KR100519595B1 - High chlorine and heat resistant spandex fiber and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a spandex fiber having excellent chlorine resistance and heat resistance, and a method of manufacturing the same, having little effect on the inherent physical properties of the spandex fiber made of a polyurethane-based polymer, comprising a melamine-coated chlorinating agent in a spandex yarn. However, the melamine-coated anti-chlorine agent is formed by coating any one anti-chlorine agent selected from the group consisting of an oxide or hydroxide of a metal selected from zinc or magnesium or a complex oxide of zinc and magnesium with a melamine-based compound.

Thus, spandex fibers having both good chlorine resistance and heat resistance are provided, and can be effectively used in sports clothing such as underwear, socks, especially swimwear and the like.

Description

High chlorine and heat resistant spandex fiber and manufacturing method

The present invention relates to a spandex fiber having excellent chlorine resistance and heat resistance, and a method of manufacturing the same, and more particularly, to a spandex fiber having excellent chlorine resistance and heat resistance with little effect on the inherent physical properties of a polyurethane-based polymer, and a method of manufacturing the same. It is about.

Spandex fibers are widely used in underwear, socks, sports clothes and the like because they maintain high rubber elasticity and have excellent physical properties such as tensile stress and recovery.

However, the polyurethane portion, which is the main component of the spandex, has a problem in that the physical properties of the polyurethane are considerably lowered when washing with chlorine bleaching. In addition, a swimsuit made by alternating spandex and polyamide has a problem in that the physical properties of the spandex itself are degraded when contacted with chlorine water (active chlorine concentration of 0.5 to 3.5 ppm) in the swimming pool.

As such, efforts to improve resistance to chlorine-induced deterioration have been made in the past. For example, U.S. Patent No. 4,340,527 describes zinc oxide, Japanese Patent Application Laid-Open No. 61-35283 refers to magnesium oxide, aluminum oxide, and the like, and Japanese Patent Publication No. 59-133248 refers to magnesium hydroxide, and the like. Japanese Patent Laid-Open No. Hei 6-81215 discloses the addition of a composite oxide of zinc oxide and magnesium oxide to a spandex yarn using a chlorine resistant agent.

However, the zinc oxide, magnesium oxide, aluminum oxide, magnesium hydroxide, composite oxide of zinc oxide and magnesium oxide, etc. are eluted from the real surface when dyed under acidic conditions (pH 3 to 6), reducing the chlorine resistance of spandex yarn There was a downside.

In addition, in the bathing suit which consists of spandex yarn and nylon yarn, in order to prevent fading of the color of a bathing suit by the chlorine contained in a swimming pool, it was treated with the fixing agent like tannin after dyeing. Since the fixation process proceeds at lower acid conditions (pH 3 to 4.5) than the acid conditions at the time of dyeing, the composite oxide of zinc oxide, magnesium oxide, aluminum oxide, magnesium hydroxide, zinc oxide and magnesium oxide is less than that at dyeing. It will elute (drop off) from the spandex yarn at a higher rate. This has the disadvantage of lowering the chlorine resistance of spandex than after dyeing.

On the other hand, when the chlorine-resistant agent of the prior art is added to a polyurethane spinning polymer solution or molten polyurethane, secondary aggregation of the chlorine-resistant agent occurs, causing problems such as clogging of the spinning filter or an increase in trimming during spinning. . The prior art US Patent No. 4,340,527 has a particle size of zinc oxide of 0.1 to 1 ㎛, Japanese Patent Publication No. 61-35283 has a particle size of magnesium oxide, aluminum oxide of 5 ㎛ or less, and Japanese Patent Publication Publication No. 6-81215 discloses that the particle size of the composite oxide of zinc oxide and magnesium oxide is 0.05 to 3 µm, but none of the prior art is clogging or spinning the radiation filter by secondary coagulation of a chlorine resistant agent. It does not mention techniques for reducing trim.

U. S. Patent No. 6,406, 788 describes the addition of zinc or magnesium oxides or hydroxides with fatty acids or the like and added to a polyurethane spinning polymer solution or molten polyurethane. The use of the coated chlorine-resistant agent is effective in preventing secondary coagulation, which reduces the clogging of the radiation filter or the trimming during spinning. However, a spandex yarn containing oxides or hydroxides of zinc and magnesium coated with fatty acids has a problem of yellowing during heat treatment.

An object of the present invention is to solve the problems of the prior art as described above, and to provide a spandex fiber excellent in chlorine resistance and heat resistance.

Spandex fiber excellent in chlorine resistance and heat resistance according to the present invention for achieving the above object is made by including a melamine-coated anti-chlorine agent in the spandex yarn, the melamine-coated anti-chlorine agent of the selected metal of zinc or magnesium It is made by coating a melamine-based compound with any one chlorine resistant agent selected from the group consisting of oxides or hydroxides or composite oxides of zinc and magnesium.

The melamine-based compound used for the coating of the melamine-coated anti-chlorine agent is a melamine compound, a melamine compound substituted with phosphorus (P), a melamine cyanurate compound, a melamine compound substituted with an organic compound having a carboxyl group, and an organic having a carboxyl group. It is selected from the group consisting of a melamine compound substituted with a compound and phosphorus (P) bonded, a melamine cyanurate compound substituted with an organic compound having a carboxyl group, or a mixture of two or more thereof.

The melamine-coated chlorine agent is preferably included in 0.1 to 10% by weight in the spandex yarn.

The melamine-based compound is preferably coated in an amount of 0.1 to 10% by weight relative to the chlorine resistant agent.

In addition, the method for producing a spandex fiber excellent in chlorine resistance and heat resistance according to the present invention, in the production of spandex fiber, (1) a group consisting of an oxide or hydroxide of a metal selected from zinc or magnesium or a composite oxide of zinc and magnesium A chlorine-resistant coating step of preparing a melamine-coated chlorine agent by coating any one chlorine-resistant chlorine compound selected from the group; (2) preparing a polyurethane spinning stock solution by mixing the melamine-coated chlorine agent obtained in the chlorine-resistant coating step with a polyurethane solution; And (3) spinning the spinning stock solution according to a conventional spandex spinning method.

Hereinafter, the present invention will be described in detail with reference to specific examples.

Spandex fiber excellent in chlorine resistance and heat resistance according to the present invention is made by including a melamine-coated anti-chlorine agent in a spandex yarn, wherein the melamine-coated anti-chlorine agent is selected from zinc or magnesium oxide or hydroxide or zinc It is characterized in that it is made by coating any one chlorine resistant compound selected from the group consisting of complex oxides of magnesium with a melamine-based compound.

The present inventors have conducted a long time research and experiment, and the prior art by adding a metal compound selected from the oxide or hydroxide of a metal selected from zinc and magnesium coated with melamine-based compound or a complex oxide of zinc and magnesium to the spandex as a chlorine-resistant agent It has been found that spandex with better chlorine and heat resistance can be produced.

When the metal compound without coating is added to the polyurethane polymer, gel generation and aggregation are very easy to occur. As a result, an increase in pack pressure and yarn breakage occurred in the spinning process, making it difficult to stabilize yarn for a long time. In addition, it was inevitable that a large amount of the metal compound, which is a chlorine-resistant agent during dyeing under the acidic conditions (pH 3 to 6) of the spandex-containing fabric and the dye fixing process (pH 3 to 4.5), which is a problem of the prior art, was eliminated. .

Compared to US Pat. No. 6,406,788, which uses the metal compound coated with stearic acid, the present invention provides a spandex having superior chlorine resistance and heat resistance than the prior art by coating with a melamine-based compound having heat resistance.

The melamine-based compound used for the coating of the chlorine-resistant agent is substituted with a melamine compound, a melamine compound in which phosphorus (P) is bonded, a melamine cyanurate compound, a melamine compound substituted with an organic compound having a carboxyl group, and an organic compound having a carboxyl group. And a melamine compound bonded with phosphorus (P), a melamine cyanurate compound substituted with an organic compound having a carboxyl group, or a mixture of two or more thereof. Melamine compounds include methylene dimelamine, ethylene dimelamine, trimethylene dimelamine, tetramethylene dimelamine, hexamethylene dimelamine, decamethylene dimelamine, dodecamethylene dimelamine, 1,3-cyclohexylene dimelamine, p-phenyl Lene dimelamine, p-xylene dimelamine, diethylene trimelamine, triethylene tetramelamine, tetraethylene pentamelamine, hexaethylene heptamelamine or those selected from the group consisting of two or more thereof can be used.

As the phosphorus-bound melamine compound, any form can be used as long as phosphoric acid (phosphoric acid) is bound to the melamine compound or phosphate (phosphate) is bound. Examples thereof include dimelamine pyrophosphate and melamine primary phosphate. , Melamine diphosphate, melamine polyphosphate or a mixture of two or more thereof may be used.

The melamine cyanurate compound is a melamine cyanurate in which unsubstituted melamine saanurate and at least one substituent are substituted with methyl, phenyl, carboxymethyl, 2-carboxyethyl, cyanomethyl, 2-cyanoethyl, and the like. Compounds and the like can be used.

It is effective to include the organic compound having a carboxyl group in the melamine-based compound. As the organic compound having the carboxyl group as an aliphatic monocarboxylic acid, for example, caprylic acid, undecanoic acid, lauryl acid, tridecanoic acid, myristic acid, penta Decanoic acid, hexadecanoic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, eicosanoic acid and behenic acid may be used, and aliphatic dicarboxylic acids, for example, malonic acid, succinic acid and glutaric acid , Adipic acid, pimelic acid, suberic acid, azelanic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecandicarboxylic acid, 1, 12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid or 1,14-tetradecanedicarboxylic acid can be used, and examples of the aromatic monocarboxylic acid include, for example, benzoic acid, phenylacetic acid, alpha- Naphthoic acid, beta-naphthoic acid, cinnamic acid, p-amino hippuric acid and 4- (2-thiazoyl sulfa ) -Phthalaninic acid (4- (2-thiazo (l) ylsulfamyl) -phthalaninoic acid) can be used, for example as aromatic dicarboxylic acid, for example terephthalic acid, isophthalic acid and phthalic acid, aromatic tricarboxylic acid. For example, trimellitic acid, 1,3,5-benzenetricarboxylic acid and tris (2-carboxyethyl) isocyanurate may be used, for example, pyromelli as aromatic tetracarboxylic acid. Pyromellitic acid and biphenyltecarboxylic acid can be used, for example cyclohexanecarboxylic acid, for example cyclohexanecarboxylic acid, cycloaliphatic dicarboxylic acid, for example 1,2-cyclohexane Dicarboxylic acids and the like can be used.

The melamine-coated chlorine agent is preferably included in 0.1 to 10% by weight in the spandex yarn. When the content of the melamine-coated anti-chlorine agent is less than 0.1% by weight, the property of imparting chlorine resistance to the spandex may be lowered. When the content of the melamine-coated anti-chlorine agent exceeds 10% by weight, the strength, elongation, There may be a problem of degrading characteristics such as modulus.

It is preferable that the said chlorine resistant agent falls in the range of 0.1-10 micrometers in average particle diameter. More preferably, it falls within the range of 0.1-5 micrometers. If the particle size of the chlorine-resistant agent exceeds 10㎛, there may be a problem that causes the pack pressure increase and trimming during spinning.

The melamine-based compound is preferably coated in an amount of 0.1 to 10% by weight relative to the chlorine resistant agent. If the coating amount of the melamine-based compound is less than 0.1% by weight compared to the chlorine-resistant agent, the chlorine-resistant agent is easy to absorb moisture, agglomerated upon addition to the polymer, trimming during spinning, wave yarn (wave yarn) generation, object It may cause nonuniformity, on the contrary, if it exceeds 10% by weight, no further coating effect can be expected.

In the coating method, the melamine-based compound is added to a solvent such as water, alcohol, ether, or dioxane so as to be 0.1 to 10% by weight of the chlorine-resistant agent, and the uncoated chlorine-resistant compound is dissolved in the solvent in which the melamine-based compound is dissolved. Input. Subsequently, the temperature of the solvent is gradually increased, followed by stirring while heating to 50 to 170 ° C. A high pressure reactor can be used if necessary. After coating by stirring for about 0.5 to 2 hours, and through a filter and drying process to obtain a coated chlorine-resistant. As another method, known methods such as a physical mixing coating method of mixing the melamine compound dissolved in a solvent as described above with the chlorine resistant agent in a conventional high speed mixer and then drying the mixture may be used.

Polyurethane polymers used in the preparation of the spandex fibers of the present invention, as known in the art, reacted with organic diisocyanate and polyol (also referred to as 'polymer diol') to prepare a polyurethane precursor, which was then dissolved in an organic solvent. It is then prepared by reacting with diamines and monoamines.

Examples of the organic diisocyanate used in the present invention include diphenylmethane-4,4′-diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, butylene diisocyanate, hydrogenated P, P-methylene diisocyanate, and the like. have. Examples of the polyol include polytetramethylene ether glycol, polypropylene glycol, polycarbonate diol, and the like. The diamines are used as chain extenders, and examples thereof include ethylenediamine, propylenediamine, hydrazine, and the like. Monoamines are also used as chain terminators, examples of which are diethylamine, monoethanolamine, dimethylamine and the like.

In the present invention, in order to prevent discoloration and deterioration of physical properties of the spandex in ultraviolet rays, atmospheric smog, heat treatment during the spandex processing process, hindered phenol compounds, benzofuran- warm compounds, semicarbazide compounds, and benzotria Sol-based compounds, hindered amine compounds, polymeric tertiary amine stabilizers such as polyurethanes with tertiary nitrogen atoms, polydialkyl aminoalkyl methacrylates and the like can be added. .

In addition to the above components, the spandex fiber of the present invention may further include additives such as titanium dioxide, magnesium stearate, and the like. The titanium dioxide may be used in the range of 0.1 to 5 wt% based on the whiteness of the spandex based on the total weight of the spandex fiber. In addition, magnesium stearate may be used in the range of 0.1 to 2% by weight based on the total weight of spandex fiber, which is added to improve the dissolvability of the spandex.

In addition, the method for producing a spandex fiber excellent in chlorine resistance and heat resistance according to the present invention, in the production of spandex fiber, (1) a group consisting of an oxide or hydroxide of a metal selected from zinc or magnesium or a composite oxide of zinc and magnesium A chlorine-resistant coating step of preparing a melamine-coated chlorine agent by coating any one chlorine-resistant chlorine compound selected from the group; (2) preparing a polyurethane spinning stock solution by mixing the melamine-coated chlorine agent obtained in the chlorine-resistant coating step with a polyurethane solution; And (3) a spinning step of spinning the spinning stock solution according to a conventional spandex spinning method.

The chlorine-resistant coating step of (1) is a step of preparing a raw material for producing a spandex having excellent chlorine resistance and heat resistance by coating with a melamine-based compound on the surface of the chlorine-resistant agent as described above For example, it consists of coating with a melamine-based compound any one chlorine-resistant agent selected from the group consisting of oxides or hydroxides of a metal selected from zinc or magnesium or complex oxides of zinc and magnesium. As the coating method, conventional fine particle coating methods known to those skilled in the art can be suitably used. That is, a known method such as mixing and stirring the particles to be coated and the material to be coated with each other, sieving as necessary, and performing drying and post-treatment may be applied.

The melamine-coated anti-chlorine agent thus obtained is mixed with the raw material of the spandex yarn, and is also spun in accordance with conventional spinning methods known to those skilled in the art to obtain spandex fibers excellent in chlorine resistance and heat resistance.

Hereinafter, preferred embodiments and comparative examples of the present invention will be described.

The invention can be better understood by the following examples, which are intended for purposes of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.

Examples 1-8

518 g of diphenylmethane-4,4'-diisocyanate and 2,328 g of polytetramethylene ether glycol (molecular weight 1,800) were reacted with stirring for 90 minutes at 80 ° C. under a nitrogen gas stream to prepare a polyurethane prepolymer having an isocyanate at the sock end. It was. After the prepolymer was cooled to room temperature, 4,269 g of dimethylacetamide was added to obtain a polyurethane prepolymer solution. Subsequently, 34.4 g of ethylene diamine, 10.6 g of propylene diamine, and 9.1 g of diethylamine were dissolved in 1117 g of dimethylacetamide, and then added to the polyurethane prepolymer solution at 10 ° C. or lower to obtain a polyurethane solution. As an additive with respect to solid content of this polymer, 1.5 weight% of ethylene bis (oxyethylene) bis- (3- (5- t -butyl-4-hydroxy m -toyl) propionate), 5,7-di- t -Butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one 0.5% by weight, 1,1,1 ', 1'-tetramethyl-4,4'-(methylene-di- p 1% by weight of phenylene) dimicarbazide, 1% by weight of poly (N, N-diethyl-2-aminoethyl methacrylate), 0.1% by weight of titanium dioxide, 0.5% by weight of magnesium stearate and Metal compounds as shown (Examples 1 to 8) were added and mixed to obtain a polyurethane spinning stock solution.

After degassing this spinning stock solution, a 4 filament 40 denier spandex fiber was prepared at a spinning temperature of 250 ° C. in a dry spinning process, and the physical properties thereof were also shown in Table 1 below.

Comparative Examples 1 to 3

As shown in Table 1, except that the coating or coating content outside the scope of the present invention was carried out in the same manner as in the above Examples, the results are also shown in Table 1 below.

Chlorine resistance and heat resistance in this Example and Comparative Example were measured as follows.

Experimental Example 1: Chlorine Resistance Test

Strong retention rate test in chlorine water: Treated for 2 hours in water at pH 4.2, 97-98 ℃ for 2 hours in a state where the spandex yarn is 50% elongated, cooled at room temperature, and then cooled to room temperature in 45L chlorine water at 3.5ppm and pH 7.5 After 24 hours of deposition at, strong retention was evaluated.

* Strong holding ratio (%) = S / S _o × 100 (S _o : strong before treatment, S: strong after treatment)

* For strong evaluation, Instron 4301 (Instron 4301; Instron, USA) was used, the sample length was 5 cm, and the cell was 1 kg using a tensile speed of 300 mm / min (Cross Head Speed). Measured in The results are shown in Table 1 below.

Experimental Example 2: Heat Resistance Test

Sample preparation for heat resistance test: Elastic yarns were knitted with spandex using a circular knitting machine (KT-400, 4 inches in diameter, 400 submerged, Nagaka Seiki Co., Japan), where the length of the sample was 5 cm. It was. Then, as a refining agent, 2 g / l of UNITOL CT-81 (Neongseong Sung, Korea) and 3 g / l of UNIITOL-SMS (Neongseong, Korea) were used as the spandex refining method using a conventional spandex refining method. The circular knitted fabric was refined. The heat resistance was measured using this circular knitted fabric sample.

Heat resistance test: Samples were treated at 200 ° C. for 10 minutes in a dry oven capable of air circulation. The yellowing value "b" of the sample was measured before and after the sample was processed by Color-view (Gardener, USA). The difference between the b value after the sample treatment and the b value before the treatment was expressed by Δb. The results are shown in Table 1 below.

division Coating Coating amount ¹ (% by weight) Chlorine-resistant Yarn content ² (% by weight) Strong retention rate (24hr) ³ (%) Heat resistance (Δb) ⁴ Example 1 DMPP + MAS-MC 4 ZnO 3 87 4.2 Example 2 DMPP + SAS-MC 4 ZnO 3 86 4.0 Example 3 MAS-MC 4 Mg (OH) ₂ 3 84 4.5 Example 4 SAS-M 4 MgO 3 85 3.5 Example 5 SAS-DMPP 4 ZnO 3 88 3.4 Example 6 Melamine 4 ZnO 3 85 4.3 Example 7 MC 4 ZnO 3 85 4.5 Example 8 DMPP 4 ZnO / MgO ⁵ 3 89 3.7 Comparative Example 1 MAS-MC 11 ZnO 3 81 3.8 Comparative Example 2 Stearic acid 4 ZnO 3 84 5.8 Comparative Example 3 none none ZnO 3 75 6.4  DESCRIPTION OF SYMBOLS 1: Coating amount is the amount of coating agent compared with chlorine-resistant agent 2: Content in the yarn of the chlorine-resistant agent coated by this invention 3: Strong retention after 24 hours treatment in chlorine water according to Experimental example 1: Experimental example The amount of change in color before and after the heat treatment (yellowing value) according to 2; The smaller the value, the less discoloration DMPP + MAS-MC: 1: 1 mixture of dimelamine pyrophosphate and myristic acid-substituted melamine cyanurate DMPP + SAS-MC: Dimelamine pyrophosphate and stearic acid substituted melamine cyanurate 1: 1 mixture MAS-MC: Mysterinic acid substituted melamine cyanurate SAS-M: Stearic acid substituted melamine SAS-DMPP: Stearic acid substituted dimelamine pyrophosphate MC: Melamine cyanurate DMPP: Dimelamine pyrophosphate

As shown in Table 1, the spandex fibers of the examples containing the metal compound coated with the appropriate amount of the melamine-based compound of the present invention is not coated with the comparative example 1 and the melamine-based compound in excess of the melamine-based compound It was confirmed that the chlorine resistance and heat resistance that are relatively better than Comparative Examples 2 and 3 at the same time.

As described above, according to the present invention has an effect that a spandex fiber having excellent chlorine resistance and heat resistance at the same time is provided.

Since the spandex fiber produced according to the present invention is excellent in chlorine resistance and heat resistance, it can be effectively used in sports clothing such as underwear, socks, especially swimwear.

Although the present invention has been described in detail only with respect to the described embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made within the technical scope of the present invention, and such modifications and modifications belong to the appended claims.

Claims (5)

Melamine-coated anti-chlorine agent is included in the spandex yarn, wherein the melamine-coated anti-chlorine agent is any one selected from the group consisting of oxides or hydroxides of a metal selected from zinc or magnesium or a complex oxide of zinc and magnesium Spandex fiber excellent in chlorine resistance and heat resistance, characterized in that the chlorine-resistant compound is coated with a melamine-based compound. The method of claim 1, The melamine-based compound used for the coating of the melamine-coated anti-chlorine agent is a melamine compound, a melamine compound substituted with phosphorus (P), a melamine cyanurate compound, a melamine compound substituted with an organic compound having a carboxyl group, and an organic having a carboxyl group. It is selected from the group consisting of a melamine compound substituted with a compound and phosphorus (P) is bonded, a melamine cyanurate compound substituted with an organic compound having a carboxyl group, or a mixture of two or more thereof. Spandex fiber. The method of claim 1, The melamine-coated chlorine agent is characterized in that the spandex yarn is comprised of 0.1 to 10% by weight of the spandex fiber, characterized in that excellent chlorine resistance and heat resistance. The method of claim 1, The melamine-based compound spandex fiber excellent in chlorine resistance and heat resistance, characterized in that the coating in an amount of 0.1 to 10% by weight relative to the chlorine agent. In the manufacture of spandex fiber, (1) A method for producing a melamine-coated anti-chlorine agent by coating a melamine-based compound with any one of the chlorine-resistant chlorine selected from the group consisting of oxides or hydroxides of zinc or magnesium or a complex oxide of zinc and magnesium Chlorine coating step; (2) preparing a polyurethane spinning stock solution by mixing the melamine-coated chlorine agent obtained in the chlorine-resistant coating step with a polyurethane solution; And (3) spinning the spinning stock solution according to a conventional spandex spinning method; Method for producing a spandex fiber excellent in chlorine resistance and heat resistance, characterized in that consisting of.