EP2484821B1 - Spandex fiber with excellent chlorine resistance, and preparation method thereof - Google Patents

Spandex fiber with excellent chlorine resistance, and preparation method thereof Download PDF

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Publication number
EP2484821B1
EP2484821B1 EP10820828.1A EP10820828A EP2484821B1 EP 2484821 B1 EP2484821 B1 EP 2484821B1 EP 10820828 A EP10820828 A EP 10820828A EP 2484821 B1 EP2484821 B1 EP 2484821B1
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EP
European Patent Office
Prior art keywords
spandex fiber
polyurethane
tertiary
butyl
acid
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EP10820828.1A
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German (de)
English (en)
French (fr)
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EP2484821A2 (en
EP2484821A4 (en
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Hyun Gee Chung
Ji Hye Hong
Yeon Soo Kang
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Hyosung Corp
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Hyosung Corp
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties

Definitions

  • the present invention relates to a spandex fiber having enhanced chlorine resistance and a production method thereof, and more particularly to a spandex fiber containing a symmetrically di-hindered hydroxyphenyl-based additive and an inorganic chlorine-resistant agent, which improve the chlorine resistance of the spandex fiber while maintaining the inherent physical properties of the polyurethane polymer of the spandex fiber.
  • Spandex a typical polyurethane elastic fiber, has high rubber-like elasticity and excellent physical properties such as tensile stress and resilience, and thus is frequently used for underwear, socks, sports and leisure wear, and the like.
  • the physical properties of the main component of spandex which is polyurethane show significant deterioration when it is bleached with chlorine, and the physical properties such as tenacity of swimwear made of spandex and polyamide deteriorate when they are used in swimming pools having an active chlorine content of 0.5-3.5 ppm or higher.
  • Chlorine-resistant agents used in spandex include zinc oxide disclosed in US Patent No. 4,340,527 , a mixture of huntite and hydromagnesite disclosed in US Patent No. 5,626,960 , calcium carbonate and barium carbonate disclosed in Korean Patent Publication No. 92-03250 , a MgO/ZnO solid solution disclosed in Japanese Unexamined Patent Publication No. Hei 6-81215 , magnesium oxide or magnesium hydroxide or hydrotalcite disclosed in Japanese Unexamined Patent Publication No.
  • Sho 59-133248 and a hydrotalcite treated with a higher fatty acid and a silane coupling agent, disclosed in Japanese Unexamined Patent Publication No. Hei 3-292364 .
  • phenolic compounds are also used as additives to improve the chlorine resistance of spandex fibers.
  • Japanese Unexamined Patent Publication No. Sho 50-004387 discloses a phenolic additive which is used as a stabilizer for spandex
  • US Patent No. 6,846,866 discloses the technology of using a mixture of an inorganic additive and an organic additive to improve the resistance to chlorine and the resistance to discoloration caused by combustion fumes.
  • the present invention has been made in order to satisfy the above technical requirement, and it is an object of the present invention to provide a spandex fiber which has improved chlorine resistance while maintaining the inherent physical properties of the polyurethane polymer of the spandex fiber.
  • Another object of the present invention is to provide a method for producing a spandex fiber, which can improve the chloride resistance of the spandex fiber while maintaining the inherent physical properties of the polyurethane polymer of the spandex fiber.
  • One aspect of the present invention for achieving the above objects is directed to a spandex fiber having excellent chlorine resistance, which contains, based on the polyurethane solid content, 0.1-5 wt% of a symmetrically di-hindered hydroxyphenyl-based compound and 0.1-10 wt% of an inorganic chlorine-resistant agent.
  • Another aspect of the present invention for achieving the above objects is directed to a method for producing a spandex fiber, comprising the steps of:
  • the spandex fiber according to the present invention has excellent discoloration resistance and chlorine resistance while maintaining the inherent physical properties of polyurethane, such as whiteness, holding power, tearing strength, bursting strength and elasticity. Thus, it can be effectively used in underwear such as shapewear, socks, and sportswear such as swimwear and gymnastic wear.
  • a spandex fiber according to one embodiment of the present invention contains, based on the polyurethane solid content, 0.1-5 wt% of a symmetrically di-hindered hydroxyphenyl-based compound and 0.1-10 wt% of an inorganic chlorine-resistant agent.
  • This spandex fiber has improved discoloration resistance and chlorine resistance while maintaining the inherent physical properties of the polyurethane polymer, and thus can be applied to various wear, such as underwear, sportswear, and casual wear.
  • the spandex fiber of the present invention is a fiber produced from a fiber-forming substance which is a long chain synthetic polymer comprised of at least 85% of segmented polyurethane.
  • a polymer which is spun into the spandex fiber is a copolymer comprising a urethane bond.
  • the polyurethane polymer which is used for the production of the spandex fiber is prepared by reacting an organic diisocyanate with a polymeric diol to prepare a polyurethane precursor, dissolving the polyurethane precursor in an organic solvent, and then reacting the polyurethane precursor with a diamine and a monoamine.
  • organic diisocyanate examples include diphenylmethane-4,4'-diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, butylene diisocyanate, hydrogenated diphenylmethane-4,4'-diisocyanate, methylene-bis(4-phenylisocyanate), 2,4-tolylene diisocyanate, methylene-bis(4-cyclohexylisocyanate), isophorone diisocyanate, tetramethylene-p-xylylene diisocyanate, and mixtures thereof.
  • examples of the polymeric diol that is used in the present invention include polytetramethylene ether glycol, polypropylene glycol, polycarbonate diol, and the like.
  • the diamine is used as a chain extender, and examples thereof include ethylenediamine, propylenediamine, hydrazine, 1,4-cyclohexanediamine, hydrogenated m-phenylenediamine (HPMD), 2-methylpentamethylenediamine (MPMD), and the like.
  • the chain extender is one or more of ethylenediamine, 1,3-propylenediamine, and 1,4-cyclohexanediamine, optionally mixed with HPMD, MPMD and/or 1,2-propylenediamine.
  • the monoamine is used as a chain terminator, and examples thereof include diethylamine, monoethanolamine, dimethylamine, and the like.
  • the symmetrically di-hindered hydroxyphenyl-based compound that is used in the present invention may be one or more selected from the group consisting of tetrakis [methylene-2-(3,5-di-tertiary-butyl-4-hydroxyphenyl) propionate]methane, tris(3,5-di-tertiary-butyl-4-hydroxy-5-methylphenyl) propionate, 3,3',3",5,5',5"-hexa-tetra-butyl-a,a',a"-(mesitylene-2,4,6-trile)tri-p-cresol, hexamethylenbis[3-(3,5-di-tertiary-butyl-4-hydroxyphenyl) propionate], 1,2-bis(3,5-di-tertiary-butyl-4-hydroxyhydroxyamyl)hydrazine, N,N'-hexamethylenbis(3,5-di-tertiary-butyl-4-
  • the symmetrically di-hindered hydroxyphenyl-based compound is preferably added in an amount of 0.1-5 wt% based on the polyurethane solid content. If the amount of the symmetrically di-hindered hydroxyphenyl-based compound that is added is less than 0.1 wt%, it will not significantly contribute to improving the chlorine resistance of the spandex fiber, and once more than 5 wt% is added, any further increase will not lead to an improvement in the effect thereof.
  • the inorganic chlorine-resistant agent that is used in the present invention may be a hydrotalcite represented by the following formula 1, a huntite represented by the following formula 2, a hydromagnesite represented by the following formula 3, zinc oxide, magnesium oxide, or the like.
  • Inorganic chlorine-resistant agents such as hydrotalcite, a physical mixture of huntite and hydromagnesite, basic magnesium carbonate, zinc oxide, and magnesium oxide, have the property of capturing halogen atoms, and thus are very effective at neutralizing chlorine.
  • Huntite and hydromagnesite are minerals which are present in the form of mixtures and are difficult to separate into pure huntite or hydromagnesite.
  • Non-limiting examples of the hydrotalcite compound represented by formula 1 include Mg 4.5 Al 2 (OH) 13 CO 3 ⁇ 3.5H 2 O, Mg 6 Al 2 (OH) 16 CO 3 ⁇ 5H 2 O, Mg 8 Al 2 (OH) 20 CO 3 ⁇ 6H 2 O, Mg 4 Al 2 (OH) 12 CO 3 ⁇ 3H 2 O, 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 , and any mixtures thereof.
  • Hydrotalcite has the property of absorbing water, and thus when it is added to a polyurethane polymer in an uncoated state, it will cause gelation and coagulation, thereby causing yarn breakage and the like in a spinning process.
  • hydrotalcite may be used after it has been coated. Even when uncoated hydrotalcite is used, sand grinding or milling of the uncoated hydrotalcite can provide the same spinning properties as those obtained when coated hydrotalcite is used.
  • Examples of the coating agent which may be used in the present invention include, but are not limited to, aliphatic alcohols, fatty acids, fatty acid salts, fatty acid esters, phosphoric acid esters, styrene/maleic acid anhydride copolymers and derivatives thereof, silane coupling agents, titanate coupling agents, polyorganosiloxanes, polyorganohydrogensiloxanes and melamine-based compounds.
  • fatty acids, fatty acid salts and/or melamine-based compounds are preferred.
  • Fatty acids and fatty acid salts exhibit excellent coating effects compared to other coating agents.
  • the coating process for hydrotalcite may be carried out by adding a coating agent to a solvent such as water, alcohol, ether or dioxane in an amount of 0.1 to 10 wt% based on the weight of hydrotalcite, adding uncoated hydrotalcite thereto and stirring the resulting solution at an elevated temperature of 60 to 180 °C (if necessary, using a high-pressure reactor) for about 20 minutes to 2 hours, followed by filtering and drying.
  • a coating process may be performed by heat-melting a coating agent without using a solvent and mixing the melted coating agent with hydrotalcite at high speed.
  • the coating process should be performed in water at a temperature of 160 °C or higher under pressure, because the melamine-based compound has a high melting point.
  • the fatty acid which may be used as the coating agent for hydrotalcite in the present invention is preferably one or more selected from mono- or poly-hydroxy fatty acids having a linear or branched hydrocarbon chain containing 3 to 40 carbon atoms.
  • Specific examples of the fatty acid include lauric acid, caproic acid, palmitic acid and stearic acid.
  • the fatty acid salt which may be used in the present invention contains either a metal selected from metals of Groups I to III of the Periodic Table or zinc.
  • the fatty acid of the fatty acid salt may be saturated or unsaturated, may contain 6 to 30 carbon atoms and may be monofunctional or bifunctional.
  • Examples of the fatty acid salt include lithium, magnesium, calcium, aluminum or zinc salts of oleic acid, palmitic acid or stearic acid, preferably magnesium stearate, calcium stearate and aluminum stearate, more preferably magnesium stearate.
  • the melamine-based compound which may be used as a coating agent in the present invention may be one or a mixture of two or more selected from melamine compounds, phosphor-containing melamine compounds and melamine cyanurate compounds, which may be substituted with an organic compound having a carboxyl group.
  • the melamine compound may be selected from methylene dimelamine, ethylene dimelamine, trimethylene dimelamine, tetramethylene dimelamine, hexamethylene dimelamine, decamethylene dimelamine, dodecamethylene dimelamine, 1,3-cyclohexylene dimelamine, p -phenylene dimelamine, p -xylene dimelamine, diethylene trimelamine, triethylene tetramelamine, tetraethylene pentamelamine, hexaethylene heptamelamine, melamine formaldehyde and the like.
  • the phosphor-containing melamine compounds comprise a phosphoric acid or phosphate coupled to the above-described melamine compounds, and specific examples thereof include dimelamine pyrophosphate, melamine primary phosphate, melamine secondary phosphate, melamine polyphosphate, and a melamine salt of bis-(pentaerythritol phosphate) phosphoric acid, etc.
  • the melamine cyanurate compounds are melamine cyanurates substituted with at least one substituent of selected from methyl, phenyl, carboxymethyl, 2-carboxyethyl, cyanomethyl, 2-cyanoethyl and the like.
  • the above melamine-based compounds preferably contain an organic compound having a carboxyl group.
  • the organic compound having a carboxyl group include aliphatic monocarboxylic acids, aliphatic dicarboxylic acids, aromatic monocarboxylic acids, aromatic dicarboxylic acids, aromatic tetracarboxylic acids, cycloaliphatic monocarboxylic acids, and cycloaliphatic dicarboxylic acids.
  • the aliphatic monocarboxylic acids include caprylic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, eicosanoic acid and behenic acid;
  • the aliphatic dicarboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebasic acid, 1,9-nonanedicarboylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid and 1,14-tetradecanedicarboxylic acid;
  • the aromatic monocarboxylic acids include benzoic acid,
  • the hydromagnesite of formula 3 may be obtained from minerals or by synthesis.
  • a coating agent which may be used for coating of hydromagnesite in the present invention include, but are not limited to, aliphatic alcohols, fatty acids, fatty acid salts, fatty acid esters, phosphoric acid esters, styrene/maleic acid anhydride copolymers and derivatives thereof, silane coupling agents, titanate coupling agents, polyorganosiloxanes, polyorganohydrogensiloxanes and melamine-based compounds.
  • fatty acids, fatty acid salts and/or melamine-based compounds are preferred.
  • Fatty acids and fatty acid salts exhibit excellent coating effects compared to other coating agents.
  • the coating process for hydromagnesite may be carried out by adding a coating agent to a solvent such as water, alcohol, ether or dioxane in an amount of 0.1 to 10 wt% based on the weight of hydrotalcite, adding an uncoated hydromagnesite thereto and stirring the resulting solution at an elevated temperature of 50 to 170 °C (if necessary, using a high-pressure reactor) for about 20 minutes to 2 hours, followed by filtering and drying.
  • the coating process may be performed by heat-melting a coating agent without using a solvent and mixing the melted coating agent with hydromagnesite at high speed.
  • the coating process should be performed in water at a temperature of 160 °C or higher under pressure, because the melamine-based compound has a high melting point.
  • the fatty acid which may be used as a coating agent for hydromagnesite in the present invention is preferably one or more selected from mono- or poly-hydroxy fatty acids having a linear or branched hydrocarbon chain containing 3 to 40 carbon atoms.
  • Specific examples of the fatty acid include lauric acid, caproic acid, palmitic acid and stearic acid.
  • the fatty acid salt which may be used in the present invention contains either a metal selected from metals of Groups I to III of the Periodic Table or zinc.
  • the fatty acid of the fatty acid salt may be saturated or unsaturated, may contain 6 to 30 carbon atoms and may be monofunctional or bifunctional.
  • Examples of the fatty acid salt include lithium, magnesium, calcium, aluminum or zinc salts of oleic acid, palmitic acid or stearic acid, preferably magnesium stearate, calcium stearate and aluminum stearate, more preferably magnesium stearate.
  • the chlorine-resistant agent which is used in the present invention is preferably added in an amount of 0.1-10 wt% based on the polyurethane solid content. If the amount added of the chlorine-resistant agent is less than 0.1 wt%, the chloride resistance of the spandex fiber will be insufficient, and if the amount is more than 10 wt%, the strength, elongation and modulus of the spandex fiber will deteriorate due to the excessive content of inorganic compounds.
  • a stabilizer may be added to the polyurethane polymer in order to prevent the discoloration and deterioration in physical properties of the spandex which result from either heat treatment during spandex processing or UV light, smog and the like.
  • Specific examples of the stabilizer include hindered phenolic compounds, benzofuranone-based compounds, semi-carbazide-based compounds, benzotriazol-based compounds, hindered amine-based compounds, polymeric tertiary amine stabilizers (e.g., a tertiary nitrogen atom-containing polyurethane, polydialkyl aminoalkyl methacrylate, etc.), and the like.
  • the spandex fiber of the present invention may further include, in addition to the above-described compounds, inorganic additives such as titanium dioxide, magnesium stearate, etc.
  • the titanium dioxide may be used in an amount of 0.1-5 wt% based on the weight of the spandex fiber, depending on the whiteness of the spandex fiber.
  • the magnesium stearate is used to enhance the unwinding property of the spandex fiber and is added in an amount of 0.1 to 2 wt% based on the weight of the spandex fiber.
  • the polyurethane spinning solution may contain other various additives for specific purposes, unless these additives interfere with the effects of the present invention.
  • additives include stabilizers, UV light absorbers, light resistant agents, antioxidants, anti-tack agents, lubricants such as mineral oil and silicone oils, antistatic agents, and the like.
  • examples of the additives include hindered phenolic stabilizers such as 2,6-di-t-butyl-4-methyl-phenol as a light stabilizer, antioxidants, phosphorus-containing chemicals, nitrogen oxide traps, light stabilizers, hindered amine stabilizers, metal salts such as magnesium stearate and barium sulfate, bactericides containing silver, zinc, or compounds thereof, deodorants, anti-static agents, and the like.
  • Another aspect of the present invention is directed to a method for producing a spandex fiber having excellent chlorine resistance.
  • an organic diisocyanate is reacted with a diol to prepare a polyurethane precursor, after which the polyurethane precursor is dissolved in an organic solvent and then reacted with a diamine and a monoamine, thereby preparing a polyurethane solution.
  • 0.1-5 wt% of a symmetrically di-hindered hydroxyphenyl-based compound and 0.1-10 wt% of an inorganic chlorine-resistant agent are added to the polyurethane solution, and the resulting mixture is spun to form a spandex yarn which is then wound.
  • the polyurethane solution may be melt-spun, dry-spun or wet-spun into spandex fibers.
  • the symmetrically di-hindered hydroxyphenyl-based compound and the inorganic chlorine-resistant agent may be added to the polyurethane polymer at any convenient point of time.
  • the inorganic chlorine-resistant agent may be added to the polyurethane solution together with other additives and be mixed with the polyurethane polymer during a sand-grinding or milling process.
  • the inorganic chlorine-resistant agent may also be mixed with the polyurethane polymer in a solvent during the sand-grinding or milling process in the absence of other additives.
  • the symmetrically di-hindered hydroxyphenyl-based compound may be added during the sand-grinding or milling process after it has been separately dissolved in a solvent.
  • a coated inorganic chlorine-resistant agent may also be added.
  • the process of sand-grinding or milling the inorganic chlorine-resistant agent can be performed by milling either a mixture of the inorganic chlorine-resistant agent, a solvent and a small amount of the polyurethane polymer or a slurry mixture of the inorganic chlorine-resistant agent, a solvent, a small amount of the polyurethane polymer, and other additives, using a conventional bead mill.
  • the small amount of the polyurethane polymer serves to increase the dispersibility of the inorganic chlorine-resistant agent.
  • the solvent used may be one or more selected from among dimethylacetamide, dimethylformamide and dimethylsulfoxide.
  • the polyurethane solution was mixed with, based on the solid content of the polyurethane solution, 1 wt% of poly(N,N-diethyl-2-aminoethyl methacrylate) as an acid dye enhancer, 0.1 wt% of titanium oxide as a light resistant agent, 0.26 wt% of magnesium stearate as an unwinding property enhancer, and 4 wt% of the chlorine-resistant agent hydrotalcite (Mg 4 Al 2 (OH) 12 CO 3 ⁇ 3H 2 O) coated with, based on the weight of the hydrotalcite, 2 wt% of stearic acid and 1 wt% of melamine phosphate.
  • the chlorine-resistant agent hydrotalcite Mg 4 Al 2 (OH) 12 CO 3 ⁇ 3H 2 O
  • the spinning solution was defoamed, after it was dry-spun at a spinning temperature of 260 °C and wound at a speed of 900 m/min, thereby producing a 4-filament 40-denier spandex yarn.
  • the chlorine resistance of the spandex yarn was evaluated, and the results of the evaluation are shown in Table 1 below.
  • the strength retention rate in chlorinated water was evaluated in the following manner.
  • the spandex yarn was stretched at a stretching ratio of 50%, treated with water (pH 4.5; 99 to 100 °C) for 2 hours, and dried and cooled at room temperature.
  • the spandex yarn was dipped in 45 l of chlorinated water (pH 7.0-7.5) containing 3.5 ppm of active chlorine at room temperature for 120 hours, and the strength retention rate thereof was calculated using the following equation.
  • the strength of the spandex yarn was measured using MEI by applying 32 kgf cell to a 20 cm-long sample at a cross head speed of 1000 mm/min.
  • Strength retention rate % S / S o ⁇ 100 wherein S o is strength before treatment, and S is strength after treatment.
  • a spandex yarn was produced in the same manner, except that 3,3',3",5,5',5"-hexa-tetra-butyl-a,a',a"-(mesitylene-2,4,6-trile)tri-p-cresol was used as the symmetrically di-hindered hydroxyphenyl-based compound.
  • the chlorine resistance of the produced spandex yarn was evaluated, and the results of the evaluation are shown in Table 1 below.
  • a spandex yarn was produced in the same manner, except that tetrakis[methylene-2-(3,5-di-tertiary-butyl-4-hydroxyphenyl)propionate]methane was used as the symmetrically di-hindered hydroxyphenyl-based compound and that 4 wt% of an uncoated hydrotalcite (Mg 4 Al 2 (OH) 12 CO 3 ⁇ 3H 2 O) was added as the chlorine-resistant agent.
  • the chlorine resistance of the produced spandex yarn was evaluated, and the results of the evaluation are shown in Table 1 below.
  • a spandex yarn was produced in the same manner, except that a mixture of huntite and hydromagnesite was used as the inorganic chlorine-resistant agent.
  • the chlorine resistance of the produced spandex yarn was evaluated, and the results of the evaluation are shown in Table 1 below.
  • a spandex yarn was produced in the same manner, except that hydromagnesite was used as the inorganic chlorine-resistant agent.
  • the chlorine resistance of the produced spandex yarn was evaluated, and the results of the evaluation are shown in Table 1 below.
  • a spandex yarn was produced in the same manner, except that 2,4-di-tertiary-butylphenyl-4'-hydroxy-3',5'-di-tertiarybutyl benzoate was used as the inorganic chlorine-resistant agent.
  • the chlorine resistance of the produced spandex yarn was evaluated, and the results of the evaluation are shown in Table 1 below.
  • a spandex yarn was produced in the same manner, except that an unsymmetrically di-hindered hydroxyphenyl-based compound was used instead of the symmetrically di-hindered hydroxyphenyl-based compound.
  • the chlorine resistance of the produced spandex yarn was evaluated, and the results of the evaluation are shown in Table 1 below.
  • a spandex yarn was produced in the same manner, except that the inorganic chlorine-resistant agent was used alone without using the symmetrically di-hindered hydroxyphenyl-based compound.
  • the chlorine resistance of the produced spandex yarn was evaluated, and the results of the evaluation are shown in Table 1 below.
  • Table 1 Examples Comparative Examples 1 2 3 4 5 6 1 2 Strength retention rate (%) 91.1 90.3 89.8 87.4 90.7 80.61 59.7 63.8
  • the inventive spandex fibers comprising both the symmetrically di-hindered hydroxyphenyl-based compound and the inorganic chlorine-resistant agent showed significantly high strength retention rates in chlorinated water compared to the conventional spandex fiber comprising either the symmetrically di-hindered hydroxyphenyl-based compound alone or the inorganic chlorine-resistant agent alone.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
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  • Artificial Filaments (AREA)
EP10820828.1A 2009-09-30 2010-09-29 Spandex fiber with excellent chlorine resistance, and preparation method thereof Active EP2484821B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020090092992A KR101130510B1 (ko) 2009-09-30 2009-09-30 내염소성이 우수한 스판덱스 섬유 및 그의 제조방법
PCT/KR2010/006634 WO2011040755A2 (ko) 2009-09-30 2010-09-29 내염소성이 우수한 스판덱스 섬유 및 그의 제조방법

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EP2484821A2 EP2484821A2 (en) 2012-08-08
EP2484821A4 EP2484821A4 (en) 2013-07-24
EP2484821B1 true EP2484821B1 (en) 2014-11-05

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KR101157328B1 (ko) * 2009-12-31 2012-06-15 주식회사 효성 내염소성 및 내변색성이 향상된 스판덱스 섬유 및 그의 제조방법
JP5688601B2 (ja) * 2011-06-23 2015-03-25 東レ・オペロンテックス株式会社 ポリウレタン糸ならびにそれを用いた布帛および水着
CN103422250A (zh) * 2013-07-30 2013-12-04 常熟市新达纬编厂 一种超耐氯泳衣面料的制备工艺
CN103380995A (zh) * 2013-07-30 2013-11-06 常熟市新达纬编厂 一种超耐氯泳衣面料
KR101684792B1 (ko) * 2015-07-10 2016-12-21 주식회사 효성 내염소성이 우수한 스판덱스 섬유
CN109790043A (zh) 2016-09-12 2019-05-21 丹石产业株式会社 合成水菱镁矿粒子及其制备方法
CN107059159A (zh) * 2017-05-19 2017-08-18 江苏华昌织物有限公司 一种防老化遮光网布的制备方法
CN114892294B (zh) * 2022-05-09 2023-08-29 西南大学 一种多功能聚氨酯纤维及其制备方法与应用
KR20240008108A (ko) * 2022-07-11 2024-01-18 (주)석경에이티 합성 헌타이트 제조방법 및 이를 이용한 폴리우레탄 섬유

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WO2011040755A2 (ko) 2011-04-07
WO2011040755A3 (ko) 2011-11-03
KR101130510B1 (ko) 2012-03-28
EP2484821A2 (en) 2012-08-08
EP2484821A4 (en) 2013-07-24
CN102666947B (zh) 2014-10-22
CN102666947A (zh) 2012-09-12

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