KR101440693B1 - Improved discolored resistant polyurethanurea - Google Patents

Abstract

The present invention relates to a method for producing a polyurethane-urea solution by spinning a polyurethane-urea spinning stock solution containing a hyperbranched polymer containing a large amount of -OH groups at the terminal of the polymer in a general polyurethaneurea solution in an amount of 1.0 wt% to 5.0 wt% The present invention provides a polyurethane-urea elastic yarn having improved dyability.

Description

Improved discolored resistant polyurethanurea < RTI ID = 0.0 >

The present invention relates to a polyurethane-urea elastic yarn having improved dyeability. More particularly, the present invention relates to a polyurethane-urea elastic yarn improved in dyeability with respect to a reactive dye by applying a hyperbranched polymer containing a large amount of -OH groups at the end of the polymer to a polyurethane-urea elastic yarn.

The polyurethane-urea elastic yarn is excellent in elongation and elastic recovery, and is used as a high stretchable knitted fabric in combination with various other fibers such as nylon, acrylic, wool, cotton and the like depending on the application, but has a problem that the dyability of the spandex fiber is insufficient.

General techniques for improving the dyeability of the polyurethane-urea elastic yarn include 1) a method of introducing tertiary nitrogen atoms into a polyurethane polymer chain (Japanese Patent Publication No. 62-23097), 2) a method of introducing an organic acid or an inorganic acid into a tertiary (Japanese Examined Patent Publication No. 7-517520), 3) a method of introducing a tertiary or quaternary nitrogen atom to the terminal of a polyurethane polymer chain No. 69-16386), and 4) a method of using a low molecular weight diamine as a chain extender (JP-A-59-108021).

However, the method 1) and the method 2) tend to become a gel during the reaction, and the method 3) has a problem that it is difficult to control the amount of nitrogen atoms introduced. In addition, the method 4) using a low molecular weight diamine as a chain extender can improve the dyeability but deteriorates the softness and elasticity. In the prior art (Patent Application No. 93-9904, titled invention: polyurethane resin composition with improved dyeability), which has been already filed, organic diisocyanate, polymer diol, low molecular diol not containing nitrogen, polymer triol, organic Although the above problems have been partially compensated for by incorporating a low molecular weight diol containing a nitrogen atom into a solvent to synthesize a polyurethane, when a certain amount of a low molecular weight diol containing nitrogen atom is added for the purpose of improving the dyeability, So that it was difficult to sufficiently improve the dyeability of the polyurethane-urea elastic yarn.

Accordingly, the present invention can improve the dyeability of reactive dyes as well as acidic dyes by applying a hyperbranched polymer containing a large amount of -OH groups at the ends of the polymer to the reactive dyes of polyurethane-urea elastic yarns to improve the dyeability of the reactive dyes. The present invention is directed to a spandex fiber.

Disclosure of Invention Technical Problem [8] The present invention has been made to solve the above problems, and it is an object of the present invention to provide a polyurethane-urea spinning stock solution to which a hyperbranched polymer containing a large amount of -OH group at a terminal of a polymer in an amount of 1.0 to 5.0 wt.% Based on the solid content of the polyurethane- And is a polyurethane urea elastic yarn improved in dyeability produced by spinning.

The polyurethane-urea elastic yarn of the present invention is an application of a hyperbranched polymer containing a large amount of -OH group at the end of a polymer. The polyurethane-urea elastomer yarn exhibits an effect of improving the dyeability by allowing the reactive dye to act as a seated seat of the reactive dye while facilitating accessibility of the reactive dye.

The polyurethane-urea elastic yarn of the present invention has excellent dyeability not only in acidic dyes but also in reactive dyes, and exhibits excellent dyeability not only in nylon but also in knitted fabrics of cotton and spandex.

The polyurethane-urea elastic yarn having improved dyability according to one embodiment of the present invention is obtained by adding a hyperbranched polymer containing a large amount of -OH group at the end of a polymer to a polyurethane-urea solution in an amount of 1.0 wt% 5.0% by weight of a spinning solution.

The polyurethane-urea polymer used in the production of the spandex fiber of the present invention may be produced by reacting an organic diisocyanate and a polymeric diol to prepare a polyurethane-urea prepolymer, dissolving the polyurethaneurea prepolymer in an organic solvent, In an organic solvent.

Examples of the organic diisocyanate used in the present invention include 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, butylene diisocyanate, hydrogenated P, and P-methylene diisocyanate. As the diol, polytetramethylene ether glycol, polypropylene glycol, polycarbonate diol and the like can be used. Examples of the diamines include ethylenediamine, propylenediamine, hydrazine, 1,2-diaminopropane, and the like. In the present invention, especially, ethylene diamine and 1,2-diaminopropane are dissolved in 80 mol % And 20 mol%, respectively. Monoamines are also used as chain terminators, examples of which include diethylamine, monoethanolamine, dimethylamine, and the like.

In the present invention, a polyurethane-urea spinning solution can be prepared by adding an antioxidant, a chlorine-containing agent in an inorganic salt, and an anti-fogging agent in order to prevent discoloration and deterioration of properties of spandex during heat treatment during ultraviolet rays, atmospheric smog, and spandex processing.

The antioxidant used in the present invention is to stabilize the polyurethane-urea spinning stock solution. For example, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -1 (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, triethyleneglycol bis- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl) -2,4,8,10-tetraoxa Bis-3- (3-tertiarybutyl-4-hydroxyphenyl) propionate is preferable from spiro [5.5] undecane 6 to triethylene glycol-bis-3- Among these, triethylene glycol bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate is most preferable and 0.01 to 10% by weight based on the weight of the polyurethane- It is good to do.

As the inorganic chlorine agent applicable to the present invention, a hydrotalcite compound particle coated with a melamine compound is used, and the hydrotalcite compound particle can be represented by the following structural formula (1).

M ^{2 +} _x Al _m (OH) _y (A ^n- ) _z (1)

In the above formula, M ^{2 +} is Mg ^{2 +} or Zn ^{2 +} , A ^{n -} is an anion having a valence of n, x and y are positive values of at least 2, and Z and m are positive values. Wherein A ^{n -} is ^{OH -, F -, Cl -} , Br -, NO 3 -, SO 4 2 -, CH 3 COO -, CO 3 2 -, HPO 4 2 -, Fe (CN) 6 3-, oxalate A late ion and a salicylate ion.]

The hydrotalcite compound particles are preferably one or more selected from the compounds represented by the following structural formulas (2) to (6), and among these, the most preferable is the following chemical formula (5).

Mg _{4 .5} Al ₂ (OH) ₁₃ CO ₃ (2)

Mg ₆ Al ₂ (OH) ₁₆ CO ₃ (3)

Mg ₈ Al ₂ (OH) ₂₀ CO ₃ (4)

Mg ₄ Al ₂ (OH) ₁₂ CO ₃ (5)

The melamine compound may be a melamine compound, a melamine compound bonded with phosphorus (P), a melamine compound substituted with an organic compound having a carboxyl group, an organic compound having a carboxyl group, It is preferable to use one or more kinds of melamine cyanurate compounds substituted with the melamine compound and the organic compound having a carboxyl group.

Examples of the melamine compound include methylene dimelamine, ethylene dimelamine, trimethylene dimelamine, tetramethylene dimelamine, hexamethylene dimelamine, decamethylene dimelamine, dodecamethylene dimelamine, 1,3-cyclohexylene dimelamine, p - phenylene dimelamine, p-xylene dimelamine, diethylenetriamine, triethylenetetramelamine, tetraethylenepentamelamine and hexaethylene heptamelamine, melamine formaldehyde and the like.

The phosphorus-linked melamine compound is not particularly limited as long as the phosphoric acid compound is bonded to the melamine compound or may be in the form of a phosphate bond. Examples thereof include dimelamine pyrophosphate, melamine primary phosphate, melamine secondary phosphate, melamine polyphosphate, bis- (Pentaryltritophosphate), melamine salt reacted with phosphoric acid, and the like.

The melamine cyanurate compound is a melamine cyanurate compound in which an unsubstituted melamine saururate and a melamine cyanurate compound in which at least one substituent is substituted with methyl, phenyl, carboxymethyl, 2-carboxyethyl, cyanomethyl, .

It is effective that the melamine compound includes an organic compound having a carboxyl group. Examples of organic compounds having a carboxyl group include aliphatic monocarboxylic acids such as caprylic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, hexadecano Succinic acid, succinic acid, glutaric acid, malonic acid, succinic acid, succinic acid, succinic acid, succinic acid, succinic acid, Adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12- 1,13-tridecanedicarboxylic acid or 1,14-tetradecanedicarboxylic acid may be employed as the aromatic monocarboxylic acid, and examples thereof include benzoic acid, phenylacetic acid, Naphthoic acid, beta- naphthoic acid, cinnamic acid, p-aminohippuric acid and 4- (2- (2-thiazo (l) ylsulfamyl) -phthalaninoic acid may be employed as the aromatic dicarboxylic acid. Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, As the aromatic tricarboxylic acid, for example, trimellitic acid, 1,3,5-benzenetricarboxylic acid and tris (2-carboxyethyl) isocyanurate may be employed, and aromatic As the tetracarboxylic acid, for example, pyromellitic acid and biphenyltetracarboxylic acid may be employed. As the alicyclic monocarboxylic acid, for example, cyclohexanecarboxylic acid, alicyclic dicarboxylic acid As the acid, for example, 1,2-cyclohexanedicarboxylic acid and the like can be employed.

According to the present invention, the hydrotalcite compound particles are preferably coated with 0.1 to 10% by weight of a melamine-based coating material.

The spandex fiber of the present invention may further contain additives such as titanium dioxide, magnesium stearate and the like as an optical agent in addition to the above components. The titanium dioxide may be used in an amount of 0.1 to 5 wt% based on the total weight of the spandex fiber, depending on the degree of white color of the spandex. Magnesium stearate may also be used in the range of 0.1 to 2% by weight based on the total weight of the spandex fiber, which is added to improve the spandex maritime.

According to one embodiment of the present invention, when the hyperbranched polymer containing a large amount of -OH group at the terminal of the polymer is contained in an amount less than 1.0% by weight in the elastic yarn, as compared with the polymer solid content of the polyurethaneurea solution, The effect of improving the dyeability is extremely small. On the other hand, when the content is more than 5.0% by weight, the modulus of the yarn is lowered, and problems such as occurrence of scum due to friction may be caused. Therefore, Most preferred.

Preferred hyperbranched polymers in the present invention include, for example, hyperbranched bis-MPA polyester-16-hydroxyl (1), hyperbranched bis-MPA polyester-32 At least one of Hyperbranched bis-MPA polyester-32-hydroxyl (Formula 2) and Hyperbranched bis-MPA polyester-64-hydroxyl (Formula 3) .

Hereinafter, the present invention will be described in more detail with reference to examples, but the following examples are for illustrative purposes only and the present invention is not limited thereto.

Example  One

455.2 g of 4,4'-diphenylmethane diisocyanate and 1926 g of polytetramethylene ether glycol (PTMG, molecular weight 1800) were reacted with stirring at 90 DEG C for 180 minutes in a nitrogen gas stream to prepare a polyurethane-urea reserve having isocyanate A prepolymer was prepared. After the prepolymer was cooled to room temperature, 4485.3 g of dimethylacetamide as a solvent was added to obtain a polyurethane urea prepolymer solution.

Then, 36.0 g (0.6 mol) of ethylenediamine, 11.1 g (0.15 mol) of 1,2-diaminopropane and 4.4 g of diethylamine as a chain terminator were dissolved in 684 g of dimethylacetamide as chain extender, Was added to the prepolymer solution to obtain a polyurethaneurea solution. 1% by weight of a hyperbranched polymer containing a large amount of -OH groups at the end of the polymer was added to the above polyurethaneurea solution and mixed at 45 DEG C for 60 minutes.

Further, 1.5 wt% of triethylene glycol-bis-3- (3-tertiarybutyl-4-hydroxyphenyl) propionate as an antioxidant and 1 wt% of melamine polyphosphate as a chlorine-containing agent in the polyurethane- 4% by weight of hydrotalcite-coated Mg ₄ Al ₂ (OH) ₁₂ CO ₃ .3H ₂ O, and 0.5% by weight of titanium dioxide as an optical agent were mixed to prepare a polyurethane-urea spinning solution.

The spinning solution thus obtained was spinnable at a spinning rate of 900 m / min by spinning (spinning temperature: 260 ° C) to produce a polyurethane-urea elastic yarn of 40 denier 3 filaments.

The physical properties of polyurethane-urea elastic yarn prepared by the above-mentioned method and properties of yarn are as follows.

(1) The tensile strength and elongation of the yarn were evaluated in accordance with KSK 0219.

(2) Modulus: The modulus value when the yarn was elongated by 200% was shown.

(3) Washing fastness: Measured by KSK 0430 AI method.

(4) L value (core color degree): The reflectance of the yarn was measured using a spectrophotometer, and then calculated using the equation of CIE 76 CIE Lab color difference equation.

The results are shown in Table 1 below.

Example  2

A polyurethane-urea elastic yarn was prepared in the same manner as in Example 1, except that 3.0 weight% of a hyperbranched polymer containing a large amount of -OH groups at the end of the polymer was added.

Example  3

A polyurethane-urea elastic yarn was prepared in the same manner as in Example 1, except that 5.0 wt% of a hyperbranched polymer containing a large amount of -OH groups at the end of the polymer in Example 1 was added.

Comparative Example  One

A polyurethane-urea elastic yarn was produced in the same manner as in Example 1, except that the hyper-branched polymer containing a large amount of -OH group at the end of the polymer was not added in Example 1.

Comparative Example  2

A polyurethane-urea elastic yarn was prepared in the same manner as in Example 1, except that 0.5 wt% of a hyperbranched polymer containing a large amount of -OH groups at the end of the polymer was added.

Comparative Example  3

A polyurethane-urea elastic yarn was prepared in the same manner as in Example 1, except that 6 wt% of a hyperbranched polymer containing a large amount of -OH groups at the end of the polymer was added.

Property classification
Example 1
(1.0%) Example 2
(3.0%) Example 3
(5.0%) Comparative Example 1
(none) Comparative Example 2
(0.5%) Comparative Example 3
(6%) Dyeability L value 53.7 75.4 90.3 24.6 36.8 94.7 Wash fastness
(class) 4.5 4.5 4 4.5 4.5 4 Yarn characteristics The tensile strength
(g / d) 1.11 1.11 1.10 1.13 1.12 1.09 Shinto (%) 550 550 545 560 555 540 Modulus 7.6 7.5 7.1 7.8 7.8 6.5

Although the preferred embodiments of the present invention have been described in detail to some extent, it is natural that various modifications can be made to them. It is therefore to be understood that the invention may be practiced otherwise than as specifically described herein without departing from the scope and spirit of the invention.

Claims (2)

In a spandex fiber produced by spinning a polyurethane-urea spinning stock solution containing a hyperbranched polymer containing -OH groups at the ends of a polymer in a usual polyurethane-urea solution,
As the hyperbranched polymer, hyperbranched bis-MPA polyester-16-hydroxyl represented by the following formula (1), hyperbranched bis-MPA polyester-32-hydroxyl represented by the following formula (2) And at least one of branched bis-MPA polyester-64-hydroxyl is selected and contained in an amount of 1.0 wt% to 5.0 wt% based on the solid content of the polyurethane-urea solution polymer.
Formula 1

(2)

(3)

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