KR101312843B1 - A Process for Preparing Polyurethaneurea Elastic Fiber having high Power and good recovery - Google Patents

Abstract

The present invention relates to a method for producing a polyurethane urea, more specifically, to prepare a prepolymer with a capping ratio (CR) of 1.50 ~ 1.60 using glycol and diisocyanate having a low number average molecular weight of 800-1300 Dalton The present invention relates to a method for producing a polyurethaneurea elastic yarn having excellent power by adding a chain extender to a prepolymer to obtain a polyurethaneurea polymer and then stirring and spinning the obtained polyurethaneurea spinning stock solution.

Description

A process for preparing Polyurethaneurea Elastic Fiber having high Power and good recovery}

The present invention relates to a method for producing a polyurethane urea, and more specifically, using a glycol and diisocyanate having a low number average molecular weight of 800-1300 Dalton to prepare a prepolymer with a capping ratio (CR) of 1.50 ~ 1.60, The present invention relates to a method of preparing a polyurethaneurea elastic yarn having excellent power by adding a chain extender to a prepolymer to obtain a polyurethaneurea polymer and 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 post-processing after knitting with other companies (nylon, cotton, silk, wool, etc.), which causes problems such as deterioration of power and resilience of the fabric. Let's go. In order to solve these problems, there is an increasing demand for polyurethane urea elastic fibers having excellent power and resilience. In particular, the use of denier elastic yarns to improve the power while reducing the weight of fabric during knitting and knitting Demand is increasing.

In response to the above problems, efforts have been made to improve the power 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 was invented to solve the above problems, the present invention is to prepare a prepolymer with a capping ratio (CR) of 1.50 ~ 1.60 using glycol and diisocyanate having a low number average molecular weight of 800-1300 Dalton, The purpose of the present invention is to provide a method for producing a polyurethane urea elastic yarn having excellent power by adding a chain extender to the prepolymer to obtain a polyurethane urea polymerized product, and then agitating and spinning the obtained polyurethane urea spinning solution. have.

According to the present invention, a method for preparing a polyurethane urea elastic yarn having excellent power is prepared by using a glycol and diisocyanate having a low number average molecular weight of 800-1300 Daltons with a capping ratio (CR) of 1.50 to 1.60, and After adding a chain extender to the polymer to obtain a polyurethane urea polymer, it is characterized in that the polyurethane urea spinning stock solution obtained by stirring it to mature and spin.

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 polytetramethylene ether glycol, polypropylene glycol, polycarbonate diol, a copolymer of polytetramethylene ether glycol with a mixture of alkylene oxide and lactone monomer, or It is 1 type, or 2 or more types chosen from the group which consists of modified polytetramethylene ether glycol which is a copolymer 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 resilience, by using the polyurethane urea elastic yarn to enable a high power of the cross-woven fabric. In addition, it is possible to reduce the weight of the fabric due to the improved modulus of the yarn, it is possible to increase the elasticity of the fabric with excellent recovery.

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 Examples of the modified polytetramethylene ether glycol, which is a copolymer of tetrahydrofuran, may be exemplified as one kind or a mixture of two or more kinds thereof, but are not necessarily limited thereto. The glycol used in the present invention is a glycol having a number average molecular weight of 800-1300 Daltons in molecular weight.

In the present invention, by using a glycol having a low number average molecular weight of 800-1300 Dalton, the amount of hard segment in the yarn is increased compared to the conventional one, and as the length of the soft segment in the yarn is shortened, the repeating unit of the hard segment is also increased. In addition, the capping ratio is lowered to suppress excessive hard segment increase, thereby obtaining a high elastic fiber having high resilience with power improvement effect. When the molecular weight is less than 800 Daltons, when the external stress is applied due to excessive increase of the hard segment, it is brittle and the solubility is lowered, making it impossible to apply the process. And elongation also has a problem that is greatly reduced. If the molecular weight exceeds 1300 Daltons, it is difficult to expect the effect of improving power and resilience.

In the present invention, to prepare a prepolymer of a glycol and diisocyanate having a number average molecular weight of 800-1300 Daltons with a capping ratio (CR) of 1.50 ~ 1.60, when the capping ratio is less than 1.50 there is a problem of insufficient power enhancement expression, the capping ratio is 1.60 If exceeded, there is a problem in process application due to solubility due to excessive increase of hard segments.

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 polyurethaneurea, amines having one functional group such as 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.

Further, the polyurethane-urea elastic yarn of the present invention may contain 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

* The strength 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 interwoven and knitted nylon / polyurethane urea elastic yarns, an automatic elongation measuring device (MEL machine, Textechno) is used. Sample width 2.5 cm * Sample length 20cm, tensile rate 100cm / min to measure 100% 5 times repeated elongation.

It was prepared using polytetramethylene ether glycol having a capping ratio (CR) of 1.55 and a molecular weight of 1000 Dalton, and 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 wt%, 1,1,1 ', 1'tetramethyl-4,4' (methylene-di- p -phenyl 1% by weight of ethylene) disemicarbazide, 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 polyurethaneurea spinning stock solution.

That is, 1250.0 g of polytetramethylene ether glycol having a molecular weight of 1000 was reacted with 484.9 g of 4,4 'diphenylmethane diisocyanate at 90 ° C. for 180 minutes in a nitrogen gas stream to prepare a polyurethane urea having an isocyanate at the sock end. It was. After cooling the prepolymer to room temperature, 3154.0 g of dimethylacetamide was added to obtain a polyurethaneurea prepolymer solution. Subsequently, 33.4 g of ethylenediamine, 10.3 g of 1,2-diopropane and 4.1 g of diethylamine were dissolved in 634.10 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.

It was prepared using polytetramethylene ether glycol having a capping ratio (CR) of 1.60 and a molecular weight of 1000 Dalton, and 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 -phenylene ) 1% by weight of dimicarbazide, 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 polyurethaneurea spinning stock solution.

That is, 1250.0 g of polytetramethylene ether glycol having a molecular weight of 1000 Daltons is reacted with 500.5 g of 4,4 'diphenylmethane diisocyanate and stirred for 90 minutes at 180 DEG C in a nitrogen gas stream to obtain a polyurethane urea having an isocyanate at the sock end. Prepared. After cooling the prepolymer to room temperature, 3138.8 g of dimethylacetamide was added to obtain a polyurethaneurea prepolymer solution. Subsequently, 36.4 g of ethylenediamine, 11.2 g of 1,2-diopropane and 4.4 g of diethylamine were dissolved in 691.7 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>

A capping ratio (CR) of 1.70 and a polyol were prepared using polytetramethylene ether glycol having a molecular weight of 1800 Dalton 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 -phenylene ) 1% by weight of dimicarbazide, 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 polyurethaneurea spinning stock solution.

That is, 319.1 g of 4,4 'diphenylmethane diisocyanate and 1350.0 g of polytetramethylene ether glycol having a molecular weight of 1800 are reacted with stirring at 90 ° C. for 180 minutes in a nitrogen gas stream to obtain a polyurethane urea having an isocyanate at the sock end. 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. .

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 &

A capping ratio (CR) of 1.80 and a polyol were prepared using polytetramethylene ether glycol having a molecular weight of 1800 Daltons 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 -phenylene ) 1% by weight of dimicarbazide, 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 polyurethaneurea spinning stock solution.

That is, 337.9 g of 4,4 'diphenylmethane diisocyanate and 1350.0 g of polytetramethylene ether glycol having a molecular weight of 1800 are reacted with stirring at 90 ° C. for 180 minutes in a nitrogen gas stream to form a polyurethane urea having an isocyanate at the sock end. Prepared. After cooling the prepolymer to room temperature, 3121.8 g of dimethylacetamide was added to obtain a polyurethaneurea prepolymer solution. Subsequently, 29.1 g of ethylenediamine, 9.0 g of 1,2-diopropane and 3.5 g of diethylamine were dissolved in 553.4 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 CR ratio NCO% burglar
[g / d] Shindo
[%] 200%
Modulus [g] 5'h
Unload at200% [g] Immediate Recovery [%] Example 1 1000 1.55 3.330 1.89 375 10.6 1.78 19.3 Example 2 1000 1.60 3.601 1.83 375 11.1 1.71 20.1 Comparative Example 1 1800 1.70 2.643 1.02 479 8.5 1.28 26.2 Comparative Example 2 1800 1.80 2.987 1.11 447 9.3 1.32 25.4

Polyuremethylene ether glycol and 4,4 'diphenylmethane isocyanate having a molecular weight of 1000 as shown in [Table 1] with a polyurethane urea elastic yarn prepared with a capping ratio (CR) of 1.50 to 1.60 shows excellent power and yarn recovery. I could confirm it.

Claims (4)

Polyurethane urea elastic yarn comprising preparing a prepolymer from a polyol and a diisocyanate polymer, adding a chain extender to the prepolymer to obtain a polyurethane urea polymer, and then aging and spinning the polyurethane urea spinning stock obtained by stirring the polymer. In the manufacturing method of
The prepolymer is a method for producing a polyurethane urea elastic yarn having excellent power, characterized in that formed by mixing a glycol and diisocyanate having a number average molecular weight of 800 ~ 1300 Dalton in a capping ratio (CR) of 1.50 ~ 1.60. delete The polyol according to claim 1, wherein the polyol used in the prepolymer is a polytetramethylene ether glycol, polypropylene glycol, polycarbonate diol, a copolymer of an alkylene oxide and a lactone monomer and a polytetramethylene ether glycol, or 3-methyl -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 modified polytetramethylene ether glycol which is a copolymer of 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.