KR20160078842A - Improved dyeability spandex fiber - Google Patents

Abstract

The present invention relates to a spandex fiber which can improve dyeability of a reactive dye in accordance with the increase in pH and by adding calcium oxide (CaO).

Description

Improved dyeability spandex fiber < RTI ID = 0.0 >

The present invention relates to a spandex fiber having improved dyeability. More particularly, the present invention relates to a spandex fiber capable of improving dyeability with respect to a reactive dye as the pH is increased by the addition of calcium oxide (CaO).

Spandex fiber is a general term of polyurethane elastic fiber. It has excellent elongation and elastic recovery rate and is used as a high stretchable knitted fabric in combination with various other fibers such as nylon, acrylic, wool, cotton etc. depending on the application. However, Has a problem.

General techniques for improving the dyeability of spandex 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 with a tertiary amine (Japanese Examined Patent Publication No. 50-17520), 3) a method of introducing a tertiary or quaternary nitrogen atom to the terminal of the polyurethane polymer chain (Japanese Patent Publication No. 44-16386 4) a method of using a low molecular weight diamine as a chain extender (JP-A-59-108021), and the like.

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 addition, Korean Patent Laid-Open Nos. 10-2009-0118997 and 10-2005-0070652 disclose a method of dyeing a specific blue acid dye containing a maleimide polymer having a maleimide polymer, or adding a talc compound, However, there was a limit to sufficiently improve the dyeability of the polyurethane.

Particularly, in the case of cotton + spandex fabrics knitted with cotton, the reactive dye is used for dyeing the fabric, but since the spandex is not dyed to the reactive dye, when the fabric is stretched, the unspun spandex becomes white.

There has been a technique for improving the dyeability of spandex to acid dyes or disperse dyes, but there is no technology to improve dyeability for reactive dyes.

In recent years, in order to improve the dyability of spandex in reactive dyes, it is possible to expect a slight improvement in dyeability by the addition of an additive having a reactive group capable of binding with a reactive dye, but the dyeability level is unsatisfactory.

Accordingly, it is an object of the present invention to provide a spandex fiber capable of improving the dyeability of a reactive dye.

In order to achieve the above object, the present invention provides a method for producing a polyurethane-urea solution by spinning a polyurethane-urea spinning stock solution containing calcium oxide (CaO) in an amount of about 0.5 wt% to about 10.0 wt% Which is a spandex fiber capable of improving the dyeability with respect to reactive dyes.

The spandex fiber to which calcium oxide is added according to the present invention has an effect of improving dyeing by increasing affinity with a reactive dye.

The spandex fiber according to one embodiment of the present invention may be prepared by adding calcium oxide (CaO) to a conventional polyurethane-urea solution in an amount of about 0.5% by weight to about 10.0% by weight based on the solid content of the polyurethane- Which is manufactured by spinning a spinning solution.

The polyurethane-urea polymer used for producing the spandex fiber of the present invention described above may be prepared by reacting an organic diisocyanate and a polymeric diol to prepare a polyurethaneurea prepolymer, dissolving the polyurethaneurea prepolymer in an organic solvent, With a monoamine.

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)

^Wherein 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 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-bonded 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 of the melamine compound 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 the embodiment of the present invention, it is possible to further improve the dyeability of reactive dyes, for example, dyes of vinylsulfone type, dyes of monochlorotriazine type or bis-monochlorotriazine type classified by chemical structure It is preferable to add calcium oxide (CaO) to the spinning solution in an amount of about 0.5% by weight to about 10.0% by weight based on the solid content of the polyurethane-urea solution polymer. In the case of reactive dyes, dyeing is performed under alkaline pH of about 11 to 12. When calcium oxide (CaO) is added to the spandex fiber, the pH level of the fabric is increased. As the pH level is higher than that of the existing spandex, the affinity with the reactive dye increases, so that the improvement in dyeability can be expected.

If calcium oxide (CaO) is added in an amount less than 0.5% by weight, the effect of improving the pH is insufficient and the effect on the reactive dye is not expected. On the contrary, when calcium oxide (CaO) is added in an amount exceeding 10% by weight There arises a problem that physical properties such as strength, elongation and modulus are lowered. Therefore, it is best to add the above-mentioned range.

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 1

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. To the polyurethane-urea solution, calcium oxide (CaO) was added in an amount of 5% by weight based on the solids content, 24.3 g (1% by weight) of the compound was added, and the mixture was stirred at 45 캜 for 60 minutes.

Further, 36.5 g (1.5% by weight) of triethylene glycol-bis-3- (3-tertiarybutyl-4-hydroxyphenyl) propionate as an antioxidant and 36.5 g 97.3 g (4.0 wt%) of hydrotalcite Mg ₄ Al ₂ (OH) ₁₂ CO ₃ .3H ₂ O coated with 1 wt% of polyphosphate and 12.16 g (0.5 wt%) of titanium dioxide as an anti- To prepare a urethane urea spinning stock 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 polyurethane-urea elastic yarn was knitted into a fabric (elastic yarn content: 100% by weight), dyed with a reactive dye (vinyl sulfone type dye: Remazol Blue RR gran dye of Dystar Co.) (L *) were measured, and the results are shown in Table 1. < tb > < TABLE >

Example 2

A polyurethane-urea elastic yarn was produced in the same manner as in Example 1, except that 10 weight% of calcium oxide (CaO) was added in Example 1.

The polyurethane-urea elastic yarn was knitted into a fabric (elastic yarn content: 100% by weight), dyed with a reactive dye (vinyl sulfone type dye: Remazol Blue RR gran dye of Dystar Co.) (L *) were measured, and the results are shown in Table 1. < tb > < TABLE >

Comparative Example 1

A polyurethane-urea elastic yarn was produced in the same manner as in Example 1, except that calcium oxide (CaO) was not added in Example 1.

The polyurethane-urea elastic yarn was knitted into a fabric (elastic yarn content: 100% by weight), dyed with a reactive dye (vinyl sulfone type dye: Remazol Blue RR gran dye of Dystar Co.) (L *) were measured, and the results are shown in Table 1. < tb > < TABLE >

Example 1 Example 2 Comparative Example 1 L * value 72.2 65.7 78.3

<Evaluation method>

1. L * value (depth of color), a * value and b * value on the chromaticity coordinates: The reflectance of the yarn was measured using a spectrophotometer and then calculated using the equation of CIE 76 CIE Lab color difference equation.

As can be seen in Table 1, the L * value is much darker than the example, because it is lower than the comparative example.

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 (3)

The present invention relates to a spandex fiber capable of improving dyeability with respect to a reactive dye, which is produced by spinning a polyurethane-urea spinning stock solution in which an additive capable of increasing the pH of a fabric is put into a usual polyurethane-urea solution. The spandex fiber according to claim 1, wherein the additive is calcium oxide (CaO). The spandex fiber according to claim 2, wherein the calcium oxide (CaO) is added in an amount of 0.5% by weight to 10.0% by weight based on the solid content of the polyurethaneurea solution polymer.