KR20120078361A - Manufacturing method of polyurethaneurea elastic fiber by high speed spinning method - Google Patents

Abstract

PURPOSE: A method for fabricating polyurethane urea elastic yarn is provided to enhance productivity without reduction of grey yarn physical property. CONSTITUTION: A method for fabricating polyurethane urea elastic yarn comprises: a step of primarily polymerizing polyol and excessive amount of diisocyanate to prepare a prepolymer; and a step of dissolving the prepolymer in organic solvent and adding chain extender for secondary polymerization to prepare polyurethane urea. The diisocyanate includes first diisocynate and second diisocyanate. The first diisocyanate is organic diisocyanate of aromatic group, aliphatic group, or cycloaliphatic group. The second diisocyanate is 1,4-bis(isocyanatomethyl)cyclohexane.

Description

 Manufacturing method of polyurethaneurea elastic fiber by high speed spinning method

The present invention relates to an elastic yarn comprising a polyol, a first diisocyanate, a second diisocyanate and a polyurethane urea based on a chain extender, wherein the first diisocyanate is one selected from aromatic, aliphatic and alicyclic diisocyanates or Two or more organic diisocyanates, the second diisocyanate is 1,4-bis (isocyanatomethyl) cyclohexane (1,4-H ₆ XDI), and the second diisocyanate is about 2 to about 2 of the total diisocyanates Containing about 25 mol%, even if high-speed spinning, the present invention relates to a method for producing high-speed spinning polyurethane urea elastic yarn similar to the existing elongation properties.

Polyurethane urea is a first polymerization reaction in which a polyol, which is a high molecular weight diol compound, and an excess of a diisocyanate compound to obtain a prepolymer having an isocyanate group at the end of the polyol, and the prepolymer is dissolved in a suitable solvent. After the diamine-based or diol-based chain extender is added to the solution and the chain terminators such as monoalcohol or monoamine are reacted, the spinning solution of the polyurethaneurea fiber is made and then subjected to dry and wet spinning. Elastic fibers are obtained.

Polyurethane urea fibers are actively used for various applications because of their inherent characteristics with high elasticity, and as the range of applications thereof expands, new additional characteristics of existing fibers continue to be demanded.

In the case of elastic fibers, manufacturing is performed by dry or wet spinning, but wet spinning is inevitably produced at a lower speed than dry spinning due to the process characteristics. In addition, dry spinning is not applicable to solids below 37% (excess solvent) due to the problem of solvent drying in high speed production. On the contrary, when solid content of more than 37% (solvent reduction) is advantageous in terms of drying, a gel or the like may be formed due to a sharp rise in the viscosity of the polymer.

In dry spinning, an elastic yarn may be manufactured by passing a polymer solution including a polymer and a solvent into a spinning chamber through a spinneret and twisting the spinneret. At this time, the gas passes through the chamber to evaporate the solvent contained in the polymer solution to prepare the elastic yarn.

The productivity of dry spinning is typically related to the winding speed, the denia of the yarn being produced and the number of yarn ends per chamber. However, these parameters are limited by the solvent and volume used in the polymer solution and the rate of solvent evaporation through each filament surface.

That is, during high-speed spinning, the solvent should be able to evaporate sufficiently in the spinning chamber, and the influence of the degree of orientation, which depends on the winding speed, the elongation in the yarn properties, the modulus, etc. should be considered.

In the present invention, in preparing a polyurethaneurea elastic yarn, the diisocyanate used in the manufacturing process includes a first diisocyanate and a second diisocyanate, and the first diisocyanate is selected from aromatic, aliphatic and alicyclic diisocyanates. Species or two or more organic diisocyanates, the second diisocyanate is 1,4-bis (isocyanatomethyl) cyclohexane, and the second diisocyanate is high-speed spinning by mixing about 2 to about 25 mole percent of the total diisocyanate Even if it is characterized by manufacturing high-speed spinning elastic yarn, which can obtain elongation properties similar to the existing.

The present invention is to produce a high-speed spinning polyurethane urea elastic yarn, it is possible to increase the productivity without lowering the yarn physical properties.

Hereinafter, the method of manufacturing the polyurethaneurea elastic yarn of this invention is demonstrated in detail. The segmented polyurethaneurea used in the preparation 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 then reacting with a diamine and a monoamine.

The diisocyanate used in the production of the polyurethaneurea elastic yarn used in the present invention includes a first diisocyanate and a second diisocyanate. The first diisocyanate is one or two or more organic diisocyanates selected from aromatic, aliphatic and alicyclic diisocyanates, specifically 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate , 1,5'-naphthalene diisocyanate, 1,4'-phenylene diisocyanate, hexamethylene diisocyanate, 1,4'-cyclohexane diisocyanate, 4,4'-dicyclohexyl methane diisocyanate, isophorone diisocyanate Etc. These may be used alone or in combination of two or more thereof.

The second diisocyanate is a diisocyanate having a steric structure different from that of the first diisocyanate, specifically 1,4-bis (isocyanatomethyl) cyclohexane (1,4-H ₆ XDI), and this content is 2 to 25 mole% of the total diisocyanate is appropriate.

In general, when producing a polyurethane urethane elastic yarn, 4,4'- diphenylmethane diisocyanate is used due to the physical properties of the fiber. However, the second diisocyanate used in a small amount in the invention has a three-dimensional structure different from that of the existing 4,4'-diphenylmethane diisocyanate. Hydrogen bonds are formed in a coarse shape, and have substantially the same effect as an increase in the content of the soft segment rather than the hard segment. Therefore, by forming a large number of soft domains (elastic fibers) excellent in elongation can be obtained, and even if the additional winding speed can be increased to prevent the physical properties of the elongation. If the content of the second diisocyanate is less than 2%, the effect of improving elongation is insufficient. If the content of the second diisocyanate is more than 25 mol%, the yarn modulus may sharply decrease.

In addition, the polymer diol may be exemplified as one kind or a mixture of two or more kinds thereof in polytetramethylene ether glycol, polypropylene glycol, polycarbonate diol and the like.

The chain extender in the present invention employs a chain extender mixture comprising at least about 80 mole percent of the total moles of the chain extender and a second chain extender other than ethylene diamine.

As the chain extender, a chain extender mixture comprising at least about 80 mole% of the total number of moles of the chain extender and a second chain extender other than ethylene diamine is used.

Second chain extenders include 1, 2-diaminopropane, 1, 3-diaminopropane, 1,4-diaminobutane, 2,3-diaminobutane, 1,5-diaminopentane, 1, 6 -1 type, or 2 or more types of these mixtures, such as hexamethylenediamine and 1, 4- cyclohexanediamine, are mentioned. Here, ethylene diamine is used more than 80 mol%, because if the content of ethylene diamine is 80 mol% or less may lower the heat resistance.

Generally diamines used as chain extenders are ethylenediamine, 1, 2-diaminopropane, 1, 3-diaminopropane, 1,4-diaminobutane, 2,3-diaminobutane, 1,5-di One kind or a mixture of two or more kinds thereof, such as aminopentane, 1, 6-hexamethylenediamine and 1,4-cyclohexanediamine, can be exemplified.

In order to control the molecular weight of the polyurethaneurea, amines 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 and deterioration of the physical properties of the polyurethane urea due to ultraviolet rays, atmospheric smog, heat treatment process associated with spandex processing, etc., the steric hindrance phenol compound, benzofuran-one compound, and semicarbazide in the spinning stock solution. 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 more detail with reference to examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.

In Examples and Comparative Examples to be described later, the NCO% measurement method of the polyurethaneurea polymer and the elongation evaluation of yarn 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.

* 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.

Capping ratio (CR) 1.70, 1,4-bis (isocyanatomethyl) cyclohexane (1,4-H ₆ XDI) 2 mol% content and 4,4'- diphenylmethane diisocyanate 98 mol% It was. Ethylenediamine and 1,2-diaminopropane were used as the chain extender, and diethylamine was used as the chain terminator. The ratio of the chain extender and the chain terminator was 12.5: 1, and the ratio of ethylenediamine and 1,2-diaminopropane was 80 mol% and 20 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 polyurethane spinning yarn of 40 denia 3 filament at a speed of 1100 m / min by dry spinning, the physical properties are shown in Table 1 below.

Except that the polyurethaneurea polymer was prepared at a ratio of 5 mol% of 1,4-bis (isocyanatomethyl) cyclohexane (1,4-H ₆ XDI) and 95% of 4,4'-diphenylmethane diisocyanate. Was carried out in the same manner as in Example 1, to prepare a polyurethane urea elastic yarn, and to evaluate the physical properties thereof are shown in Table 1 together.

Except for preparing the polyurethaneurea polymer at a ratio of 10 mol% of 1,4-bis (isocyanatomethyl) cyclohexane (1,4-H ₆ XDI) and 90% of 4,4'-diphenylmethane diisocyanate Was carried out in the same manner as in Example 1, to prepare a polyurethane urea elastic yarn, and to evaluate the physical properties thereof are shown in Table 1 together.

Except for preparing the polyurethaneurea polymer at 25 mol% of 1,4-bis (isocyanatomethyl) cyclohexane (1,4-H ₆ XDI) and 75% of 4,4'-diphenylmethane diisocyanate. Was carried out in the same manner as in Example 1, to prepare a polyurethane urea elastic yarn, and to evaluate the physical properties thereof are shown together in Table 1 below.

< Comparative example  1>

Except for preparing the polyurethaneurea polymer at a content ratio of 30 mol% of 1,4-bis (isocyanatomethyl) cyclohexane (1,4-H ₆ XDI) and 70% of 4,4'-diphenylmethane diisocyanate Was carried out in the same manner as in Example 1, to prepare a polyurethane urea elastic yarn, and to evaluate the physical properties thereof are shown in Table 1 together.

< Comparative example  2>

Except adding 1,4-bis (isocyanatomethyl) cyclohexane (1,4-H ₆ XDI), except that 40 urea 3 filament polyurethane urea elastic yarn was produced at a speed of 900 m / min. Prepared under the same conditions as in Example 1.

< Comparative example  3>

It was prepared under the same conditions as in Example 1 except that 1,4-bis (isocyanatomethyl) cyclohexane (1,4-H ₆ XDI) was not added.

Table 1

1st diisocyanate: 4,4'-diphenylmethane diisocyanate

Second diisocyanate: 1,4-bis (isocyanatomethyl) cyclohexane (1,4-H ₆ XDI)

As confirmed through Table 1, 1,4-bis (isocyanatomethyl) cyclohexane (1,4-H ₆ XDI) content of the polyurethane urea elastic yarn prepared by mixing at least 2 mol% It was confirmed that the productivity can be improved without deterioration of elongation and 200% modulus, and when the second diisocyanate exceeds 25 mol%, the elongation is improved, but the modulus decreases to confirm the strict physical property difference with the existing elastic yarn. there was.

Claims (3)

Polyurethane urea elastic yarn to prepare a polyurethane urea by primary polymerization of the polyol and an excess of diisocyanate to obtain a prepolymer, followed by secondary polymerization by adding a chain extender to the solution obtained by dissolving the prepolymer in an organic solvent. In the manufacturing method of
The diisocyanate includes a first diisocyanate and a second diisocyanate, and the first diisocyanate is one or two or more organic diisocyanates selected from aromatic, aliphatic and alicyclic diisocyanates, and the second diisocyanate. Is 1,4-bis (isocyanatomethyl) cyclohexane, and the second diisocyanate is present in the range of 2 to about 25 mol% of the total diisocyanate. . The method of claim 1, wherein the first diisocyanate is 4,4'-diphenylmethane diisocyanate, 1,5'-naphthalene diisocyanate, 1,4'-phenylene diisocyanate, hexamethylene diisocyanate, 1,4 ' Method for producing a high-speed spinning polyurethane urea elastic yarn characterized in that one or more selected from the group consisting of -cyclohexane diisocyanate, 4,4'-dicyclohexyl methane diisocyanate, isophorone diisocyanate . The polyurethane urea according to claim 1, wherein a chain extender mixture comprising a chain extender mixture comprising at least 80 mol% of the total number of moles of the chain extender and a second chain extender other than ethylene diamine is used. Manufacturing method of elastic yarn