KR101941317B1 - Polyurethaneurea elastic fiber with low temperature workability - Google Patents

Abstract

TECHNICAL FIELD The present invention relates to a low-temperature processable polyurethane-urea elastic yarn, and more particularly, to a process for producing a polyurethane-urea elastomeric yarn by a first-order polymerization of a polyol and a diisocyanate to form a prepolymer, the prepolymer, Wherein the first chain extender is at least one selected from aromatic, aliphatic and alicyclic amines, and the second chain extender is at least one selected from the group consisting of aromatic, aliphatic, And at least one selected from low-molecular-weight diols. The polyurethane-urea elastic yarn of the present invention improves yarn uniformity and workability and improves the heat setting property, so that thermal setting is performed at a low temperature so that thermal embrittlement of the counterpart yarn does not occur and the touch of the fabric can be improved And it is possible to prevent the change of the processed paper after heat setting.

Description

POLYURETHANEUREA ELASTIC FIBER WITH LOW TEMPERATURE WORKABILITY [0002]

The present invention relates to a low-temperature processable polyurethane-urea elastic yarn.

The polyurethaneurea is prepared by a first-stage polymerization reaction in which a polyol, which is a high molecular weight diol compound, is reacted with an excessive diisocyanate compound to obtain a prepolymer having isocyanate groups at both terminals of the polyol, And then adding a chain terminator such as a diamine type or diol type chain extender and a monoalcohol or monoamine to the solution and reacting the resultant solution to prepare a spinning solution of the polyurethaneurea fiber, followed by dry and wet spinning Lt; RTI ID = 0.0 > polyurethane < / RTI >

The polyurethane-urea fiber thus produced is crosslinked and knitted with polyamide fibers, polyester fibers, and natural fibers because of its inherent characteristics of high elasticity, and is actively used in a variety of clothing fields such as undergarments and sportswear. As a result of the enlargement, new additional characteristics of the existing fibers are continuously required.

In general, polyurethane urea fibers have a problem of thermal embrittlement of heat sensitive nylon, cotton, silk, wool, and the like in the post-processing after knitting with high heat setting temperature. There is an increasing demand for polyurethane-urea fibers that can be set at low temperatures to prevent such problems and to improve the shape of fabrics.

Conventional techniques for a polyurethane-urea fiber capable of setting at low temperatures can be understood by exemplifying the following Patent Document 1. As a result, all of the contents of Patent Document 1 are cited as prior arts in this specification.

Patent Document 1 discloses a spandex made of a mixture of 23 to 55 mol% of 2,4'-diphenylmethane diisocyanate and 4,4'-diphenylmethane diisocyanate, a polyether glycol and a chain extender, , When the content of 4'-diphenylmethane diisocyanate is greatly increased to 23 to 55 mol%, the thermosetting property of the polyurethane-urea elastic yarn is improved, but the modulus and elastic recovery rate are largely lowered and the yarn uniformity is insufficient. It is disadvantageous.

US Registration No. 6,472,494

An object of the present invention is to provide a polyurethane-urea elastic yarn having a characteristic of excellent heat settability at low temperatures.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art,

A polyol, and a diisocyanate are first polymerized to form a prepolymer,

A polyurethane-urea elastic yarn formed by secondary polymerization of the prepolymer, the first chain extender, and the second chain extender,

The first chain extender may be at least one selected from aromatic, aliphatic, and alicyclic amines,

The second chain extender is at least one selected from aromatic, aliphatic and low molecular weight diols.

In the present invention, the diisocyanate may be at least one selected from the group consisting of 4,4'-diphenylmethane diisocyanate, 1,5'-naphthalene diisocyanate, 1,4'-phenylene diisocyanate, hexamethylene diisocyanate, 1,4'- Wherein the polyurethaneurea is one selected from the group consisting of hexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate and isophorone diisocyanate.

 In the present invention, the polyol is at least one selected from polytetramethylene ether glycol, polypropylene glycol, and polycarbonate diol.

In the present invention, the first chain extender may be at least one selected from the group consisting of ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, Diaminopentane, 1,6-hexamethylenediamine, and 1,4-cyclohexanediamine. The polyurethaneurea elastic yarn is characterized in that it is at least one selected from the group consisting of polyoxyethylene, polyoxyethylene, 5-diaminopentane, 1,6-hexamethylene diamine and 1,4-cyclohexane diamine.

In the present invention, the second chain extender may be at least one selected from the group consisting of ethylene glycol, 1,2- and 1,3-propanediol, 1,4-butanediol, 2,2,4-trimethylpentane- , 6-hexanediol, 1,8-octanediol, and the like; Wherein the polyurethaneurea is at least one member selected from the group consisting of diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyoxyethylene diol, and polyoxypropylene diol.

The present invention also provides a polyurethane elastic fiber mixed knit fabric woven with a polyurethaneurea elastic yarn.

The polyurethane-urea elastic yarn of the present invention improves yarn uniformity and workability and improves the heat setting property, so that thermal setting is performed at a low temperature so that thermal embrittlement of the counterpart yarn does not occur and the touch of the fabric can be improved And it is possible to prevent the change of the processed paper after heat setting.

Hereinafter, the present invention will be described in detail.

In the present invention, a polyol and a diisocyanate are first polymerized to form a prepolymer,

A polyurethane-urea elastic yarn formed by secondary polymerization of the prepolymer, the first chain extender, and the second chain extender,

The first chain extender may be at least one selected from aromatic, aliphatic, and alicyclic amines,

Wherein the second chain extender is at least one selected from aromatic, aliphatic and low molecular weight diols.

The segment polyurethaneurea used in the production of the elastic yarn of the present invention is prepared by reacting an organic diisocyanate with a polymer diol to prepare a prepolymer, dissolving it in an organic solvent, and reacting it 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, 2,4'-diphenylmethane diisocyanate, 1,5'-naphthalene diisocyanate , 1,4'-phenylene diisocyanate, hexamethylene diisocyanate, 1,4'-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, etc. Among these diisocyanates, 4 , 4'-diphenylmethane diisocyanate may be used singly or in combination of two or more diisocyanates.

Further, the polymer diol may be exemplified by one kind of polytetramethylene ether glycol, polypropylene glycol, polycarbonate diol, or a mixture of two or more thereof.

As the chain extender, diamines or low molecular weight diols can be used.

Examples of the diamines include ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 2,3-diaminobutane, 1,5-diaminopentane, , 6-hexamethylenediamine, and 1,4-cyclohexanediamine, or a mixture of two or more thereof.

In order to control the molecular weight of the polyurethaneurea, amines having one functional group such as diethylamine, monoethanolamine, dimethylamine and the like can be used.

The low molecular weight diol component should have a molecular weight of 750 Da or less. Preferably, such a molecular weight is 500 Da or less, more preferably 200 Da or less. These low molecular weight components may be monomers, i.e. alkylene glycols, or oligomers, i.e. polyoxyethylene glycols or polyoxypropylene glycols. Preferably, low molecular weight glycol ethers such as diethylene glycol or triflophenylene glycol are used. Examples of suitable low molecular weight components include ethylene glycol, 1,2- and 1,3-propanediol, 1,4-butanediol, 2,2,4-trimethylpentane-1,5-diol, 1,6- Aliphatic glycols such as 1,8-octanediol and the like; Aliphatic ethers such as diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol and the like; Such as polyoxyethylene diols, polyoxypropylene diols, and block and irregular polyoxyethylene / polyoxypropylene diols having a molecular weight of 750 Da or less, preferably 500 Da or less, more preferably about 200 Da or less And oligomeric polyoxyalkylene. One or more low molecular weight diols may be used.

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 contain additives such as titanium dioxide, magnesium stearate and the like in addition to the above components.

Also, in the present invention, the chain extender is characterized by producing the polyurethaneurea elastomer produced by mixing the first chain extender and the second chain extender.

The first chain extender of the present invention may be one or more diamines such as ethylenediamine or 1,3-propanediamine, and the second chain extender may be one or more diethylene glycol or tri- Is characterized by the use of the same low molecular weight glycol ether.

Hereinafter, the present invention will be described in more detail by way of examples. The following examples are for the purpose of illustrating the present invention and are not intended to limit the scope of the present invention.

Example

In the following Examples and Comparative Examples, the NCO% measurement method of the polyurethaneurea polymer, the heat setting property of the yarn and the edge curl of the fabric were measured as follows.

* NCO % Measurement method

NCO% = [100 * 2 * NCO chemical formula * (capping ratio-1)] / {(diisocyanate molecular weight * capping ratio) + high molecular weight diol molecular weight}

In the above formula, the capping ratio is the diisocyanate molar ratio / the high molecular weight diol molar ratio.

* Of yarn Heat Set Sex

The initial yarn L0 was subjected to 100% elongation (L1) in a state exposed to the atmosphere, followed by dry heat treatment at 150 ° C for 1 minute, cooling to room temperature, and then 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

* 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.

* Cursive ( Curling )

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 a nylon yarn of 40 denier and a elastic yarn of 20 denier manufactured by the above, and the content of elastic yarn was 10% of the total knitted fabric weight.

The circular knitted fabric made of Nylon / polyurethane urea elastic yarn is pre-settled, dyed, and final-set. The side is marked with an equilateral triangle having a length of 5 cm, and then the two sides are cut An appropriate amount of water was sprayed on the fabric and then dried. It is calculated as the ratio of the area rolled up from the measuring fabric after drying and the area of the initial equilateral triangle.

Curling Percent% = (Area of curled triangle / area of original equilateral triangle) X 100

If the ratio of the area to be rolled up is within 10%, it generally means that the margin edging is good.

* Heat fusion force  Evaluation method

Nylon yarn 40 denier and pre-setting circular knitted fabric manufactured by a circular knitting machine having a diameter of 32 inches, a diameter of 28 gauge, and a feeder of 96 feeders using the elastic yarn 20 denier manufactured by the above. ), Dyeing and final-setting treatment, the presetting temperatures were treated at different treatment temperatures of 130 °, 150 °, 170 ° and 190 °, respectively.

The degree of thermal fusion between the elastic yarn and the elastic yarn and between the elastic yarn and NY yarn was visually evaluated while the fabrics were subjected to the heat treatment. The degree of thermal fusion was expressed as follows. When the yarn is completely bonded and the yarn is not fallen, it is "○". If the yarn is not fixed to each other and the yarn is not easily fixed, Quot; x ".< / RTI >

[ Example 1 ]

A first polymer was prepared by mixing polytetramethylene ether glycol having a capping ratio (CR) of 1.61 and a molecular weight of 1800 with 4,4'-diphenylmethane diisocyanate. Ethylene diamine was used as the first chain extender, ethylene glycol was used as the second chain extender, and diethylamine was used as the chain terminator. The ratio of the first chain extender and the second chain extender was set to 7: 3. The mixture of the first chain extender, the second chain extender and the chain termination agent used was adjusted to a total concentration of 7 mol% Dimethylacetamide was used as a solvent. That is, 35.2 g of polytetramethylene ether glycol having a molecular weight of 1800 and 7.8 g of methylene diisocyanate were reacted with stirring at 90 DEG C for 180 minutes in a nitrogen stream to prepare a polyurethane-urea prepolymer having isocyanates at both terminals.

After the prepolymer was cooled to room temperature, 55.3 g of dimethylacetamide was added to 43.1 g of the prepolymer to obtain a polyurethane-urea prepolymer solution. Then, 30.3 g of ethylenediamine, 4.3 g of diethylamine and 13.4 g of ethylene glycol were dissolved in 1860 g of dimethylacetamide and added to the prepolymer solution at 10 ° C or lower to obtain a polyurethaneurea solution.

1.5 wt% of ethylene bis (oxyethylene) bis- (3- (5-t-butyl-4-hydroxy-m-tolyl) -propionate) as an additive to the solids content of the polymer, 5,7- 0.5% by weight of 1,1,1 ', 1'-tetramethyl-4,4'- (methylene-di-p-butyl) -3- (3,4-dimethylphenyl) 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 1 filament was produced at a speed of 700 m / min by dry spinning of the fiber stock solution obtained as described above, and physical properties thereof were evaluated and shown in Table 1 below.

[ Example 2 ]

The polyurethaneurea elastic yarn was prepared in the same manner as in Example 1, except that the ratio of 1,3-propanediamine to ethylene glycol as the second chain extender was 7: 3 as the first chain extender.

[ Example 3 ]

The polyurethaneurea elastic yarn was prepared in the same manner as in Example 2, except that the capping ratio (CR) of the polytetramethylene ether glycol having a molecular weight of 1800 and 4,4'-diphenylmethane diisocyanate was changed to 1.7.

[ Example 4 ]

The polyurethaneurea elastic yarn was prepared in the same manner as in Example 3, except that the ratio of 1,3-propanediamine to ethylene glycol as the second chain extender was 5: 5.

[ Example 5 ]

Polyurethane-urea elastic yarn was prepared in the same manner as in Example 3, except that the ratio of 1,3-propanediamine to ethylene glycol as the second chain extender was 3: 7 as the first chain extender.

[ Example 6 ]

The capping ratio (CR) for mixing polytetramethylene ether glycol having a molecular weight of 1,800 and 4,4'-diphenylmethane diisocyanate was changed to 1.85, and the first chain extender was changed to 1,3-propanediamine to a second chain Polyurethaneurea elastic yarn was prepared in the same manner as in Example 1, except that the ratio of the polyurethane-urea elastomer to the ethylene glycol used as the extender was 7: 3.

[ Example 7 ]

Using the same method as in Example 6, the ratio of the first chain extender to 1,3-propanediamine to ethylene glycol as the second chain extender was 6: 4, the polyurethaneurea elastic yarn .

[ Comparative Example 1 ]

Was prepared under the same conditions as in Example 1, except that the second chain extender was not added. Namely, a capping ratio (CR) was 1.70, and 12.93 kg of 4,4'-diphenylmethane diisocyanate and 55.8 kg of polytetramethylene ether glycol (molecular weight 1,800) were reacted with stirring at 90 ° C for 90 minutes in a nitrogen gas stream A polyurethane-urea prepolymer having isocyanates at both terminals was prepared. After the prepolymer was cooled to room temperature, dimethylacetamide was supplied at 44.57 g / min and 65.66 g / min to obtain a polyurethane-urea prepolymer solution. Next, an amine solution prepared from 979 g of ethylenediamine, 119.1 g of diethylamine and 18.6 kg of dimethylacetamide was added to the prepolymer solution at 10 ° C or lower to obtain 122.8 g of polyurethaneurea solution per minute. Polyurethane-urea elastic yarn of 20 denier 1 filament was produced at a speed of 700 m / min by dry spinning of the fiber stock solution obtained as described above, and physical properties thereof were evaluated and shown in Table 1 below.

[ Comparative Example 2 ]

In the same manner as in Comparative Example 1, except that the second chain extender was not added, the carbonization ratio (CR) was 1.65, the ratio of ethylenediamine and 1,3-propanediamine was 8: 2, Elastic yarn was produced.

Unlike Comparative Example 1 and Comparative Example 2, the polyurethane-urea elastic yarn prepared by using the second chain extender such as the low molecular diol as shown in Table 1 was found to have an excellent heat setting property even at 150 degrees, It was confirmed that the difference in physical properties between the polyurethane-urea elastic yarn prepared using only the polyurethane-urea elastic yarn was not large.

As shown in Table 2, the fabric prepared from the yarns of Example 1, Example 2 and Example 3 in the production of the nylon circular knitted fabric had a heat setting temperature of about Even if the temperature is lowered by 30 ° C or more, the edge curl does not occur. As a result, Nylon does not cause thermal embrittlement, and the material of the fabric is very good and the cost is reduced by lowering the heat setting temperature.

As shown in Table 3, the polyurethane-urea elastic yarn produced by using diamines was almost not thermally fused, but in Examples 1, 2, 4, and 5 in which the low molecular weight diol was applied, Resulting in fusion. Also, as the content of low molecular weight diols increased, the heat resistance deteriorated, and at 170 degrees or higher, the polyurethane urea elastic yarn was brittle due to heat, and the heat fusion strength could not be confirmed.

Claims (6)

A polyol, and a diisocyanate are first polymerized to form a prepolymer,
A polyurethane-urea elastic yarn formed by secondary polymerization of the prepolymer, the first chain extender, and the second chain extender,
The first chain extender may be at least one selected from aromatic, aliphatic, and alicyclic amines,
The second chain extender is at least one selected from aromatic, aliphatic, and low molecular weight diols of 750 Da or less,
Wherein the polyurethane-urea elastic yarn does not cause edge curl of the fabric during production of the circular knitted fabric with the counterpart yarn, and the polyurethane-urea elastic yarn is excellent in thermal fusion strength at 130 to 190 占 폚. The method of claim 1, wherein the diisocyanate is selected from the group consisting of 4,4'-diphenylmethane diisocyanate, 1,5'-naphthalene diisocyanate, 1,4'-phenylene diisocyanate, hexamethylene diisocyanate, 1,4'- Wherein the polyurethaneurea is one selected from the group consisting of hexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate and isophorone diisocyanate. The polyurethane-urea elastic yarn according to claim 1, wherein the polyol is at least one selected from polytetramethylene ether glycol, polypropylene glycol, and polycarbonate diol. The method of claim 1, wherein the first chain extender is selected from the group consisting of ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 2,3- Diaminopentane, 1,6-hexamethylenediamine, and 1,4-cyclohexanediamine. The polyurethane-urea elastic yarn according to claim 1, The method of claim 1, wherein the second chain extender is selected from the group consisting of ethylene glycol, 1,2- and 1,3-propanediol, 1,4-butanediol, 2,2,4-trimethylpentane- , 6-hexanediol, 1,8-octanediol, and the like; Wherein the polyurethaneurea is at least one member selected from the group consisting of diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyoxyethylene diol, and polyoxypropylene diol. A polyurethane elastic fiber mixed knit fabric woven with a polyurethane-urea elastic yarn according to any one of claims 1 to 5.