KR101238603B1 - Discoloration-resistant and chlorine-resistant Spandex Fiber and Preparation Method thereof - Google Patents

Abstract

The present invention is a symmetric di-hindered hydroxyphenyl-based additives and mono-hinne of the following particle size after grinding of the hydrotalcite compound, huntite and hydromagnesite mixed mineral, hydromagnesite, zinc oxide, magnesium oxide, etc. The present invention relates to a spandex fiber having improved chlorine resistance and discoloration resistance, including a hydroxyphenyl-based compound and a phosphorus antioxidant, and a method for producing the same. It can be used more effectively.

Description

Spandex fiber with improved chlorine resistance and discoloration resistance and its manufacturing method {Discoloration-resistant and chlorine-resistant Spandex Fiber and Preparation Method}

The present invention relates to a spandex fiber with improved chlorine resistance and discoloration resistance, and a method for manufacturing the same, and more particularly, to a symmetrical di-hindered hydroxyphenyl-based additive and a mono-hindered hydroxyphenyl-based additive and particles to a predetermined size or less. The present invention relates to a spandex fiber having improved chlorine resistance and discoloration resistance while maintaining the conventional physical properties of a polyurethane-based polymer containing a ground inorganic chlorine and phosphorus antioxidant.

Spandex, which is a typical polyurethane elastic fiber, maintains high rubber elasticity and has excellent physical properties such as tensile stress and recovery property. Therefore, it is widely used in underwear, socks, sports leisure clothing, and the like. However, polyurethane, which is a major component of spandex, exhibits a significant decrease in physical properties during chlorine bleaching. Swimsuits made by alternating spandex and polyamide have strong physical properties such as strength when used in swimming pools where the active chlorine content is usually 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 chlorine resistance and discoloration resistance by combustion by mixing additives and organic additives are disclosed.

However, there are no additives that can significantly improve the chlorine resistance and discoloration resistance of the spandex fiber, and thus further improvement is required.

The present invention meets the technical requirements described above, and one object of the present invention is to provide a spandex fiber with improved chlorine resistance and discoloration resistance while maintaining the inherent physical properties of the polyurethane polymer.

Another object of the present invention is to provide a method for producing a spandex fiber that can improve the chlorine resistance and discoloration resistance while maintaining the inherent physical properties of the polyurethane polymer.

According to one aspect of the present invention for achieving the above object,

0.1 to 5% by weight of symmetrical di-hindered hydroxyphenyl-based compound; And

0.1 to 5% by weight of a mono hindered hydroxyphenyl compound and

0.1 to 10% by weight of an inorganic chlorine resistant agent having a particle size of 0.3 to 0.5 μm added after grinding and

0.1 to 3% by weight of phosphorus antioxidant

It relates to a spandex fiber containing improved chlorine resistance and discoloration resistance.

Another aspect of the present invention for achieving the above object is to prepare a polyurethane precursor by reacting an organic diisocyanate and diol, and then prepared by dissolving the polyurethane precursor in an organic solvent and then reacted with diamine and monoamine Preparing a urethane solution;

0.1 to 5 wt% of the symmetrical di-hindered hydroxyphenyl compound and 0.1 to 5 wt% of the mono-hindered hydroxyphenyl compound in the polyurethane solution and an inorganic chlorine agent having 0.3 to 0.5 μm of particles added after grinding It relates to a method for producing spandex fibers with improved chlorine resistance and discoloration resistance, characterized in that it comprises the step of spinning by adding 0.1 to 10% by weight, 0.1 to 3% by weight phosphorus antioxidant.

The spandex according to the present invention has improved the discoloration resistance and chlorine resistance while maintaining excellent polyurethane properties such as whiteness, gripping force, tear strength, bursting strength, elasticity, etc. It can be effectively used in sports clothing, such as gymnastics. In addition, since it is possible to prevent the dropping of additives and the reduction of the chlorine resistance by the refining method using an organic solvent to remove the uncontaminated matter and contaminants, there is an effect that can be applied to all fabric processing processes without being obtained.

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

The spandex fiber of the embodiment of the present invention comprises 0.1 to 5% by weight of symmetrical di-hindered hydroxyphenyl-based compound based on the polyurethane polymer; And 0.1 to 5 wt% of a mono hindered hydroxyphenyl compound; 0.1 to 10% by weight of an inorganic chlorine resistant agent whose primary particles are ground to 0.5 mu m; 0.1 to 3% by weight of a phosphorus antioxidant. 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-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 [3,5-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 can be used. The mono hindered hydroxyphenyl-based compound is (4,4'-butylenedenebis (6-tertiary-3-methylphenol)), n-octadecyl-3- (4-hydroxy-3-tertiary-part Phenyl) propionate, triethylene glycol bis [3- (3-tert-butyl-4-hydroxyphenyl) propionate], ethylene, 1,2-bis (3,3-bis [3-tertary) -Butyl-4-hydroxyphenyl] butyrate) 2,4-di-tert-butylphenyl-4'hydroxy-3 'tert-butylbenzoate, 2,4,6-tris (3-tertary- One or more types selected from the group consisting of butyl-4-hydroxybenzyl) isocyanurate can be used.

In the present invention, the amount of the symmetric di-hindered hydroxyphenyl compound and the mono-hindered hydroxyphenyl compound is preferably 0.1 to 5% by weight relative to the polyurethane polymer, and less than 0.1% by weight of the chlorine resistance of the spandex. It is not preferable because there is little property contributing to improvement and there is no improvement effect on excessive input when it exceeds 5 weight%.

As the inorganic chlorinating agent, hydrotalcite of Formula 1, huntite of Formula 2, hydromagnesite represented by Formula 3, zinc oxide, magnesium oxide, and the like may 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 in harming chlorine. In addition, the main effect of the technology characterized in this invention is to manage the size of the inorganic chlorine-resistant particles added after grinding in order to apply the inorganic chlorine-resistant agent to 0.3 ~ 0.5㎛. If the size of the particles is less than 0.3㎛ entanglement between the particles occurs there is a problem that may affect the spinning processability, if the size exceeds 0.5㎛ there is a problem that there is no improvement effect on the chlorine resistance compared to the existing.

[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.

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

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.

A non-limiting example of a hydrotalcite compound of formula (I) are the _{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,} include _{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 mixture thereof.

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 And one or more selected from the group consisting of siloxane 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 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, 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 .

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-bound melamine compound is a form in which phosphoric acid is bound to the melamine compound or phosphate is bound. Tol 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 Sophthalic acid and phthalic acid, and aromatic tricarboxylic acids include trimellitic acid, 1,3,5-benzenetricarboxylic acid and tris (2-carboxyethyl) isocyanurate. Are pyromellitic acid and biphenyl tetracarboxylic acid, cycloaliphatic monocarboxylic acid is cyclohexanecarboxylic acid, and cycloaliphatic dicarboxylic acid is 1,2-cyclohexane dicarboxylic acid.

Hydromagnesite of Formula 3 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, polyors It includes, but is not necessarily limited to, one or more selected from the group consisting of ganohydrogensiloxane and melamine-based compounds. 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 160 ° 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 property of imparting chlorine resistance to the spandex fiber, when exceeding 10% by weight excessive inorganic It is not preferable because the content lowers the strength, elongation and modulus of the spandex fiber.

In addition, as a phosphorus antioxidant for improving discoloration resistance, tetrakis (2,4-di-t-butylphenyl) 4,4'biphenyldiphosphonite, tris (2,4-di-t-butylphenyl) phosphate, One kind selected from the group consisting of tris (3-t-butyl-4-hydroxyphenyl) phosphate can be used. In addition, the phosphorus antioxidant is preferably 0.1 to 3% by weight compared to the polyurethane polymer, when less than 0.1% by weight is less characteristic of imparting discoloration resistance to the spandex fibers, when exceeding 3% by weight of excessive additives Due to the lowering of the strength and modulus when processing the fabric containing the spandex fiber is not preferred.

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, phosphorus chemicals, nitric oxide scavengers, light stabilizers, hindered amine stabilizers Agents, metal salts such as magnesium stearate and barium sulfate, silver, zinc or compound containing bactericides, 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. Polyurethane solutions may be melt spun, dry spun or wet spun into spandex.

In preparing the spandex of the present invention, the symmetrical di-hindered hydroxyphenyl-based compound, the mono-hindered hydroxyphenyl-based compound, the inorganic chlorine resistant agent, and the phosphorus antioxidant 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, mono-hindered hydroxyphenyl-based compound, phosphorus antioxidant may also be added during the sand grinding or milling process, 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, and a dispersant may be additionally added.

In the technique of the present invention, the inorganic chlorine-resistant grinding has been managed by the filtering test in a certain size of the sieve, but the size and grinding level of the particles have been managed, but in order to make the particles smaller, the following additional tests are required.

The completion of milling is checked by a filtering test. The filtering test was carried out as follows.

After milling a hydrotalcite slurry with smaller particles was sampled, 2 kg were sampled. The upper outlet can be pressurized, and the lower outlet is equipped with a 15 μm stainless steel nonwoven sieve with a diameter of 4 cm to inject a 2 kg slurry into a closed vessel that can pressurize and leave the slurry only through the sheave. And when applied at a constant air pressure of 1.5kgf / cm ² , the flow rate of the slurry for 2 minutes is measured. The secondary flocculated particle size of the hydrotalcite slurry, which had a small particle size when all 2 kg of slurry passed through the sieve, is considered to be less than the size of each sieve. At this time, the size of the sieve is evaluated differently according to the size of the beads used at the time of slurry milling. It is determined as passing that all 2 kg of slurry passed through the sheave, and failing not to pass all 2 kg of slurry. Slurry results of less than 100% in the filtering test are considered to be poor in storage stability and are not applied to the process.

[Table 1]

Under the above conditions, the present inventors confirmed that the hydrotalcite partially dehydrated also had no problem in the spandex manufacturing process when milling in order to reduce the particle size.

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 ° C. for 95 minutes in a nitrogen gas stream to prepare a polyurethane prepolymer having an isocyanate at both ends. 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 hydrotalcite Mg ₄ Al ₂ (with particle size of 0.3 ~ 0.5㎛) OH) ₁₂ CO ₃ .3H ₂ O was added and mixed with 4% by weight. Additionally 1.5 wt% of (tetrakis [methylene-2- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane) as a symmetric di hindered hydroxyphenyl compound in the slurry, 1.5% by weight of mono-hindered hydroxyphenyl compound (4,4'-butyledenebis (6-tertiary-3-methylphenol)) and phosphorus antioxidant (tetrakis (2,4-di-t 0.5 wt% of -butylphenyl) 4,4'biphenyldiphosphonite) 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.

Under 50% elongation of spandex yarn, A condition was treated in a bath of 1g / L refiner and 1 g / L of NaOH at 80 ° C. for 20 minutes, and then treated with water at pH 4.5 and 99-100 ° C. for 1 hour. Tetrachloroethylene) for 60 seconds and then treated with water at the same pH and temperature for 1 hour and dried at room temperature and then cooled. After immersing in 45 L of chlorine water of 3.5 ppm of active chlorine and pH 7.0-7.5 at room temperature for 180 hours, the intensity retention was calculated by the following formula. 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 rate (%) = S / S _o × 100

(S _o : strong before treatment, S: strong after treatment) Also, in order to evaluate the discoloration resistance of spandex, discoloration (measurement of color difference) caused by 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 at 80 ° C. for 20 minutes in a bath of A condition: 1g / L of refinery and 1g / L of NaOH, and 60 hours at room temperature with B condition of organic solvent (Tetrachloroethlylene), followed by natural drying for 12 hours.

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

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

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

Discoloration degree by a Color-view a Red value at the time was measured raw using the ^TM a _1, Yellow to Red value after the values b _1, process a _2, Yellow value of BYK Gardner社to b ₂ △ a = _{a 2 -a 1, △ b =} b 2 -b ₁ are shown after calculation as the discoloration resistance difference (color difference).

Lower value of Δa indicates less redness, and lower value of Δb indicates less yellowing.

Example 2

As a symmetric dihindered hydroxy phenyl-based compound, 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

The same polymer as in Example 1, except that (2,4,6-tris- (3-tertary butyl-4-hydroxy benzyl) isocyanurate) was used as the mono hindered hydroxy phenyl compound. Using to prepare a spandex, and evaluated the chlorine resistance the results are shown in Table 1 together.

Example 4

Except for using tris (2,4-di-t-butylphenyl) phosphate as the phosphorus antioxidant, using the same polymer as in Example 1 to prepare a spandex, to evaluate the chlorine resistance and the results are shown in the following table 1 is shown together.

Example 5

Symmetrical di hindered hydrophenyl group compounds (tetrakis [methylene-2- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane), mono hindered hydroxyphenyl series Spandex was prepared using the same polymer as in Example 1, except that it was used as a compound (4,4'-butylenedenebis (6-tertiary-3-methylphenol)) and an uncoated inorganic chlorine resistant agent. To prepare and evaluate the chlorine resistance, the results are shown in Table 1 together.

Example 6

Except for using the mineral mixture of the huntite and hydromagnesite as an inorganic chlorine 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 7

Except for using 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.

Comparative Example 1

 Except for using the particle size of the inorganic chlorine-resistant chlorine added after grinding to the same polymer as in Example 1 except that the particle size was prepared and evaluated the chlorine resistance and the results are shown in Table 1 below. Shown together.

Comparative Example 2

Spandex yarn was prepared using the same polymer as in Example 1, except that only the mono-hindered hydroxyphenyl-based compound was used instead of the symmetric dihindered hydroxyphenyl-based compound, and the chlorine resistance was evaluated. It is shown together in Table 1 below.

Comparative Example 3

Except for using the di-hindered hydroxyphenyl compound instead of the mono-hindered hydroxyphenyl compound, a spandex yarn was prepared using the same polymer as in Example 1, and evaluated for chlorine resistance. It is shown together in Table 1 below.

Comparative Example 4

A spandex yarn was prepared using the same polymer as in Example 1, except that only the inorganic chlorine-resistant compound and the antioxidant were used without the symmetric dihindered hydroxyphenyl compound and the mono hindered hydroxyphenyl compound. Chlorine resistance

And are shown together in Table 1 below.

Comparative Example 5

Except not using a phosphorus-based antioxidant, using the same polymer as in Example 1 to prepare a spandex yarn, to evaluate the chlorine resistance and the results are shown in Table 1 together.

[Table 1]

Chlorine resistance evaluation result

A condition: 20 minutes treatment at 80 degreeC in the bath of 1 g / L of refiners and 1 g / L of NaOH.

B condition: 60 seconds in organic solvent (Tetrachloroethylene).

[Table 2]

Discoloration resistance evaluation result

A condition evaluation result

B condition evaluation result

As confirmed through the results of Table 1, the spandex yarn of the present invention containing both a symmetric di hindered hydroxyphenyl-based compound and an inorganic chlorine-resistant compound using only an inorganic chlorine-resistant or asymmetric di hindered hydroxy phenyl Compared with the conventional spandex containing a system compound, the strong retention in chlorine water was improved significantly.

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 scope of protection of the present invention should be defined by the appended claims and their equivalents.

Claims (8)

Polyurethane Polymer Solids Contrast
0.1 to 5% by weight of symmetrical di-hindered hydroxyphenyl-based compound; And
0.1 to 5 wt% of a mono hindered hydroxyphenyl compound; And
0.1 to 10% by weight of an inorganic chlorine resistant agent having a particle size of 0.3 to 0.5 µm added after grinding; And
0.1 to 3% by weight of phosphorus antioxidant
Spandex fiber excellent in chlorine resistance to contain.
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-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- (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 excellent in chlorine resistance to be made. The mono-hindered hydroxyphenyl-based compound according to claim 1, wherein the mono hindered hydroxyphenyl compound is (4,4'-butylenedenebis (6-tertiary-3-methylphenol)), n-octadecyl-3- (4-hydroxy 3-tert-butylphenyl) propionate, triethylene glycol bis [3- (3-tert-butyl-4-hydroxyphenyl) propionate], ethylene, 1,2-bis (3,3 -Bis [3-tert-butyl-4-hydroxyphenyl] butyrate) 2,4-di-tert-butylphenyl-4'hydroxy-3'tert-butylbenzoate, 2,4,6- Tridex (3-tert-butyl-4-hydroxybenzyl) isocyanurate Spandex fiber excellent in chlorine resistance, characterized in that at least one member selected from the group consisting of.
The chlorine resistance of claim 1, wherein the inorganic chlorine agent is at least one selected from the group consisting of a hydrotalcite compound, a mixed mineral of huntite and hydromagnesite, hydromagnesite, zinc oxide, and magnesium oxide. This is an excellent spandex fiber.
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, Spandex fiber excellent in chlorine resistance characterized by at least one member selected from the group consisting of tris (3-t-butyl-4-hydroxyphenyl) phosphate.
The method of claim 4, wherein said 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) from a group consisting of O _{0.6 0 .4} Spandex fiber with improved chlorine resistance, characterized in that at least one selected. The method of claim 4, wherein the hydro-magnesite 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 , and MgCO ₃ Spandex fiber with improved chlorine resistance, characterized in that at least one selected from the group consisting of.
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