KR101407153B1 - Improved chlrorine and discolored resistant spandex fiber and method for preparing the same - Google Patents

Abstract

The present invention solves the problem that the chlorine-resistant spandex fiber to which chlorine-containing inorganic chlorine agent is applied is easily discolored when it is left in the air, and the phenomenon that the effect of chlorine resistance is short-term or temporary and the inherent characteristic of only spandex fiber is lost In order to solve the problem, as an organic additive for improving chlorine resistance in addition to the production of common chlorine-spon- tering spandex fiber, at least one of a symmetrical di- hindered hydroxyphenyl compound and a mono-hindered hydroxyphenyl compound An additive comprising a semi-dicarbazide compound having heat resistance and radical scavenger function, and a urethane additive including a tertiary butyl group acting as a secondary antioxidant in a slurry of a polyurethane solution To prepare a spinning stock solution, and after defoaming, dry spinning and spinning Excellent in chlorine resistance and discoloration resistance, comprising a step of production by the spandex fiber, and to provide a production method thereof.

Description

[0001] The present invention relates to a spandex fiber excellent in chlorine resistance and discoloration resistance and a method of producing the spandex fiber and a discolored resistant spandex fiber.

The present invention relates to a spandex fiber excellent in chlorine resistance and discoloration resistance, and a method for producing the spandex fiber. More particularly, the present invention relates to a method for producing a chlorine-containing chlorine-containing organosilicon compound, which is capable of preventing yellowing and deterioration of physical properties due to various environmental factors, Spandex fibers improved in discoloration at the same time, and a method for producing the same.

Spandex fiber refers to synthetic fibers made of elastic fibers of polyurethane fibers and is a high value-added fiber compared to synthetic fibers such as nylon and polyester. Spandex fiber has been widely used to make lingerie, trousers, sportswear, stockings, baby diapers and so on. Therefore, there is a growing interest in spandex fibers not only in international textile manufacturers but also in domestic synthetic fibers manufacturers. However, the production technology of spandex fiber of domestic synthetic fiber is lower than that of other synthetic fibers, because the spinning and post-processing technology is weaker than other countries. Therefore, basic technology is secured through continuous research and high quality elastic yarn production technology is required It is also a field.

However, the major disadvantage of spandex fibers is their low thermal resistance and chlorine resistance, which is expected to serve as a major obstacle to the development of the elastic fiber market in the future. The solution to these problems is to expand the market for elastic fibers and elastomers I think it will make a significant contribution.

Research on the development of chlorine-spandex spandex fiber has been actively carried out to meet the demand characteristics of this market. In general, spandex has been actively used as chlorine (for example, chlorine disinfection pool, chlorine- Bleaching agent), the decomposition of the fiber chain occurs, and the elasticity, which is a special advantage of the spandex, is lowered. Therefore, the chlorine-resistant spandex is a product designed to withstand the fiber damage caused by the chlorine component and maintain the inherent elasticity of the spandex, and it is indispensable to maintain the life of the swimwear and maintain the elasticity.

BACKGROUND ART Conventionally, most of chlorine-resistant spandex fibers such as Korean Patent Laid-Open Publication No. 10-2006-0005814 (color-changing and chlorine-resistant spandex fiber and its manufacturing method) and Korean Patent Laid-Open Publication No. 10-2006-0066689 Spandex fibers containing partially dehydrated and oxidized hydrotalcite) are used to basically apply a chlorine agent in inorganic such as hydrotalcite, hydro-magneite and hydro-magneite and a Hunting mix mineral to sustain or enhance chlorine resistance However, spandex fibers are exposed to various environmental factors such as ultraviolet rays, heat and atmospheric smog, so that yellowing and physical properties are damaged, or they are left in air, NO _x gas, UV rays, It tends to be easily discolored by exhaust gas or the like.

When the chlorine agent is applied to the spandex fiber as described above, the chlorine resistance is improved, but the persistence thereof is limited. Thus, there is a tendency that the chlorine agent is applied only in the short term or only temporarily. Especially, when the chlorine agent is applied, It is difficult to secure a sufficient amount of water. Although organic additives may be added to maintain persistence of chlorine resistance, it may be somewhat effective in improving persistence of chlorine resistance, but there are also limitations in improving discoloration, The organic additive is dropped depending on the processing conditions of the organic solvent, thereby failing to exhibit the effect.

Accordingly, the present invention solves the problem that the chlorine-containing spandex fiber to which the chlorine-containing inorganic agent is applied is exposed to various environmental factors or easily discolored when left in the air, and the phenomenon that the effect of chlorine resistance is short- Which solves the problem that the inherent characteristic of the fiber is lost, and it is an object of the present invention to provide a chlorine-resistant and chlorine- And a spandex fiber excellent in discoloration resistance, and a method for producing the spandex fiber.

The spandex fiber excellent in chlorine resistance and discoloration resistance according to the present invention,

In addition to the preparation of conventional chlorine-sponge spandex fibers, the addition of a symmetrically di-hindered hydroxyphenyl group and a mono-hindered hydroxyphenyl group as additives for enhancing chlorine resistance A semi-dicarbazide-based material having heat resistance and radical scavenger function and an additive including a tertiary butyl group serving as a secondary antioxidant, as an organic additive in a compound selected from at least one of them, To prepare a spinning stock solution, defoaming the spinning solution, and then spinning and spinning it.

Further, the present invention is characterized in that it is a spandex fiber excellent in chlorine resistance and discoloration resistance produced by the above method.

Although the prior art spandex has been emphasized on imparting chlorine resistance, the present invention is further directed to a semi-dicarbazide-based material having a heat-resistant, radical scavenger capable of exhibiting excellent characteristics in terms of NO _x gas and sunlight, The addition of a compound containing a silylbutyl group further improves discoloration compared to conventional products. As a result, it is impossible to apply the product by discoloration during processing of the fabric, for example, pretreatment, post-processing, There is an effect that can be applied to applications that have been used.

According to the production of the spandex fiber excellent in chlorine resistance and discoloration resistance according to the present invention, the first step is a step of producing a polyurethane prepolymer solution, which comprises mixing diphenylmethane-4,4'-diisocyanate and Polyurethane prepolymer having an isocyanate at both ends is first prepared by reacting polytetramethylene ether glycol having a molecular weight of 1,000 to 3000 and then adding and dissolving dimethylacetamide to prepare a polyurethane prepolymer solution.

The second step is a step of preparing a polyurethane solution from the polyurethane prepolymer solution, wherein a solution of ethylenediamine and diethylamine dissolved in dimethylacetamide is added to the prepolymer solution to prepare a polyurethane solution.

In the third step, the additive is added to the polymer of the polyurethane solution to prepare a spinning solution. As the additive, an irradiating stock solution is prepared by applying an anti-light agent, a chlorine-containing agent, and a chlorine- .

In the present invention, the light-resisting agent includes titanium dioxide, and its use range is preferably in the range of 0.1 to 1.0% by weight, particularly preferably 0.3 to 0.6% by weight, based on the solid content of the polyurethane solution polymer .

In the present invention, as the inorganic chlorine agent, hydrotalcite represented by the following formula (1), a hydro-magneite compound represented by the following formula (2) or a mixture of hydro-magneite and huntingite represented by the following formula (3) 5.0% by weight, of which hydrotalcite compounds are most suitable.

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

According to the present invention, the hydrotalcite compound particles are, for _{example, Mg 4 Al 2 (OH)} 12 CO 3 · H 2 O, Mg 4 .5 Al 2 (OH) 13 CO 3 · 3.5H 2 O, Mg _{6 Al 2 (OH) 16 CO} 3 · H 2 O, Mg 8 Al 2 (OH) 20 CO 3 · H 2 O, Mg 4 Al 2 (OH) 12 CO 3 · H2O, Mg 4 .5 Al 2 (OH _{) 13 CO 3, Mg 6 Al} 2 (OH) 16 CO 3, Mg 8 Al 2 (OH) 20 CO 3, Mg 4 Al 2 (OH) 20 CO 3, Mg 4 .5 Al 2 (OH) 13 (CO _{3) 0.6 O 0 .4, Mg} 6 Al 2 (OH) 16 (CO 3) 0.7 O 0 .3, Mg 4.5 Al 2 (OH) 12.2 (CO 3) 0.8 O 0.6, Mg 4 Al 2 (OH) 12 (CO ₃ ) _0.6 O _{0 .4,} among which Mg ₄ Al ₂ (OH) ₁₂ CO ₃ .H ₂ O is most preferred.

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

In the present invention, examples of the compound represented by the general formula of the hydro-magnesite is _{Mg 4 (CO 3) 4 ·} Mg (OH) 2 · H 2 O, Mg 3 (CO 3) 3 · Mg (OH) 2 3H 2 O , Mg ₄ (CO ₃ ) ₄ .Mg (OH) ₂ , and Mg ₃ (CO ₃ ) ₃ .Mg (OH) ₂ and MgCO ₃ .

The chlorine-containing inorganic agent which can be used in the present invention is obtained by hydrotalcite-coated hydrotalcite with 1 to 3% by weight of stearic acid and 0.5 to 2% by weight of a melamine-based compound in the hydrotalcite compound, 10% by weight of the melamine-based compound is preferably added and mixed. As the melamine-based compound, melamine polyphosphate is preferably selected and used.

When the stearic acid and the melamine-based compound are respectively employed in an amount of less than 1 wt% or less than 0.5 wt%, the coating effect is lost. On the contrary, when the content of the stearic acid and the melamine compound is more than 3 wt% or 10 wt% There is no difference, which is not preferable from the viewpoint of economy.

Further, in the production of the spandex fiber excellent in the resistance to chlorine and discoloration according to the present invention, a symmetrical di-hindered hydroxyphenyl compound, for example, tetrakis [ Methylene-2- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, mono-hindered hydroxyphenyl compounds such as 1,1,3-tris '-Methyl-4'-hydroxy-5'-t-butylphenyl) butane may be used, and it is preferably 0.1 wt% to 2.0 wt% with respect to the solid content of the symmetrical dihydroxyphenyl compound. The mono-hindered hydroxyphenyl compound is preferably 0.1% by weight to 3.0% by weight, preferably 0.5% by weight to 1.5% by weight, based on the solids content of the polymer.

In addition, in the production of spandex fibers excellent in chlorine resistance and discoloration resistance according to the present invention, semidicarbazide-based compounds having heat resistance and radical scavenger function, for example, hindered amine compounds 1,1, 1, 1'-tetramethyl-4,4'- (methylene-di-p-phenylene) semidicarbazide or 1,6-hexamethylenebis (N, N-dimethyl semicarbazide) % To 3.0 wt.%, Preferably 1.0 wt.% To 2.0 wt.

Further, in the production of the spandex fiber excellent in chlorine resistance and discoloration resistance according to the present invention, urethane-based additives including a tertiary butyl group which further acts as a secondary antioxidant, for example, t-butyl diethanolamine and 4,4 '-Methylenebis (cyclohexyl isocyanate) may be mixed and added in the range of about 0.1 wt% to 1.0 wt%.

As described above, when the spinning raw material solution obtained by mixing and injecting the inorganic chlorinating agent with the additives and the organic additives for improving the function of the polyurethane solution is defoamed and then spun and wound in the dry spinning process, And a span-tex fiber excellent in discoloration resistance can be produced.

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

Example  One

518 g of diphenylmethane-4,4'-diisocyanate and 2328 g of polytetramethylene ether glycol (molecular weight 1800) were reacted in a stream of nitrogen at 90 DEG C for 95 minutes with stirring to prepare a polyurethane prepolymer having isocyanates at both ends. After cooling the prepolymer to room temperature, 4269 g of dimethylacetamide was added and dissolved to obtain a polyurethane prepolymer solution.

Then 43 g of ethylenediamine and 9.1 g of diethylamine were dissolved in 1889 g of dimethylacetamide and added to the prepolymer solution at 9 DEG C or lower to obtain a polyurethane solution.

As a additive to the solids content of the polymer, hydrotalcite [Mg ₄ Al ₂ (OH) ₁₂ (0.1% by weight) coated with 0.1% by weight of titanium dioxide as an optical agent, 2% by weight of stearic acid versus hydrotalcite as a chlorine agent, and 1% by weight of melamine polyphosphate CO ₃ .H ₂ O] was added and mixed in an amount of 4% by weight. Further, a slurry containing tetrakis [methylene-2- (3,5-di-tertiary- -Butyl-4-hydroxyphenyl) propionate] methane as a monohindered hydroxyphenyl compound, 1,1,3-tris (2'-methyl-4'- 1.0% by weight of t-butylphenyl) butane, 1,1,1 ', 1'-tetramethyl-4,4'- (methylene-di-p-phenylene) semidicarbazide as a semi- 1.5% by weight of t-butyldiethanolamine and 0.5% by weight of 4,4'-methylenebis (cyclohexyl isocyanate) were added and mixed to obtain a spinning solution.

After defoaming the spinning solution, the yarn spinning was carried out at a spinning speed of 900 m / min at a spinning temperature of 260 ° C in a dry spinning process to produce a 3 filament 40 denier spun-tex yarn.

The results of evaluating the chlorine resistance of the spandex yarn prepared above are shown in Table 1 below.

In order to evaluate the chlorine resistance of the spandex yarn obtained above, the strength retention in chlorine water was evaluated by the following method.

The spandex yarn was treated for 1 hour in water at pH 4.5, 99 to 100 ° C under 50% elongation, dried and cooled at room temperature, dipped in 80 l chlorine water having an active chlorine content of 3.5 ppm and pH 7.6 for 120 hours, The strength retention ratio was calculated. Was used for the MEL strength evaluation, a sample length of 10cm, and using the cell of 32kg _f was measured at a tensile speed of 1000mm / min (Cross head speed) .

Strength retention (%) = S / S _o x 100

(S _o : strength before treatment, S: strength after treatment)

On the other hand, in order to evaluate discoloration resistance of Spanex, the difference in discoloration (color difference measurement) due to three discoloration factors was measured by the following method.

The spandex yarn of each experimental example was woven in the form of a fabric, and then a sample was prepared at a width of 3 cm and a length of 10 cm. Each sample was treated in a bath of 1 g / l of a scouring agent and 1 g / l of NaOH at 80 DEG C for 20 minutes and air-dried for 12 hours.

(1) Heat treatment conditions: Heat treatment in an oven at 200 ° C for 10 minutes

(2) UV lamp treatment conditions: UV-B lamps were allowed to stand for 24 hours.

(3) NO _x gas treatment conditions after the NO _x gas generated by using sodium nitrate and phosphoric acid were allowed to stand for 24 hours under the same conditions.

The degree of discoloration was measured using a Color-view ^TM manufactured by BYK Gardner. The discoloration difference was calculated as Δb = b ₂ -b ₁ where b ₁ is the yellow value at the time of untreated treatment and b ₂ is the treated yellow value. Color difference). The lower the value of Δb, the less yellowing is present.

Example  2

2.0% by weight of 1,1,1 ', 1'-tetramethyl-4,4' - (methylene-di-p-phenylene) disilecarbazide was applied as the disilicon carbide compound in Example 1 Spandex yarn was produced using the same polymerizate as in Example 1, and chlorine resistance and discoloration resistance were evaluated under the same conditions as in Example 1, and the results are shown in Table 1 below.

Example  3

A spandex yarn was produced using the same polymeric material as in Example 1, except that 1,6-hexamethylene bis (N, N-dimethyl-semicarbazide) was added as the disilicon carbide compound in Example 1, The chlorine resistance and discoloration resistance were evaluated under the same conditions as in Example 1, and the results are shown in Table 1 below.

Example  4

Except that 1.0 wt% of t-butyl diethanolamine and 4,4'-methylene bis (cyclohexyl isocyanate) polyurethane were used in Example 1, and spandex yarn The chlorine resistance and discoloration resistance were evaluated under the same conditions as in Example 1, and the results are shown in Table 1 below.

Example  5

A spandex yarn was produced using the same polymeric material as in Example 1 except that a mixed mineral of huntite and hydro-magneite was applied as a chlorine-containing agent in Example 1, Chlorine resistance and discoloration resistance were evaluated, and the results are shown in Table 1 below.

Example  6

A spandex yarn was produced using the same polymeric material as in Example 1, except that hydro-magneite was applied as a chlorine-containing agent in Example 1, and chlorine resistance and discoloration resistance were evaluated under the same conditions as in Example 1 The results are shown in Table 1 below.

Comparative Example  One

A spandex yarn was produced using the same polymeric material as in Example 1, except that the urethane additive containing a disilicon carbide compound and a tertiary butyl group was not used in Example 1, and the same spandex yarn as that in Example 1 The chlorine resistance and discoloration resistance were evaluated under the conditions, and the results are shown in Table 1 below.

Comparative Example  2

A spandex yarn was produced using the same polymeric material as in Example 1, except that the urethane type additive including a tertiary butyl group was not used in Example 1. The sponge yarn was produced under the same conditions as in Example 1, The results are shown in Table 1 below.

Comparative Example  3

In Example 1, only a chlorine-containing agent was used without using a urethane-based additive including a mono-hindered hydroxyphenyl compound, a symmetric dedifferentihydroxyphenyl compound, a disicarbazide compound and a tertiary butyl group Spandex yarn was produced using the same polymerizate as in Example 1, and chlorine resistance and discoloration resistance were evaluated under the same conditions as in Example 1, and the results are shown in Table 1 below.

Evaluation of chlorine resistance and discoloration resistance division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Thermal discoloration (? B) 5.1 4.2 5.7 5.2 5.3 5.3 18.2 4.8 19.8 UV discoloration (? B) 11.1 12.1 11.1 11.8 11.6 11.9 14.1 11.6 26.6 NOx gas discoloration (DELTA b) 10.5 10.1 12.1 9.5 9.8 11.8 30.4 21.4 15.7 Strong retention (%) 80.9 81.3 76.1 74.9 81.9 83.4 82.4 82.7 61.3

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 (5)

In addition to the production of conventional chlorine-spon- taneous spandex fiber, an organic additive for improving chlorine resistance, which comprises a symmetrical di- and multimeric hindered hydroxyphenyl compound and a mono-hindered hydroxyphenyl compound and has heat resistance and radical scavenger An additive containing a semi-dicarbazide compound having a function and a urethane additive including a tertiary butyl group serving as a secondary antioxidant are added and mixed in a slurry of a polyurethane solution to prepare a spinning solution, Followed by dry spinning and coiling. The method for producing spandex fiber according to claim 1, The method according to claim 1, wherein the symmetric dihydroxyphenyl compound is tetrakis [methylene-2- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (2'-methyl-4'-hydroxy-5'-t-butylphenol) is used as the monohindered hydroxyphenyl compound in an amount of 0.1 wt% to 2.0 wt% Butylphenyl) butane is used in an amount of 0.1% by weight to 3.0% by weight based on the solids content of the polyurethane solution polymer. The method of claim 1, wherein the semi-dicarbazide compound is a hindered amine hindered amine compound selected from the group consisting of 1,1,1 ', 1'-tetramethyl-4,4' - (methylene- ) Semidicarbazide or 1, 6-hexamethylene bis (N, N-dimethyl semicarbazide) is applied in an amount of 0.5 to 3.0 wt.% Based on the total weight of the spandex fiber Gt; The urethane additive according to claim 1, wherein the tertiary butyl group-containing urethane additive serving as the secondary antioxidant is a compound obtained by copolymerizing t-butyl diethanolamine and 4,4'-methylene bis (cyclohexyl isocyanate) % To 1.0% by weight based on the total weight of the spandex fiber. A spandex fiber excellent in chlorine resistance and discoloration resistance produced by the method according to any one of claims 1 to 3.