KR101157335B1 - A Process for Preparing Polyurethaneurea Elastic Fiber having high Power - Google Patents

Abstract

The present invention relates to a method for preparing a polyurethane urea, and more particularly, to prepare a prepolymer using glycol and diisocyanate having a number average molecular weight of 800 to 1300 Dalton, and to add a chain extender to the prepolymer The present invention relates to a method for producing a polyurethaneurea elastic yarn having excellent power by obtaining a urethane urea polymerized product, then stirring and spinning the obtained polyurethaneurea spinning stock solution.

Polyurethane Urea Elastic Yarn, High Power

Description

A process for preparing Polyurethaneurea Elastic Fiber having high Power

The present invention relates to a method for preparing a polyurethane urea, and more particularly, to prepare a prepolymer using glycol and diisocyanate having a number average molecular weight of 800 to 1300 Dalton, and to add a chain extender to the prepolymer The present invention relates to a method for producing a polyurethaneurea elastic yarn having excellent power by obtaining a urethane urea polymerized product, then stirring and spinning the obtained polyurethaneurea spinning stock solution.

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, 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 polyurethane urea elastic fibers, and in particular, the demand to improve the power while reducing the weight of fabric during knitting / knit using denier elastic yarn It is increasing.

In response to the above problem, efforts have been made to improve the breaking 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 production of polymers for elastic yarn production. However, when the power is improved in the above manner, the elongation of the yarn is lowered, and there is a limit in that the process management is not easy due to a sudden increase in viscosity and a decrease in solubility due to the formation of the polymer gel. . That is, there is no way to establish a method for improving the power of the polyurethane-based elastic fiber while securing yarn elongation and maintaining a stable polymer.

According to the present invention, a method for producing a polyurethane urea elastic yarn having excellent power is prepared by preparing a prepolymer using glycol and diisocyanate having a number average molecular weight of 800 to 1300 Dalton, and adding a chain extender to the prepolymer to obtain a polyurethane. After the urea polymer is obtained, the polyurethane urea spinning stock solution obtained by stirring the aging is characterized by spinning.

According to another preferred feature of the invention, the diisocyanate is 4,4'-diphenylmethane diisocyanate, 1,5'-naphthalene diisocyanate, 1,4'-phenylene diisocyanate, hexamethylene diisocyanate, 1,4 ' One or more selected from the group consisting of -cyclohexane diisocyanate, 4,4'-dicyclohexyl methane diisocyanate, or isophorone diisocyanate is used.

According to another preferred feature of the present invention, the polyol used in the prepolymer is a polytetramethylene ether glycol, polypropylene glycol, polycarbonate diol, a copolymer of a poly (tetramethylene ether) glycol and a mixture of alkylene oxide and lactone monomer, Or one or two or more selected from the group consisting of copolymers of 3-methyl-tetrahydrofuran and tetrahydrofuran.

According to another preferred feature of the invention, the chain extender is ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 2,3-diaminobutane, 1, It is 1 type, or 2 or more types chosen from the group which consists of 5-diaminopentane, 1, 6- hexamethylenediamine, and 1, 4- cyclohexanediamine.

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 of the cross / knitted fabric. In addition, due to the improved modulus of the yarn, it is possible to reduce the weight of the fabric.

Hereinafter, the method of manufacturing the polyurethaneurea elastic yarn of this invention is demonstrated in detail. Polyurethane urea used in the preparation of the elastic yarn of the present invention is prepared by reacting a diisocyanate with a polyol to prepare a prepolymer, 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'-cyclohexanediisocyanate, 4,4'-dicyclohexyl methane diisocyanate, isophorone diisocyanate and the like, and these are used alone or in combination.

In addition, the polyol used in the present invention is polytetramethylene ether glycol, polypropylene glycol, polycarbonate diol, copolymer of alkylene oxide and lactone monomer and 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. The molecular weight of the glycol used in the present invention has a number average molecular weight of about 800 to 1300 Daltons.

 In the present invention, by using a glycol having a number average molecular weight of 800 to 1300 Daltons, the elongation of the yarn was improved by increasing the amount of hard segment in the yarn than before. When glycol having a number average molecular weight of 800 to 1300 Dalton is used, as the length of the yarn segment becomes shorter, the repeating unit of the hard segment increases, thereby obtaining high power elastic fibers such as an effect of increasing the capping ratio. will be. When the molecular weight is less than 800, when the external stress is applied due to excessive increase of the hard segment, it is easy to be broken and its solubility is degraded, making it impossible to apply the process. And elongation also has a problem that is greatly reduced. When the molecular weight exceeds 1300, it is difficult to expect a power improvement effect.

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.

Hereinafter, one or more exemplary embodiments of the present invention will be described in detail with reference to specific examples and comparative examples, which should not be construed as limiting the scope of the present invention as merely illustrative 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 of the yarn 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

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 the elastic yarn was 8% of the total knit weight.

Pre-setting → dyeing → Final-setting of circular knitting fabric made of cross-woven / knitted nylon / polyurethane urea elastic yarn, and then using an automatic elongation measuring device (MEL machine, Textechno) Sample width 2.5 cm * Sample length 20cm, tensile rate 100cm / min to measure 100% 5 times repeated elongation.

<Example 1>

A capping ratio (CR) of 1.70 and polyol were prepared using polytetramethylene ether glycol (PTMG, molecular weight 1000) and prepared using 4,4'-diphenylmethane diisocyanate. 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. Ethylenebis (oxyethylene) bis- (3- (5- t -butyl-4-hydroxy- m -toyl) -propionate) 1.5% by weight, 5,7-di- t as an additive relative to the solid content of the polymer -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) dimicarbazide, 1 weight% of poly (N, N-diethyl-2-aminoethyl methacrylate), and 0.1 weight% of titanium dioxide were added and mixed, and the polyurethaneurea spinning stock solution was obtained.

That is, 452.2 g of 4,4'-diphenylmethane diisocyanate and 1070.0 g of polytetramethylene ether glycol (molecular weight 1000) are reacted with stirring at 90 ° C. for 180 minutes in a nitrogen gas stream and a polyurethane urea having an isocyanate at the sock end. Was prepared. After cooling the prepolymer to room temperature, 2666.3 g of dimethylacetamide was added to obtain a polyurethaneurea prepolymer solution. 36.0 g (0.6 mole) of ethylenediamine, 11.1 g (0.15 mole) of 1,2-dioanopropane, and 4.4 g of diethylamine were dissolved in 684 g of dimethylacetamide and added to the prepolymer solution at 10 ° C. or lower. To obtain a polyurethaneurea 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 are shown in Table 1 below.

<Example 2>

Capping ratio (CR) 1.70 and polyol were prepared using polytetramethylene ether glycol (PTMG, molecular weight 800) and prepared using 4,4'-diphenylmethane diisocyanate. 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. Ethylenebis (oxyethylene) bis- (3- (5- t -butyl-4-hydroxy- m -toyl) -propionate) 1.5% by weight, 5,7-di- t as an additive relative to the solid content of the polymer -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) dimicarbazide, 1 weight% of poly (N, N-diethyl-2-aminoethyl methacrylate), and 0.1 weight% of titanium dioxide were added and mixed, and the polyurethaneurea spinning stock solution was obtained.

That is, 455.2 g of 4,4'-diphenylmethane diisocyanate and 856 g of polytetramethylene ether glycol (molecular weight 800) are reacted with stirring at 90 ° C. for 180 minutes in a nitrogen gas stream to obtain a polyurethaneurea having an isocyanate at the end of the socks. Prepared. After cooling the prepolymer to room temperature, 2211.6 g of dimethylacetamide was added to obtain a polyurethaneurea prepolymer solution. 36.0 g (0.6 mole) of ethylenediamine, 11.1 g (0.15 mole) of 1,2-dioanopropane, and 4.4 g of diethylamine were dissolved in 684 g of dimethylacetamide and added to the prepolymer solution at 10 ° C. or lower. To obtain a polyurethaneurea solution. The obtained spinning stock solution was spun at a speed of 900 m / min to prepare a polyurethane urea elastic yarn of 40 denier 3 filaments, and the physical properties are shown in Table 1 and 2.

<Comparative Example 1>

Capping ratio (CR) 1.70 and polyol were prepared using polytetramethylene ether glycol (PTMG, molecular weight 1800) and prepared using 4,4'-diphenylmethane diisocyanate. 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. Ethylenebis (oxyethylene) bis- (3- (5- t -butyl-4-hydroxy- m -toyl) -propionate) 1.5% by weight, 5,7-di- as an additive relative to the solid content of the polymer 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.

That is, 455.2 g of 4,4'- diphenylmethane diisocyanate and polytetramethylene ether glycol (molecular weight 1800)

1926 g was reacted with stirring at 90 ° C. for 180 minutes in a nitrogen gas stream to prepare a polyurethaneurea having an isocyanate at the sock end. After cooling the prepolymer to room temperature, 4485.3 g of dimethylacetamide was added to obtain a polyurethaneurea prepolymer solution. 36.0 g (0.6 mole) of ethylenediamine, 11.1 g (0.15 mole) of 1,2-dioanopropane, and 4.4 g of diethylamine were dissolved in 684 g of dimethylacetamide and added to the prepolymer solution at 10 ° C. or lower. To obtain a polyurethaneurea solution. Same as Example 1. The obtained spinning stock solution was spun at a speed of 900 m / min to prepare a polyurethane urea elastic yarn of 40 denier 3 filaments, and the physical properties are shown in Table 1 and 2.

 The obtained spinning stock solution was spun at a speed of 900 m / min to prepare a polyurethane urea elastic yarn of 40 denier 3 filaments, the physical properties are shown in Table 1 to evaluate the properties.

<Comparative Example 2>

Capping ratio (CR) 1.70 and polyol were prepared using polytetramethylene ether glycol (PTMG, molecular weight 2000) and prepared using 4,4'-diphenylmethane diisocyanate. 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. Ethylenebis (oxyethylene) bis- (3- (5- t -butyl-4-hydroxy- m -toyl) -propionate) 1.5% by weight, 5,7-di- t as an additive relative to the solid content of the polymer -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) dimicarbazide, 1 weight% of poly (N, N-diethyl-2-aminoethyl methacrylate), and 0.1 weight% of titanium dioxide were added and mixed, and the polyurethaneurea spinning stock solution was obtained.

That is, 455.2 g of 4,4'- diphenylmethane diisocyanate and polytetramethylene ether glycol (molecular weight 2000)

2134 g was reacted with stirring at 90 ° C. for 180 minutes in a nitrogen gas stream to prepare a polyurethaneurea having an isocyanate at the sock end. After cooling the prepolymer to room temperature, 4940.1 g of dimethylacetamide was added to obtain a polyurethaneurea prepolymer solution. 36.0 g (0.6 mole) of ethylenediamine, 11.1 g (0.15 mole) of 1,2-dioanopropane, and 4.4 g of diethylamine were dissolved in 684 g of dimethylacetamide and added to the prepolymer solution at 10 ° C. or lower. To obtain a polyurethaneurea solution. The obtained spinning stock solution was spun at a speed of 900 m / min to prepare a polyurethane urea elastic yarn of 40 denier 3 filaments, and the physical properties are shown in Table 1 and 2.

PTMG
Molecular Weight NCO% burglar
[g / d] Shindo
[%] 200%
Modulus
[g] 5th
Unload at
200% [g] Heat resistance
[%] Example 1 1000 4.127 1.24 419 12.2 1.53 58 Example 2 800 4.801 1.02 383 13.3 1.68 60 Comparative Example 1 1800 2.643 1.17 479 8.5 1.28 45 Comparative Example 2 2000 2.425 1.02 550 7.8 1.04 41

Polytetramethylene ether glycol (molecular weight 1000) was used as shown in Table 1, and the polyurethaneurea elastic yarn prepared by mixing 4,4'-diphenylmethane isocyanate showed excellent power.

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

Presetting temperature (℃) Final setting temperature (℃) Fabric weight [g / m2] Fabric power
5th unload at
50%
[g / m2] Example 1 190 180 252 115.4 Comparative Example 1 190 180 249 97.4

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 2 even when pre-set at 190 ° C.

Claims (4)

In the production method of polyurethane urea elastic yarn composed of a polyol and a diisocyanate polymer, A prepolymer having a capping ratio (CR) of 1.70 was prepared using glycols and diisocyanates having a number average molecular weight of 800 to 1300 Daltons, and a chain extender and a chain terminator were added to the prepolymer in a ratio of 10: 1. A method for producing a polyurethaneurea elastic yarn having excellent power, characterized in that after the polyurethaneurea polymer is obtained, the polyurethaneurea spinning stock solution obtained by stirring it is aged and dried. 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 having excellent power, characterized by using one or two or more selected from the group consisting of diisocyanate, 4,4'-dicyclohexyl methane diisocyanate, or isophorone diisocyanate. 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 -Method for producing a polyurethaneurea elastic yarn having excellent power, 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 having excellent power, characterized in that one or two or more selected from the group consisting of aminopentane, 1,6-hexamethylenediamine and 1,4-cyclochlorodiamine.