KR101396107B1 - Polyurethaneurea elastic fiber with improved heat setting property and manufacturing method thereof - Google Patents

Abstract

The present invention relates to poly (tetramethylene ether) glycol; One or more organic diisocyanates selected from aromatic, aliphatic and alicyclic diisocyanates; Chain extenders; And n-butylamine; To provide a polyurethane urea elastic yarn with improved heat set properties.

Description

TECHNICAL FIELD [0001] The present invention relates to a polyurethane-urea elastic yarn having improved heat set properties, and a method for producing the same.

The present invention relates to a process for producing a polyurethane-urea elastic yarn excellent in heat setting property, and more particularly, to a process for producing a polyurethaneurea elastic yarn excellent in heat setting property by using butylamine as a chain endbearing agent, To a polyurethane-urea elastic yarn having improved heat setting properties and a method for producing the same.

Generally, a polyurethane urea is obtained by reacting a polyol with an excess of a diisocyanate compound to obtain a prepolymer, and a spinning solution of the polyurethane-urea fiber is prepared by appropriately reacting with the prepolymer, followed by spinning to obtain a elastic yarn.

These polyurethane-urea elastic yarns are actively used for various purposes because of their inherent characteristics with high elasticity, and as the range of use thereof is expanded, new additional characteristics are continuously required in existing fibers.

In general, the elastic yarn exhibits an increase in strength and modulus of the yarn due to the polymerization process after a lapse of time, while the physical properties such as elongation and Max DR of the yarn may be reduced.

Particularly, when yarns having different production periods are mixed and used, there is a problem that the difference in the degree of the set of the fabric and the streak of the fabric are caused.

Disclosure of Invention Technical Problem [8] The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a polyurethane-urea elastic yarn excellent in heat setting property and little change in physical properties with time, have.

One aspect of the present invention relates to a poly (tetramethylene ether) glycol; One or more organic diisocyanates selected from aromatic, aliphatic and alicyclic diisocyanates; Chain extenders; And n-butylamine; To provide a polyurethane urea elastic yarn with improved heat set properties.

Another aspect of the present invention relates to a process for producing a prepolymer, comprising the steps of: first polymerizing a polyol and a diisocyanate to obtain a prepolymer; Dissolving the prepolymer in an organic solvent, adding a chain extender and a chain terminator to perform a secondary polymerization to obtain a spinning solution; And dry or wet spinning the spinning solution to obtain a polyurethane-urea elastic yarn; Wherein the diisocyanate comprises one or more organic diisocyanates selected from aromatic, aliphatic and alicyclic diisocyanates, and the chain terminator comprises at least one polyisocyanate selected from the group consisting of polyurethane A process for producing urea elastic yarn is provided.

In one embodiment of the present invention, the chain terminator may comprise 10 to 80 mol% of n-butylamine.

According to one embodiment of the present invention, by using n-butylamine as the chain terminator, heat setting is performed at low temperature at a low temperature by performing heat setting at a low temperature so as to fabricate a fabric that is sensitive to heat and sensitive to heat, So that there is an effect that there is little change in the physical properties of the yarn due to a change over time, and no curling or streaking occurs in the knitting fabric.

Hereinafter, preferred embodiments of the present invention will be described. However, the embodiments of the present invention can be modified into various other forms, and the scope of the present invention is not limited to the embodiments described below.

Embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art.

In addition, to include an element throughout the specification does not exclude other elements unless specifically stated otherwise, but may include other elements.

In the elastic yarn according to one embodiment of the present invention, a prepolymer is obtained by first polymerizing an excess of diisocyanate with a high molecular weight polyol.

Next, after dissolving the prepolymer in an organic solvent, a chain lengthener and a chain terminator are added to the solution, and a secondary polymerization is carried out to prepare a spinning solution. At this time, the chain extender and the chain extender may be added all at once or in two or more stages.

Next, the spinning stock solution is dry-spun or wet-spun to produce a polyurethane-urea elastic yarn.

The diisocyanate used in this embodiment is one or more organic diisocyanates selected from aromatic, aliphatic and alicyclic diisocyanates, and examples thereof include 4,4'-ditenylmethane diisocyanate, 2,4'-diphenylmethane Diisocyanate, 1,5'-naphthalene diisocyanate, 1,4'-phenylene diisocyanate, hexamethylene diisocyanate, 1,4'-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone Diisocyanate, and the like.

In general, the 2,4'-MDI has a stereostructure, and exhibits the same effect as increasing the content of the soft segment by weakening the intermolecular hydrogen bond or the intramolecular hydrogen bond in the hard segment , And a lot of soft domains are formed thereon, so that an elastic yarn having excellent set property can be obtained.

The polyol usable in the present invention may be at least one selected from the group consisting of polytetramethylene ether glycol, polypropylene glycol, polycarbonate diol, and combinations thereof, but the present invention is not limited thereto. The molecular weight of the polyol may be from 500 to 8000, and more preferably from 1200 to 3000. [

The diamines used in the chain extender may be selected from the group consisting of ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 2,3-diaminobutane, Aminopentane, 1,6-hexamethylenediamine, 1,4-cyclohexanediamine, and the like, and the present invention is not limited thereto.

On the other hand, a chain terminator is used to control the molecular weight of the polyurethaneurea. When diethylamine alone is used as the chain terminator, an increase in post polymerization and a post- The physical properties such as yarn elongation, Max DR, and set properties can be reduced while the post-polymerization process over time causes increase in the physical properties such as strength and modulus of the yarn.

In addition, when mixed yarns having different production periods are used, the difference in the set of the fabric and the streak of the fabric can be caused.

Thus, in the present embodiment, n-butylamine is used as the chain terminator, and the n-butylamine improves the heat setting property by minimizing the change of physical properties due to the post polymerization, so that the heat setting is performed at a low temperature The thermal decoupling of the opponent yarn does not occur, so that the state of the fabric can be improved as compared with the conventional method, and occurrence of curling in the processed paper after the heat setting can be prevented.

At this time, the chain terminator may preferably include 10 to 80 mol% of n-butylamine with respect to the full-chain terminator.

If the amount of the chain terminator used is less than 10 mol%, the promotion of the post polymerization may not be controlled due to excessive diethylamine. If the amount of the chain terminator used exceeds 80 mol%, excessive polymerization may be inhibited It may be feared that the polymer viscosity rise for modulus and radiation is suppressed.

In addition, in the present invention, in order to prevent discoloration and deterioration of physical properties of polyurethane-urea by heat treatment accompanying ultraviolet rays, atmospheric smog, and spandex processing, it is preferable to add a phenolic compound, a benzofuran- Based compound, a benzotriazole-based compound, a polymeric tertiary amine stabilizer, and the like.

Further, the polyurethane-urea elastic yarn of the present invention may further contain additives such as titanium dioxide, magnesium stearate and the like, an antioxidant, a dyeability-improving agent, a thermal oxidation stabilizer, an antibacterial agent, a light stabilizer or an antistatic agent. There is no particular limitation on the method of adding these other additives, and conventional methods such as proper mixing can be used.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples.

Example 1:

A capping ratio (CR) of 1.65, a content of 5 mol% of 2,4'-diphenylmethane diisocyanate and a content of 4,4'-diphenylmethane diisocyanate of 95 mol%. The chain extender used was the above-mentioned ethylenediamine and 1,2-diaminopropane, and the chain terminator used was diethylamine and n-butylamine. The ratio of the chain extender and the chain terminator was 12.5: 1, the ratio of ethylenediamine to 1,2-diaminopropane was 80 mol% and 20 mol%, the ratio of n-butylamine and diethylamine was 10 Mol% and 90 mol%, respectively. The amine used was adjusted to 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.

Polyurethane-urea elastic yarn of 20 denier was produced at a speed of 900 m / min by dry spinning the fiber stock solution obtained as described above, and physical properties thereof were evaluated and shown in the following Tables 1 and 2.

Example 2:

A polyurethane-urea elastic yarn was prepared in the same manner as in Example 1, except that a polyurethane-urea polymer was produced in a proportion of 50 mol% of n-butylamine and diethylamine and 50 mol% of diethylamine, The properties thereof were evaluated and are shown together in Tables 1 and 2 below.

Example 3:

A polyurethane urea elastic yarn was prepared in the same manner as in Example 1, except that a polyurethane urea polymer was produced in a proportion of 80 mol% of n-butylamine and diethylamine and 20 mol% of diethylamine, The properties thereof were evaluated and are shown together in Tables 1 and 2 below.

Comparative Example 1:

except that n-butylamine was not added and 20 denier polyurethane-urea elastic yarn was produced at a speed of 900 m / min.

Comparative Example 2:

except that n-butylamine was added in an amount of 100 mol% and 20 denier polyurethane-urea elastic yarn was produced at a rate of 900 m / min.

* 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. We also measured the strength over time.

* Thermal set of yarns

The initial yarn L0 was subjected to 100% elongation (L1) in a state exposed to the atmosphere, followed by dry heat treatment at 170 ° C for 1 minute, cooling to room temperature and measuring the length (L2) of the yarn. Dry heat treated yarn is heat treated at 100 ℃ for 30 minutes in a relaxed state and then dried at room temperature to measure the length (L3) of the yarn and calculate the heat set efficiency and heat setting efficiency (HSE) of the yarn according to the following formula Respectively.

Dry heat setting property (%) = {(L2-L0) / (L1-L0)} X 100

HSE (%) = {(L3-L0) / (L1-L0)} X100

* Lab . Viscosity aging rate

The polymer having a viscosity of 2000 Poise prepared according to the type and content of the chain extender and the different chain terminators was added to the laboratory reactor in an amount of 700 g and stirred at a speed of 8 rpm for 72 hours with a double helical type stirrer . At this time, 40 ° C. water was passed through the laboratory reactor, and the viscosity was measured every 24 hours to measure the viscosity retention rate. The viscosity retention rate was calculated by the difference between the viscosity (V1) and the initial viscosity (V0, 2000 Poise) .

Viscosity Loss Percentage (Poise / hr) = (V1-V0) / 72hr

* Evaluation of recycled products

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 knitted fabric was knitted using PET yarn 100 denier and elastic yarn 20 denier manufactured by the above, and the content of elastic yarn was 8% to be.

The circular knitted fabrics made of cross-linked PET / polyurethane urea elastic yarn were subjected to pre-setting, dyeing and final-setting, and then evaluated for the quality of the circular knitted fabric of 5 m. same.

3mm or more streak: -10 points

Streak less than 2 ~ 3mm: -5 points

1 mm streak: -1 point

burglar
[g / d] Shindo
[%] Modulus
[g] HSE
[%] Lab. Viscosity over time [P / hr] Grade point
[point] Example 1 1.18 503 4.0 56 53 84 Example 2 1.20 512 4.0 60 52 87 Example 3 1.18 515 3.8 67 53 86 Comparative Example 1 1.20 495 4.0 50 52 80 Comparative Example 2 1.23 545 3.3 72 23 87

Hourly Time burglar Shindo 200% M HSE (%) Example 1 0 days 1.18 503 4.0 56 10 days 1.20 506 4.0 56 30 days 1.19 505 4.0 56 Example 2 0 days 1.20 512 4.0 60 10 days 1.20 511 4.1 59 30 days 1.21 514 4.0 60 Example 3 0 days 1.18 515 3.9 67 10 days 1.17 515 4.0 66 30 days 1.19 518 3.9 66 Comparative Example 1 0 days 1.20 495 4.0 50 10 days 1.25 480 4.2 48 30 days 1.28 472 4.3 46 Comparative Example 2 0 days 1.23 545 3.3 72 10 days 1.22 543 3.4 70 30 days 1.22 548 3.3 71

The present invention is not limited to the above-described embodiments but is intended to be limited by the appended claims.

It will be apparent to those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. something to do.

Claims (4)

Poly (tetramethylene ether) glycol;
One or more organic diisocyanates selected from aromatic, aliphatic and alicyclic diisocyanates;
Chain extenders; And
In the polyurethane-urea elastic yarn comprising a chain ending agent,
Wherein the chain terminating agent is a mixture of n-butylamine and diethylamine in an amount of 10 mol% to 80 mol% and 20 mol% to 90 mol%, and is used together. The thermosetting polyurethane Urea. delete Polymerizing a polyol and a diisocyanate to obtain a prepolymer;
Dissolving the prepolymer in an organic solvent, adding a chain extender and a chain terminator to perform a secondary polymerization to obtain a spinning solution; And
A method for producing a polyurethane-urea elastic yarn by dry or wet spinning the spinning solution,
Wherein the chain terminating agent is a mixture of n-butylamine and diethylamine in an amount of 10 mol% to 80 mol% and 20 mol% to 90 mol%, and is used together. The thermosetting polyurethane Method of manufacturing urea elastic yarn.
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