KR20110079357A - Anti-chlorine and anti-discoloration spandex fiber and preparation method thereof - Google Patents

Abstract

PURPOSE: A spandex fiber with improved chlorine resistance and discoloration resistance and a manufacturing method thereof are provided to improve chlorine resistance and discoloration resistance while keeping specific physical property of the polyurethane polymer. CONSTITUTION: The polyurethane polymer includes symmetric di hindered hydroxyphenyl system compound of 0.1 - 5% weight, phosphorus antioxidant of 0.1 - 3% weight, di semicarbazide compound of 0.1 - 3% weight, and inorganic antichlorine of 0.1 - 10% weight. The inorganic antichlorine is selected in a group consisting of hydrotalcit compound, huntite and hydromagnesite mixed mineral, hydromagnesite, zinc oxide, magnesium oxide etc.

Description

Anti-chlorine and anti-discoloration Spandex Fiber and Preparation Method etc.

The present invention relates to a spandex fiber with improved chlorine resistance and discoloration resistance and a method for producing the same, and more particularly, a symmetrical di-hindered hydroxyphenyl-based additive, a phosphorus-based antioxidant, and a dismicarbazide-based compound and an inorganic chlorine-resistant agent. The present invention relates to a spandex fiber containing a polyurethane polymer having improved chlorine resistance and discoloration resistance while maintaining conventional physical properties, and a method of manufacturing the same.

Spandex, which is a typical polyurethane elastic fiber, maintains high rubber elasticity and is excellent in physical properties such as tensile stress and recoverability. Therefore, spandex is widely used in underwear, socks, sports and leisure clothing. However, polyurethane, which is a major component of spandex, exhibits a significant decrease in physical properties in chlorine bleaching. Swimsuits made from alternating spandex and polyamide have strong physical properties such as strength when used in swimming pools with active chlorine content of 0.5 to 3.5 ppm or more. Is lowered.

Efforts have been made to improve the resistance of spandex fibers to degradation due to chlorine. As a chlorine resistant agent used in spandex, US Patent No. 4,340,527, zinc oxide, US Patent No. 5,626,960, a mixture of huntite and hydromagnesite, and Korean Patent Publication No. 92-03250, calcium carbonate and barium carbonate, 6-81215 is treated with MgO / ZnO solid solution, Japanese Patent Application Laid-Open No. 59-133248 with magnesium oxide, magnesium hydroxide or hydrotalcite, and Japanese Patent Application Laid-open No. 3-292364 with higher fatty acid and silane coupling agents. Hydrotalcites are disclosed, respectively.

In addition, in order to improve the chlorine resistance of spandex fibers, phenolic compounds may be used as additives. For example, Japanese Patent Publication No. 50-004387 discloses a phenolic additive as a stabilizer for spandex, and US Pat. Techniques for improving the chlorine resistance and discoloration by combustion by mixing additives and organic additives are disclosed.

However, there is no additive combination and composition that can significantly improve the chlorine resistance and discoloration resistance of the spandex fiber at this time, and thus further improvement is required.

The present invention satisfies the above technical requirements, and one object of the present invention is to provide a spandex fiber and a method of producing the same, while improving the chlorine resistance and discoloration resistance while maintaining the inherent physical properties of the polyurethane polymer.

Spandex fibers with improved chlorine resistance and discoloration resistance according to the present invention are 0.1 to 5% by weight of symmetrical di-hindered hydroxyphenyl compound, 0.1 to 3% by weight of phosphorus antioxidant, 0.1 to 3% by weight of di semicarbazide-based compound , Inorganic chlorine-resistant 0.1 to 10% by weight characterized in that it comprises.

According to the present invention, a method for preparing spandex fiber having improved chlorine resistance and discoloration resistance is obtained by reacting an organic diisocyanate and diol to prepare a polyurethane precursor, and then dissolving the polyurethane precursor in an organic solvent. Preparing a polyurethane solution prepared by reacting; And spinning to the polyurethane solution by adding 0.1 to 5% by weight of a symmetrical di-hindered hydroxyphenyl compound and 0.1 to 10% by weight of an inorganic chlorine agent on the basis of the polyurethane polymer.

The spandex according to the present invention is excellent in discoloration and chlorine resistance while maintaining excellent polyurethane properties such as whiteness, gripping force, tear strength, tear strength, elasticity, and so on. It can be effectively used in sports clothing, such as gymnastics.

Hereinafter, the present invention will be described in more detail.

Spandex fiber of the embodiment of the present invention is based on the polyurethane polymer 0.1 to 5% by weight of symmetrical di- hindered hydroxyphenyl-based compound, 0.1 to 3% by weight phosphorus antioxidant and 0.1 to 3% by weight of the di semicarbazide-based compound 0.1 to 10% by weight of chlorine resistant agent. The spandex fiber is improved in discoloration resistance and chlorine resistance while maintaining its inherent excellent physical properties, and can be applied to various clothes such as underwear, sports clothing, and everyday clothes.

The spandex of the present invention is a fiber made from a fiber forming material which is a long chain synthetic polymer composed of at least 85% segmented polyurethane. That is, the polymer spun into spandex fibers is a copolymer comprising urethane bonds. Polyurethane polymers used in the preparation of spandex are prepared by reacting organic diisocyanates and polymer diols to produce polyurethane precursors, which are then dissolved in organic solvents and then reacted with diamines and monoamines.

Examples of the organic diisocyanate include diphenylmethane-4,4'-diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, butylene diisocyanate, hydrogenated diphenylmethane-4,4'-diisocyanate, methylene-bis (4 -Phenyl isocyanate), 2,4-tolylene diisocyanate, methylene-bis (4-cyclohexyl isocyanate), isophorone diisocyanate, tetramethylene-p-xylylene diisocyanate and mixtures thereof.

In addition, polytetramethylene ether glycol, polypropylene glycol, polycarbonate diol, or the like may be used as the polymer diol. Diamines are used as chain extenders, for example ethylenediamine, propylenediamine, hydrazine, 1,4-cyclohexanediamine, hydrogenated m-phenylenediamine (HPMD), 2-methylpentamethylenediamine (MPMD), and the like. There is this. Chain extenders are one or more ethylenediamine, 1,3-propylenediamine and 1,4-cyclohexanediamine, optionally mixed with HPMD, MPMD and / or 1,2-propylenediamine. On the other hand, monoamine is used as a chain terminator, for example, diethylamine, monoethanolamine, dimethylamine, and the like.

In the present invention, the symmetric di hindered hydroxyphenyl compound is tetrakis [methylene-2- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane or 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-tril) tri-p-cresol, hexamethylenebis [3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,2- Bis (3,5-di-tert-butyl-4-hydroxyhydroxyanoyl) hydrazine, N, N'-hexamethylenebis (3,5-di-tert-butyl-4-hydroxyhydrocinama Mead), 2,4-di-tert-butylphenyl-4'-hydroxy-3 ', 5'-di-tert-butyl benzoate can be used one or more selected from the group consisting of.

In the present invention, the amount of the symmetric di-hindered hydroxyphenyl-based compound is preferably 0.1 to 5% by weight relative to the polyurethane polymer. When the amount of the symmetric di-hindered hydroxyphenyl-based compound is less than 0.1% by weight, the properties that contribute to improving the chlorine resistance of the spandex are small. In case of more than 5% by weight, there is no improvement effect on the excessive input. If the P-based antioxidant is less than 0.1% by weight, there is little contribution to the improvement of discoloration resistance, and if it exceeds 3% by weight, it is not effective due to the excessive input. It is small and the effect of over input is insignificant when over 3% by weight.

In the present invention, 'phosphorus antioxidant' refers to a trivalent phosphorus compound including a structure of phosphate, phosphonate, phosphonite, and the like.

The polyurethanes of the present invention contain a combination of two additives, both of which act synergistically. Specific examples of the first additives include tetrakis (2,4-di-t-butylphenyl) 4,4'-biphenyldiphosphonite, tris (2,4-di-t-butylphenyl) phosphate, bis (2,4-di-t-butylfetyl) pentaerythritol diphosphite), tris (3-t-butyl-4-hydroxyphenyl) phosphate and the like.

Examples of chemical structures of useful first additives are shown below.

Tetrakis (2,4-di-t-butylphenyl) 4,4'-biphenyldiphosphonite (phosphorus antioxidant-1)

Tris (2,4-di-t-butylphenyl) phosphate (phosphorus antioxidant-2)

Bis (2,4-di-t-butylfetyl) pentaerythritol diphosphite (phosphorus antioxidant-3)

In the present invention, the amount of phosphorus antioxidant added is preferably 0.1 to 3% by weight compared to the polyurethane polymer. When the amount is less than 0.1% by weight, it contributes to the improvement of the chlorine resistance of the spandex. It is not preferable because there is no improvement effect.

As the inorganic chlorine-resistant agent, those represented by the following formulas (1), (2) and (3), and zinc oxide, magnesium oxide, and the like can be used. Physical mixtures of hydrotalcite, huntite and hydromagnesite, and inorganic chlorine agents such as basic magnesium carbonate, zinc oxide, and magnesium oxide have the property of trapping halogen, which is very effective for harming chlorine.

M ^{2 +} _x Al ₂ (OH) _y (A ^n- ) _z O _k ? MH ₂ O

[Wherein, M ^{2 +} is Mg ^{2 +,} Ca ^{2 +} or Zn ^{2 +} a, A ^{n -} is an anion having a valence of n, x, y are two or more positive values, Z is a positive value equal to or less than 3 and, k is a positive number of 0 or more than 3, m is 0 or a positive number, a ^{n -} is ^{OH -, F -, Cl -} , Br -, NO 3 -, SO 4 2 -, CH 3 COO -, _{^{CO 3 2-, HPO 4 2 -}} , oxalate ion, salicylate ion, silicate ion or Im.

Non-limiting examples of the hydrotalcite compound of 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 including any mixture thereof do.

Hydrotalcite has a feature of absorbing moisture, and when it is added to a polyurethane polymer without coating, gel generation and aggregation may occur and cause trimming in the spinning process. Hydrotalcite can be coated and used to prevent water absorption and improve dispersibility of hydrotalcite to improve the release pressure and trimming during the spinning process. Even in the case of using uncoated hydrotalcite, when the sand grinding or milling is performed, the same radioactivity can be obtained as in the case of using the coated hydrotalcite.

Examples of coatings that can be used include aliphatic alcohols, fatty acids, fatty acid salts, aliphatic esters, phosphate esters, styrene / maleic anhydride copolymers and derivatives thereof, silane coupling agents, titanate coupling agents, polyorganosiloxanes, polyorganohydrogens One or more selected from the group consisting of siloxane and melamine-based compounds, but is not necessarily limited to these. The coating agent is preferably a fatty acid, fatty acid salt and / or melamine based compound. In the case of fatty acids or fatty acid salts, the effect of the coating is superior to other coating materials. In the coating of hydrotalcite, an appropriate amount of coating agent is added to a solvent such as water, alcohol, ether, dioxane, and the like so that the amount of the coating agent is 0.1 to 10% by weight based on the weight of hydrotalcite, and then uncoated hydrotalcite is added. The temperature is increased and stirred for 20 minutes to 2 hours at 60 to 180 ° C. (using a high pressure reactor if necessary), followed by filtering and drying after stirring. Another method is a method in which the coating agent is heated and dissolved without solvent, and then mixed with hydrotalcite at a high speed to coat the coating agent.

In the case of coating with a melamine-based compound, since the melting point of the melamine-based compound is high, it should be coated under pressure at 160 ° C or higher in water.

In the present invention, the fatty acid used as the coating agent of the hydrotalcite is preferably one or two or more selected from monovalent or polyvalent fatty acids of straight or branched chain hydrocarbons having 3 to 40 carbons. Examples of specific fatty acids are lauric acid, caproic acid, palmitic acid, stearic acid.

Fatty acid salts are those in which the metal is a metal selected from Groups I to III of the periodic table or zinc. Fatty acids of fatty acid salts may be saturated or unsaturated, contain up to 6 or less than 30 carbon atoms, and may be monofunctional or difunctional. Examples of fatty acid salts are the lithium, magnesium, calcium, aluminum or zinc salts of oleic acid, palmitic acid or stearic acid, preferably magnesium stearate, calcium stearate or aluminum stearate, more preferably magnesium stearate .

The melamine-based compound used as the coating agent in the present invention is 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, an organic compound having a carboxyl group, and phosphorus It is preferable to use the melamine cyanurate compound substituted with the melamine compound (P) couple | bonded and the organic compound which has a carboxyl group individually or in mixture.

Melamine compounds are 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 and hexaethylene heptamelamine, melamine formaldehyde and the like.

Phosphorus-bonded melamine compound is a form in which phosphoric acid is bound to the melamine compound or phosphate is bound. Lytol phosphate) and melamine salts reacted with phosphoric acid.

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

It is effective that the melamine-based compound contains an organic compound having a carboxyl group. Examples of the organic compound having a carboxyl group include aliphatic monocarboxylic acid, aliphatic dicarboxylic acid, aromatic monocarboxylic acid, aromatic dicarboxylic acid, aromatic tetracarboxylic acid, alicyclic monocarboxylic acid and alicyclic dicarboxylic acid. Etc. For example, as the aliphatic monocarboxylic acid, 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, and aliphatic dicarboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-no Nandicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid and 1,14- Tetradecanedicarboxylic acid, and aromatic monocarboxylic acids include benzoic acid, phenylacetic acid, alpha-naphthoic acid, beta-naphthoic acid, cinnamic acid, p-amino hippuric acid and 4- (2- Thiazoyl sulfamoyl) -phthalanoic acid (4- (2-thiazo (l) ylsulfamyl) -phthalaninoic acid), and aromatic dicarboxylic acids include terephthalic acid and Phthalic acid and phthalic acid, aromatic tricarboxylic acids include trimellitic acid, 1,3,5-benzenetricarboxylic acid and tris (2-carboxyethyl) isocyanurate, and aromatic tetracarboxylic acids. Are pyromellitic acid and biphenyl tetracarboxylic acid, cycloaliphatic monocarboxylic acid is cyclohexanecarboxylic acid, and cycloaliphatic dicarboxylic acid is 1,2-cyclohexane dicarboxylic acid.

Mg ₃ Ca (CO ₃ ) ₃ (Huntite) (1)

_{Mg 4 (CO 3) 4 Mg} (OH) 2 · 5H 2 0 ( hydro magnesite) (2)

Huntite and hydromagnesite are present in the form of mixtures when present as minerals and are difficult to separate into pure huntite or pure hydromagnesite.

_{^{M 2 + x (A n -}} ) y M 2 + (OH) z? mH ₂ 0 (hydromagnesite)

(Wherein, M ^{2 +} is Mg ^{2 +} or Ca ^{2 +,} A ^{n -} is CO ₃ ^{2 -,} x is 1 ~ 5, z is 0 ~ 2, m is 0 to 5.)

Hydromagnesite can also be obtained as a mineral and can also be obtained through synthesis. Examples of coatings that can be used for hydromagnesite include aliphatic alcohols, fatty acids, fatty acid salts, aliphatic esters, phosphate esters, styrene / maleic anhydride copolymers and derivatives thereof, silane coupling agents, titanate coupling agents, polyorganosiloxanes, poly And one or more selected from the group consisting of organohydrogensiloxanes and melamine-based compounds, but are not necessarily limited thereto. The coating agent is preferably a fatty acid, fatty acid salt and / or melamine based compound. In the case of fatty acids or fatty acid salts, the effect of the coating is superior to other coating materials. In the coating of hydromagnesite, an appropriate amount of coating agent is added to a solvent such as water, alcohol, ether, dioxane, etc. so that the amount of coating agent is 0.1 to 10% by weight based on the weight of hydromagnesite, the uncoated hydromagnesite is added, and then the temperature is increased. After stirring for 10 minutes to 2 hours at 50 ~ 170 ℃ (using a high-pressure reactor if necessary), after stirring and made through a filtering and drying process. As another method, the coating agent is heated and dissolved without solvent, and then mixed with hydromagnesite at a high speed to coat.

In the case of coating with a melamine-based compound, since the melting point of the melamine-based compound is high, it should be coated under pressure at 150 ° C or higher in water.

In the present invention, the fatty acid used as the coating agent of the hydromagnesite is preferably one or two or more selected from monovalent or polyvalent fatty acids of straight or branched chain hydrocarbons having 3 to 40 carbons. Examples of specific fatty acids are lauric acid, caproic acid, palmitic acid, stearic acid.

Fatty acid salts are those in which the metal is a metal selected from Groups I to III of the periodic table or zinc. Fatty acids of fatty acid salts may be saturated or unsaturated, may contain from 6 to 30 carbon atoms, and may be monofunctional or difunctional. Examples of fatty acid salts are the lithium, magnesium, calcium, aluminum or zinc salts of oleic acid, palmitic acid or stearic acid, preferably magnesium stearate, calcium stearate or aluminum stearate, more preferably magnesium stearate .

In the present invention, the inorganic chlorine agent is preferably 0.1 to 10% by weight compared to the polyurethane polymer, when less than 0.1% by weight is less characteristic of imparting chlorine resistance to the spandex fiber, when exceeding 10% by weight excessive inorganic Oiling is not preferred because it lowers the strength, elongation and modulus of spandex fibers.

The spandex of the present invention includes a hindered phenol compound, a benzofuran-one compound, a semicarbazide compound, in order to prevent discoloration or deterioration of physical properties of the spandex due to heat treatment during the spandex processing process or other ultraviolet rays, atmospheric smog, or the like. , Benzotriazole compounds, hindered amine compounds, polymeric tertiary amine stabilizers (e.g., polyurethanes with tertiary nitrogen atoms, polydialkyl aminoalkyl methacrylates), and the like, may be added to the polyurethane polymer. Can be.

In addition to the above components, the spandex of the present invention may further include an inorganic additive such as titanium dioxide and magnesium stearate. Titanium dioxide can be used in the range of 0.1 to 5% by weight, depending on the whiteness of the fiber. In addition, magnesium stearate may be used in the range of 0.1 to 2% by weight, which is added to improve the dissolvability of spandex.

A variety of other additives may be added to the polyurethane spinning stock for certain purposes, so long as it does not interfere with the effects of the present invention. Among these additives are stabilizers, ultraviolet light absorbers, light agents, antioxidants, anti-sticking agents, lubricants such as mineral oils and silicone oils, antistatic agents and the like. Examples of additives are hindered phenolic stabilizers such as 2,6-di-t-butyl-4-methylphenol, antioxidants, nitric oxide scavengers, light stabilizers, hindered amine stabilizers, magnesium stearate And metal salts such as barium sulfate, silver, zinc or compound-containing fungicides, deodorants, antistatic agents and the like.

Another aspect of the present invention relates to a method for producing spandex fiber having excellent chlorine resistance. In the case of preparing spandex fiber according to the method of the present invention, a polyurethane is prepared by reacting an organic diisocyanate and a diol to prepare a polyurethane precursor, and then dissolving the polyurethane precursor in an organic solvent and then reacting with a diamine and a monoamine. Prepare urethane solution. Subsequently, 0.1 to 5% by weight of the symmetrical di-hindered hydroxyphenyl compound and 0.1 to 10% by weight of the inorganic chlorine-resistant compound are added to the polyurethane solution, followed by spinning to form a spandex yarn. The polyurethane solution may be melt spun, dry spun or wet spun into the spandex.

In preparing the spandex of the present invention, the symmetrical di-hindered hydroxyphenyl-based compound, phosphorus antioxidant, and disemicarbazide-based compound and inorganic chlorine resistant agent may be added to the polyurethane polymer at any convenient time. For example, the inorganic chlorine resistant agent may be added to the solution together with other additives and mixed with the polyurethane polymer during the sand grinding or milling process, or separately during the sand grinding or milling process in the solvent separately from the other additives. It may also be mixed with polyurethane polymers. In addition, the symmetric di hindered hydroxyphenyl-based compound, P-based antioxidant and dissemicabazide-based compound may also be added during the sand grinding or milling process, it may be added separately dissolved in a solvent. In order to improve the dispersibility of the inorganic chlorine agent, a coated inorganic chlorine agent may be added.

The process of sand grinding or milling an inorganic chlorine agent is performed by mixing and milling an inorganic chlorine agent, a solvent and a small amount of polyurethane polymer using a conventional bead mill, or an inorganic chlorine agent, a solvent and other additives. And a small amount of polyurethane polymer can be mixed to make a slurry and milled. Here, a small amount of polyurethane polymer serves to improve the dispersibility of the inorganic chlorine agent. As a solvent, 1 or more types of dimethylacetamide, dimethylformamide, and dimethyl sulfoxide can be selected and used.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. The following examples are for illustrative purposes only and are not intended to limit the invention. All parts, percentages, etc., are by weight unless otherwise indicated.

Example 1

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

Subsequently, 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 ° C. or lower to obtain a polyurethane solution. 1% by weight of poly (N, N-diethyl-2-aminoethyl methacrylate) as a dye enhancer as an additive relative to the solid content of the polymer, 0.1% titanium dioxide as a light-resistant agent, 0.26% by weight magnesium stearate as a disintegration enhancer, and 2% by weight of stearic acid and 1% by weight of melamine polyphosphate as a chlorinating agent, and ₄ % by weight of hydrotalcite Mg ₄ Al ₂ (OH) ₁₂ CO ₃ · 3H ₂ O coated with 1% by weight. Additionally 0.5 wt% of (tetrakis [methylene-2- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane as symmetrical di-hindered hydroxyphenyl-based compound in the slurry, Phosphorus antioxidant As a phosphorus antioxidant, 0.5 wt% of (tetrakis (2,4-di-t-butylphenyl) 4,4'-biphenyldiphosphonite) and an aliphatic dissemicabazide-based mixture (1,6- Hexamethylene bis (N, N-dimethyl semicarbazide) 0.5 wt% was added and mixed to obtain a spinning solution.

After degassing the spinning stock solution, the spinning temperature was 260 ° C. in the dry spinning process, and the winding speed was wound at 900 m / min to prepare 3 filament 40 denier spandex yarn, and its chlorine resistance was evaluated and shown in Table 1 below.

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

The spandex yarn was treated for 1 hour in water at pH 4.5 and 99-100 ° C. under 50% elongation, dried and cooled at room temperature, immersed in 45 L chlorine water at 3.5 ppm of active chlorine and pH 7.0-7.5 at room temperature for 120 hours. The intensity retention was calculated by the following equation. MEL was used for the strength evaluation, and the sample length was 20 cm and measured at a cross head speed of 1000 mm / min using a cell of 32 kgf.

Strong retention (%) = S / S _o × 100

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

In addition, in order to evaluate the discoloration resistance of the spandex yarn, the difference in discoloration (measurement of color difference) due to three discoloration factors was measured by the following method.

After weaving the spandex yarn of each experimental example in the form of a fabric, a sample was prepared with a width of 3cm and a length of 10cm. Each sample was treated at 80 ° C. for 20 minutes in a bath of 1 g / L of refiner and 1 g / L of NaOH, and naturally dried for 12 hours.

   (1) Heat treatment condition: The heat treatment was performed for 10 minutes in a 200 ℃ oven.

   (2) UV Lamp treatment conditions: left for 24 hours in the UV-B Lamp.

   (3) NOX GAS treatment condition: NOX GAS was generated using Sodium Nitrate and Phosphoric acid and left for 24 hours under the same conditions.

Discoloration degree is to a Red value Color-view was measured using the ^TM, the Red value when untreated a1, the Yellow value b1, after the treatment of the BYK Gardner社by a2, the Yellow value b2 △ a = a2-a1, The color difference (color difference) was shown after calculation by (b) b2-b1.

  Lower values of Δa indicate less redness, and lower values of Δb indicate less yellowing.

Example 2

Symmetric dihindered hydroxy phenyl-based compounds were prepared using 3,3 ', 3 ", 5,5', 5" -hexa-tetra-butyl-a, a ', a "-(mesitylene-2,4,6- Except for using tril) tri-p-cresol to prepare a spandex yarn using the same polymer as in Example 1, to evaluate the chlorine resistance and the results are shown in Table 1 together.

Example 3

Spandex was prepared using the same polymer as in Example 1, except that 4 wt% of Mg ₄ Al ₂ (OH) ₁₂ CO ₃ .3H ₂ O was added to the uncoated hydrotalcite as an inorganic chlorine-resistant agent. To evaluate the chlorine resistance, the results are shown in Table 1 together.

Example 4

Except for the inorganic chlorine agent using a mixed mineral of huntite and hydromagnesite was prepared spandex yarn using the same polymer as in Example 1, and evaluated the chlorine resistance and the results are shown in Table 1 together.

Example 5

Except for the use of hydromagnesite as an inorganic chlorine-resistant agent was prepared spandex yarn using the same polymer as in Example 1, and evaluated the chlorine resistance and the results are shown in Table 1 together.

Example 6

A spandex yarn was prepared using the same polymer as in Example 1 except that the phosphorus antioxidant compound (tris (2,4-di-t-butylphenyl) phosphate) was used, and the chlorine resistance thereof was evaluated. It is shown together in Table 1 below.

Comparative Example 1

A spandex yarn was prepared using the same polymer as in Example 1, except that only a symmetrical dihindered hydroxy phenyl compound was used without using a phosphorus antioxidant and an aliphatic disamicarbazide compound, and evaluated chlorine resistance. The results are shown in Table 1 together.

Comparative Example 2

Phosphorus-based antioxidants and aliphatic disamicarbazide-based compounds are used, except that asymmetric di-hindered hydroxyphenyl-based compounds are not used and asymmetric di-hindered hydroxyphenyl-based compounds are used. Spandex yarn was prepared using the polymer, and chlorine resistance was evaluated. The results are shown in Table 1 together.

Comparative Example 3

Spandex yarn was prepared using the same polymer as in Example 1, except that only an inorganic chlorine-resistant compound was used without using a symmetrical dihindered hydroxyphenyl compound and a phosphorus antioxidant and an aliphatic dimicarbazide compound. To evaluate the chlorine resistance, the results are shown in Table 1 together.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Δa 0.6 0.9 1.1 1.0 1.3 1.5 6.9 5.5 3.6 Δb 2.1 2.6 1.9 1.7 2.3 2.5 8.5 6.9 10.2 Strong retention rate (%) 88.1% 87.5% 88.5% 89.2% 87.6% 85.3% 88.3% 75.8% 62.1%

Although the embodiments of the present invention have been described in detail above, these are merely for illustrative purposes and should not be construed as limiting the present invention. It will be apparent to those skilled in the art that many variations and modifications of the above embodiments are possible without departing from the spirit and scope of the invention. The protection scope of the invention should be defined by the appended claims and their equivalents.

Claims (8)

Based on the polyurethane polymer, symmetrical di-hindered hydroxyphenyl-based compound 0.1 to 5% by weight, phosphorus antioxidant 계 0.1 to 3% by weight, disemicabazide compound 계 0.1 to 3% by weight, inorganic chlorine-resistant 0.1 to 10% by weight Spandex fiber with improved chlorine resistance and discoloration resistance, comprising%. The method of claim 1, wherein the symmetric di hindered hydroxyphenyl compound is tetrakis [methylene-2- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane or tris ( 3,5-di-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 3,3 ', 3 ", 5,5', 5" -hexa-tetra-butyl-a, a ' , a ”-(mesitylene-2,4,6-tril) tri-p-cresol, hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,2-bis (3,5-di-tert-butyl-4-hydroxyhydroxyanoyl) hydrazine, N, N'-hexamethylenebis (3,5-di-tert-butyl-4- Hydroxyhydrocinamide), 2,4-di-tert-butylphenyl-4'-hydroxy-3 ', 5'-di-tert-butyl benzoate, and at least one member selected from the group consisting of Spandex Fiber with Excellent Chlorine Resistance The method of claim 1, wherein the phosphorus antioxidant is tetrakis (2,4-di-t-butylphenyl) 4,4'-biphenyldiphosphonite, tris (2,4-di-t-butylphenyl) phosphate And at least one member selected from the group consisting of tris (3-t-butyl-4-hydroxyphenyl) phosphate The inorganic chlorine-resistant chlorine resistance is excellent in chlorine resistance, characterized in that at least one selected from the group consisting of hydrotalcite compounds, huntite and hydromagnesite mixed minerals, hydromagnesite, zinc oxide, magnesium oxide and the like. Spandex fiber The method of claim 4, wherein the hydrotalcite compound is 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, and _{Mg 4 Al 2 (OH) 12} (CO 3) 1 type of compound selected from the group consisting of O _{0.6 0 .4} Spandex fiber with improved chlorine resistance, characterized by above. The method of claim 4, wherein the hydromagnesite is Mg ₄ (CO ₃ ) ₄ · Mg (OH) ₂ · 4H ₂ O, Mg ₃ (CO ₃ ) ₃ · Mg (OH) ₂ 3H ₂ O, Mg ₄ (CO _{3 ) 4 · Mg (OH) 2} , Mg 3 (CO 3) 3 · Mg (OH) 2, the improved spandex fibers chlorine resistance, characterized in that at least one member selected from the group consisting of MgCO _3. The method of claim 1, wherein the inorganic chlorinating agent is aliphatic alcohol, fatty acid, fatty acid salt, aliphatic ester, phosphate ester, styrene / maleic anhydride copolymer and derivatives thereof, silane coupling agent, titanate coupling agent, polyorganosiloxane Spandex fiber, characterized in that the coating by at least one coating agent selected from the group consisting of polyorganohydrogensiloxane and melamine-based compounds. Preparing a polyurethane solution by reacting an organic diisocyanate and a diol to prepare a polyurethane precursor, and then dissolving the polyurethane precursor in an organic solvent and then reacting with a diamine and a monoamine to prepare a polyurethane solution. Chlorine resistance comprising the step of spinning by adding 0.1 to 5% by weight of symmetrical di- hindered hydroxyphenyl-based compound and 0.1 to 10% by weight of inorganic chlorine-resistant compound to the polyurethane solution Process for producing excellent spandex island oil.