyanate weight ratio of the prepolymer is 1.75% to 4.13%. Polyurethane urea elastic yarn manufactured by the method of claim 1, having a load on the yarn based on 40 deniers at the time of 200% elongation during recovery after 300% 5 repeated elongation, and having a heat resistance of 50% or more after heat treatment. .