KR101255453B1 - A Process for Preparing Polyurethaneurea Elastic Fiber having high Power and elongation - Google Patents

Abstract

The present invention relates to a method for producing a polyurethane urea, more specifically, a glycol having a low number average molecular weight of 800 ~ 1300 Dalton and a glycol having a number average molecular weight of 1600 ~ 2000 Dalton mass ratio 2: 1 ~ 7: 1 After mixing, the prepolymer was prepared using diisocyanate, and a chain extender was added to the prepolymer to obtain a polyurethaneurea polymer, followed by stirring and spinning the obtained polyurethaneurea spinning stock solution. It relates to a method for producing a polyurethane urea elastic yarn having a.

Description

Process for Preparing Polyurethaneurea Elastic Fiber having high Power and elongation

The present invention relates to a method for producing a polyurethane urea, more specifically, a glycol having a low number average molecular weight of 800 ~ 1300 Dalton and a glycol having a number average molecular weight of 1600 ~ 2000 Dalton mass ratio 2: 1 ~ 7: 1 After mixing, the prepolymer was prepared using diisocyanate, and a chain extender was added to the prepolymer to obtain a polyurethaneurea polymer. After stirring, the polyurethaneurea spinning stock solution obtained by stirring was aged to give excellent power. Eggplant relates to a method for producing a polyurethaneurea elastic yarn.

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 these problems, the demand for high power polyurethane urea elastic fibers is increasing, and in particular, the demand to improve the power while reducing the weight of fabric during knitting and knitting 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.

The present invention has been invented to solve the above problems, the present invention is a glycol having a low number average molecular weight of 800 ~ 1300 Dalton and glycol having a number average molecular weight of 1600 ~ 2000 Dalton mass ratio 2: 1 ~ 7: 1 After mixing, the prepolymer was prepared using diisocyanate, and a chain extender was added to the prepolymer to obtain a polyurethaneurea polymer. After stirring, the polyurethaneurea spinning stock solution obtained by stirring was aged to give excellent power. The purpose is to provide a method for producing a polyurethane urea elastic yarn.

According to the present invention, a method for producing a polyurethane urea elastic yarn having excellent power may include glycol having a low number average molecular weight of 800 to 1300 Dalton and glycol having a number average molecular weight of 1600 to 2000 Dalton in a mass ratio of 2: 1 to 7: 1. After mixing, a prepolymer is prepared using diisocyanate, and a chain extender is added to the prepolymer to obtain a polyurethane urea polymer, and then the polyurethane urea spinning stock solution obtained by stirring is aged to spin. do.

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 invention, the polyols used in the prepolymer are poly (tetramethylene ether) glycol, polypropylene glycol, polycarbonate diol, a mixture of alkylene oxide and lactone monomer and poly (tetramethylene ether) glycol. One or two or more selected from a group consisting of copolymers or 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 and elongation, by using the polyurethane urea elastic yarn enables high power of the interwoven, 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 poly (tetramethylene ether) glycol, polypropylene glycol, polycarbonate diol, copolymer of a mixture of alkylene oxide and lactone monomer and poly (tetramethylene ether) glycol, 3-methyl- tetrahydro In the copolymer of furan and tetrahydrofuran, etc., it can be illustrated as 1 type, or 2 or more types thereof, but it is not necessarily limited to these. The glycols used in the present invention are glycols having a number average molecular weight of 800 to 1300 Daltons and glycols having a number average molecular weight of 1600 to 2000 Daltons.

 In the present invention, by using a glycol having a low number average molecular weight of 800 ~ 1300 Dalton and glycol having a number average molecular weight of 1600 ~ 2000 Dalton in a mass ratio of 2: 1 to 7: 1 by using the amount of hard segment in the yarn than conventional As the length of the soft segment in the yarn is shortened, the repeating unit of the hard segment also increases to obtain a high-power elastic fiber, such as an effect of increasing the capping ratio. When using a molecular weight of 800 Daltons or less, when an external stress is applied due to excessive increase of hard segments, it is easy to be broken and its solubility is lowered, making it impossible to apply the process. And elongation also has a problem that is greatly reduced. When the molecular weight exceeds 2000 Daltons, it is difficult to expect a power improvement effect.

When the mass ratio is 2: 1 or less, there is a problem that the yarn power improvement is insufficient. When the mass ratio is 7: 1, the yarn power is improved, but there is a problem that it becomes difficult to express the elongation of 400% or more.

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, 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.

* Of 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

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

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

After pre-setting → dyeing → final-setting of circular knitting fabric made of cross-woven knitted nylon / polyurethane urea elastic yarn, using 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.

Capping ratio (CR) 1.70, polyol was mixed with a poly (tetramethylene ether) glycol having a molecular weight of 1000 and a poly (tetramethylene ether) glycol having a molecular weight of 1800 in a mass ratio of 4: 1, 4,4'-diphenylmethanedi Prepared using isocyanate. 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 12.5: 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) 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.

Namely, 100 ° C. of poly (tetramethylene ether) glycol having a molecular weight of 1000 and 250.0 g of poly (tetramethylene ether) glycol having a molecular weight of 1800 were prepared at 90 ° C. in 531.8 g of 4,4′-diphenylmethane diisocyanate and nitrogen gas streams. The reaction was stirred for 180 minutes to prepare polyurethaneurea having isocyanate at the sock end. After cooling the prepolymer to room temperature, 3108.4 g of dimethylacetamide was added to obtain a polyurethaneurea prepolymer solution. Then, 42.5 g of ethylenediamine, 13.1 g (0.15 mole) of 1,2-diopropane and 5.2 g of diethylamine were dissolved in 807.0 g of dimethylacetamide and added to the prepolymer solution at 10 ° C. or lower to the polyurethane. A urea solution was obtained.

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.

Capping ratio (CR) 1.70, polyol was mixed with poly (tetramethylene ether) glycol having a molecular weight of 1000 and poly (tetramethylene ether) glycol having a molecular weight of 1800 in a mass ratio of 5: 1, 4,4'-diphenylmethanedi Prepared using isocyanate. 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 12.5: 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) 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.

Namely, 1041.7 g of poly (tetramethylene ether) glycol having a molecular weight of 1000 and 208.3 g of poly (tetramethylene ether) glycol having a molecular weight of 1800 were used at 90 ° C in 53,4 g of 4,4'-diphenylmethane diisocyanate and nitrogen gas groups. The reaction was stirred for 180 minutes to prepare polyurethaneurea having isocyanate at the sock end. After cooling the prepolymer to room temperature, 3108.4 g of dimethylacetamide was added to obtain a polyurethaneurea prepolymer solution. Then, 42.5 g of ethylenediamine, 13.1 g (0.15 mole) of 1,2-diopropane and 5.2 g of diethylamine were dissolved in 807.0 g of dimethylacetamide and added to the prepolymer solution at 10 ° C. or lower to the polyurethane. A urea solution was obtained.

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>

A capping ratio (CR) of 1.70 and a polyol were prepared using poly (tetramethylene ether) glycol having a molecular weight of 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 12.5: 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) 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, 319.1 g of 4,4'-diphenylmethane diisocyanate and 1350.0 g of poly (tetramethylene ether) glycol having a molecular weight of 1800 are reacted with stirring at 90 ° C. for 180 minutes in a nitrogen gas stream to carry poly with isocyanate at the end of the sock. Urethane urea was prepared. After cooling the prepolymer to room temperature, 3624.2 g of dimethylacetamide was added to obtain a polyurethaneurea prepolymer solution. Subsequently, 25.5 g of ethylenediamine, 7.9 g of 1,2-diopropane and 3.1 g of diethylamine were dissolved in 484.2 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.

&Lt; Comparative Example 2 &

Capping ratio (CR) 1.70, polyol was mixed poly (tetramethylene ether) glycol having a molecular weight of 1000 and poly (tetramethylene ether) glycol having a molecular weight of 1800 in a mass ratio of 2: 1, 4,4'-diphenylmethanedi Prepared using isocyanate. 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 12.5: 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) 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.

Namely, 833.3 g of poly (tetramethylene ether) glycol having a molecular weight of 1000 and 416.7 g of poly (tetramethylene ether) glycol having a molecular weight of 1800 were prepared at 90 ° C. in 531.8 g of 4,4′-diphenylmethane diisocyanate and nitrogen gas streams. The reaction was stirred for 180 minutes to prepare polyurethaneurea having isocyanate at the sock end. After cooling the prepolymer to room temperature, 3108.4 g of dimethylacetamide was added to obtain a polyurethaneurea prepolymer solution. Subsequently, 42.5 g of ethylenediamine, 13.1 g of 1,2-diopropane and 5.2 g of diethylamine were dissolved in 807.0 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.

Poly (tetramethylene ether) glycol having a molecular weight of 1000 and a poly (tetramethylene ether) glycol having a molecular weight of 1800 as a mixture of 4,4'-diphenylmethane isocyanate It was confirmed that the urethane urea elastic yarn exhibited excellent power, and the elongation was maintained at 400% or more.

The following [Table 2] shows the processing conditions and power of the fabric fabricated by post-processing the circular knitted fabric.

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)

Prepolymers are prepared by using polyols and diisocyanates having different number average molecular weights, and a chain extender is added to the prepolymers to obtain a polyurethaneurea polymer. In the manufacturing method of the polyurethane urea elastic yarn which consists of:
The prepolymer is prepared by mixing a glycol having a low number average molecular weight of 800 ~ 1300 Dalton and a glycol having a high number average molecular weight of 1600 ~ 2000 Dalton in a mass ratio of 2: 1 to 7: 1. The manufacturing method of the polyurethane urea elastic yarn which has. 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 poly (tetramethylene ether) glycol, polypropylene glycol, polycarbonate diol, copolymer of a mixture of alkylene oxide and lactone monomer and poly (tetramethylene ether) glycol, or , 3-methyl-tetrahydrofuran and tetrahydrofuran copolymer of tetrahydrofuran is one or two or more selected from the group consisting of a method for producing a polyurethane urea elastic yarn having excellent power. 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.