WO2015088059A1 - Polyurethaneurea elastic yarn having improved thermosetting properties, and production method therefor - Google Patents

Abstract

The present invention provides a polyurethaneurea elastic yarn having improved thermosetting properties and comprising: poly(tetramethylene ether) glycol; one or more kinds of organic diisocyanates selected from among aromatic, aliphatic, and alicyclic diisocyanates; a chain extender; and a chain terminator including n-butylamine.

Description

Polyurethane urea elastic yarn with improved heat setability and manufacturing method

The present invention relates to a method for producing a polyurethane urea elastic yarn having excellent heat setability, and more particularly, by using butylamine as a chain terminator, it is possible to improve the problem of the thermal withdrawal of the thermally sensitive partner yarns, The present invention relates to a polyurethaneurea elastic yarn having improved heat setability capable of minimizing changes due to the present invention and a method of manufacturing the same.

In general, polyurethaneurea obtains a prepolymer by reacting a polyol with an excess of diisocyanate compound, and makes an elastic yarn by spinning after making a spinning stock solution of polyurethaneurea fiber through an appropriate reaction to the prepolymer.

These polyurethaneurea elastic yarns are actively used for various uses because of their inherent characteristics of high elasticity, and as the use range thereof is expanded, new additional characteristics of existing fibers are continuously required.

In general, the elastic yarn may exhibit physical properties such as strength and modulus of yarn due to post-polymerization process over time, while reducing elongation of yarn and physical properties such as Max DR.

In particular, when using a mixture of yarns with different production times, there was a problem of causing a difference in the degree of set of the fabric and streaks of the fabric.

The present invention is to solve the above-mentioned problems, the main purpose is to improve the streak generation and quality of the fabric by producing a polyurethane urea elastic yarn having excellent heat setability and little change in physical properties over time have.

One aspect of the present invention, poly (tetramethylene ether) glycol; One or two or more organic diisocyanates selected from aromatic, aliphatic and alicyclic diisocyanates; Chain extenders; And chain dispersants including n-butylamine; It provides a polyurethane urea elastic yarn improved heat setability comprising a.

Another aspect of the invention, the first step of polymerizing the polyol and diisocyanate to obtain a prepolymer; Dissolving the prepolymer in an organic solvent and adding a chain extender and a chain terminator to perform secondary polymerization to obtain a spinning stock solution; And drying or wet spinning the spinning stock solution to obtain a polyurethaneurea elastic yarn; Wherein the diisocyanate comprises one or two or more organic diisocyanates selected from aromatic, aliphatic and cycloaliphatic diisocyanates, and the chain terminator is n-butylamine-enhanced thermosettable polyurethane Provided is a method for producing a urea elastic yarn.

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

According to an embodiment of the present invention, by using n-butylamine as a chain terminator, heat-setability is excellent even at low temperature, and heat-sensitive fibers are heat-set by performing heat setting at low temperature on the heat-sensitive fibers and interwoven fabrics. It does not embrittle, and the change of yarn properties with the change over time has the effect of preventing edge curling or streaks in the fabric.

The best mode of the present invention was the elastic yarns of Examples 1-3.

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

The embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

In addition, the inclusion of any component throughout the specification means that it may further include other components, except to exclude other components unless specifically stated otherwise.

The elastic yarn according to one embodiment of the present invention is first polymerized with a high molecular weight polyol to an excess of diisocyanate to obtain a prepolymer.

Next, after dissolving the prepolymer in an organic solvent, a chain extender and a chain terminator are added to the solution to perform secondary polymerization to prepare a spinning stock solution. At this time, the chain extender and chain stopper may be added all at once or in two or more steps.

Next, a polyurethane urea elastic yarn is manufactured by dry spinning or wet spinning the spinning solution.

The diisocyanate used in this embodiment is one or two or more organic diisocyanates selected from aromatic, aliphatic and alicyclic diisocyanates, such as 4,4'-ditenylmethane diisocyanate, 2,4'-diphenylmethane Diisocyanate, 1,5'-naphthalene diisocyanate, 1,4'-phenylenedi isocyanate, hexamethylene diisocyanate, 1,4'-cyclohexanediisocyanate, 4,4'-dicyclohexyl methane diisocyanate, isophorone Diisocyanate and the like.

In general, 2,4'-MDI has a three-dimensional structure is weakened between the intramolecular hydrogen bonds or intramolecular hydrogen bonds in the hard segment, thereby exhibiting the same effect as increasing the content of the soft segment To this end, a large number of soft domains are formed, thereby obtaining an elastic yarn having excellent setability.

The polyol usable in the present invention may illustrate at least one or more 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 500 to 8000, more preferably 1200 to 3000.

Diamines used in the chain extender include ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 2,3-diaminobutane, 1,5-di One or two or more mixtures selected from aminopentane, 1,6-hexamethylenediamine, 1,4-cyclohexanediamine and the like can be exemplified, but the present invention is not limited thereto.

On the other hand, a chain terminator is used to control the molecular weight of polyurethaneurea. When only diethylamine is used as a conventional terminator, the postpolymerization time and post-calcination time are increased according to the high calorific value during the spinning process. Due to the post-polymerization process over time, the physical properties such as the strength and modulus of the yarn may be expressed, while the elongation, the Max DR, and the properties of the yarn may decrease.

In addition, the use of different yarns in the production time may cause a difference in the degree of set of fabric and streaks of the fabric.

Therefore, in the present embodiment, n-butylamine is used as a chain terminator, and since the n-butylamine minimizes the change of physical properties due to postpolymerization to improve thermosetability, heat setting is performed at low temperature. Even if the other party's thermal withdrawal does not occur, the appearance of the fabric can be improved as compared with the conventional one, and the curled paper can be prevented from occurring in the processed paper after heat setting.

In this case, the chain terminator may preferably comprise 10 to 80 mol% of n-butylamine relative to the total chain terminator.

If the amount of the chain terminator is less than 10 mol%, it is not possible to control the promotion of the postpolymerization due to the excess diethylamine, and if the amount of the chain terminator is more than 80 mol%, It may be concerned that the rise in polymer viscosity for modulus and spinning is suppressed.

In addition, in the present invention, in order to prevent discoloration of the polyurethane urea and degradation of physical properties due to ultraviolet rays, atmospheric smog, heat treatment process associated with spandex processing, etc., the steric hindrance phenol compound, benzofuran-one compound, semicarbazide, etc. 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 further include additives such as titanium dioxide and magnesium stearate, antioxidants, dyeing enhancers, thermal oxidation stabilizers, antibacterial agents, light stabilizers or antistatic agents, if necessary. There is no particular limitation on the method of adding these other additives, and conventional methods such as titration mixing can be used.

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

Example 1:

Capping ratio (CR) was prepared at a content of 1.65, 5 mol% of 2,4'-diphenylmethane diisocyanate and 95 mol% of 4,4'-diphenylmethane diisocyanate. The chain extender used ethylenediamine and 1,2-diamino propane mentioned above, and the chain stopper used diethylamine and n-butylamine. The ratio of chain extender and chain dispersant was 12.5: 1, the ratio of ethylenediamine and 1,2-diamino propane was 80 mol% and 20 mol%, and the ratio of n-butylamine and diethylamine was 10. It was set as mol% and 90 mol%. The amine used was prepared in a total concentration of 7 mol%, and dimethylacetamide was used as a 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.

The spinning stock solution obtained as described above was prepared by 20 spines of polyurethane urea elastic yarn at a speed of 900 m / min by dry spinning, and the physical properties are shown in Table 1 and Table 2 below.

Example 2:

A polyurethaneurea elastic yarn was prepared in the same manner as in Example 1, except that the polyurethaneurea polymer was prepared in a ratio of 50 mol% of n-butylamine and diethylamine and 50 mol% of diethylamine. The physical properties were evaluated and 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 the polyurethane urea polymer was prepared in a ratio of 80 mol% of n-butylamine and diethylamine and 20 mol% of diethylamine. The physical properties were evaluated and shown together in Tables 1 and 2 below.

Comparative Example 1:

Without the addition of n-butylamine, it was prepared under the same conditions as in Example 1 except that 20 denia polyurethane urea elastic yarn was prepared at a speed of 900 m / min.

Comparative Example 2:

100 mol% of n-butylamine was added, and it manufactured by the same conditions as Example 1 except having manufactured 20 denia polyurethane urea elastic yarn at a speed | rate of 900 m / min.

* 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. In addition, the elongation was measured over time.

* Heat Setability of Yarn

The initial yarn (L0) was 100% elongated (L1) while exposed to the atmosphere, and then subjected to dry heat treatment at 170 ° C. for 1 minute, cooled to room temperature, and then the length (L2) of the yarn was measured. Dry heat-treated yarn was moist heat treated at 100 ° C. for 30 minutes in a relaxed state and dried at room temperature to measure the length (L3) of the yarn, and the dry heat setability and heat set efficiency (HSE) of the yarn was calculated according to the following equation. It was.

Dry Heat Setability (%) = {(L2-L0) / (L1-L0)} X 100

HSE (%) = {(L3-L0) / (L1-L0)} X 100

Lab. Viscosity elapsed rate

The polymer of viscosity 2000 Poise, prepared according to the type and content of chain extenders and different chain dispersants, was stirred at 8 rpm for 72 hours using a double helical stirrer after adding 700 g to a laboratory reactor. . At this time, 40 degrees of water was passed through the laboratory reactor, and the viscosity was measured every 24 hours to measure the viscosity lapse rate, and the viscosity lapse rate was calculated by the difference between the viscosity (V1) and the initial viscosity (V0, 2000 Poise) after 72 hours. .

Viscosity Tracing Rate (Poise / hr) = (V1-V0) / 72hr

* Flight Rating

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. This circular knitted fabric was knitted using 100 denier of PET yarn and 20 denier of elastic yarn prepared above, and the content of the 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 and knitted PET / polyurethane urea elastic yarn, the quality of circular knitting fabric of 5m was evaluated. same.

3mm or more streak: -10 points

2 ~ 3mm streaks: -5 points

1mm streak: -1 point

Table 1

	Strength [g / d]	Elongation [%]	Modulus [g]	HSE [%]	Lab. Viscosity lapse rate [P / hr]	Grade score [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

TABLE 2

	Time	burglar	Shinto	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

It is intended that the present invention not be limited by the above embodiments, but rather by the claims appended hereto.

Accordingly, various forms of substitution, modification, and alteration may be made by those skilled in the art without departing from the technical spirit of the present invention described in the claims, which are also within the scope of the present invention. something to do.

According to the present invention, a polyurethane urea elastic yarn having improved heat setability can be obtained.

Claims (4)

1. Poly (tetramethylene ether) glycol;

   One or two or more organic diisocyanates selected from aromatic, aliphatic and alicyclic diisocyanates;

   Chain extenders; And

   chain terminators including n-butylamine; Polyurethane urea elastic yarn improved heat setability, including.
2. The method of claim 1,

   The chain dispersant is a polyurethane urea elastic yarn with improved heat setability, characterized in that it comprises 10 to 80 mol% of n-butylamine with respect to the total chain dispersant.
3. First polymerizing the polyol and the diisocyanate to obtain a prepolymer;

   Dissolving the prepolymer in an organic solvent and adding a chain extender and a chain terminator to perform secondary polymerization to obtain a spinning stock solution; And

   Dry or wet spinning the spinning stock solution to obtain a polyurethaneurea elastic yarn; Including;

   The diisocyanate includes one or two or more organic diisocyanates selected from aromatic, aliphatic and alicyclic diisocyanates,

   The chain terminating agent is a method for producing a polyurethane urea elastic yarn improved thermosetability comprising n-butylamine.
4. The method of claim 3,

   The chain dispersant comprises 10 to 80 mol% of n-butylamine with respect to the total chain dispersant, characterized in that the thermosetability improved polyurethane urea elastic yarn manufacturing method.