KR20060066689A - Spandex fibers containing partially dehydroxylated hydrotalcites - Google Patents

Abstract

The present invention relates to a spandex fiber having excellent discoloration resistance and chlorine resistance while retaining the inherent physical properties of a polyurethane-based polymer, wherein the partially dehydrated hydrotalcite is about 0.1 to 10% by weight of the total weight of the spandex fiber. Since the spandex fiber of the present invention is excellent in discoloration resistance and chlorine resistance, it can be effectively used in sports clothing such as underwear and socks, especially swimwear.

Spandex fiber, partially dehydrated hydrotalcite, discoloration resistance, chlorine resistance

Description

Spandex fiber containing partially dehydrated hydrotalcite {SPANDEX FIBERS CONTAINING PARTIALLY DEHYDROXYLATED HYDROTALCITES}

1 is a schematic diagram showing the structure of hydrotalcite.

FIG. 2 shows hydrotalcite (Mg ₈ Al ₄ (OH) ₂₄ (CO ₃ ) ₂ · 6H ₂ O) used in Preparation Example 2 using ²⁷ Al magic angle spinning nuclear magnetic resonance (MAS NMR). FIG. This is a graph analyzed by).

FIG. 3 is a graph of partially dehydrated hydrotalcite (Mg ₈ Al ₄ (OH) ₁₆ O ₄ (CO ₃ ) ₂ ) obtained in Preparation Example 2 by ²⁷ Al MAS NMR.

Figure 4 is a graph of the spandex yarn prepared in Example 2 analyzed by ²⁷ Al MAS NMR.

FIG. 5 is a graph of hydrotalcite extracted from a spandex yarn prepared in Example 2 using ²⁷ Al MAS NMR. FIG.

FIG. 6 is a graph of hydrotalcite (Mg ₈ Al ₄ (OH) ₂₄ (CO ₃ ) ₂ .6H ₂ O) used in Preparation Example 2 analyzed by infrared spectroscopy.

FIG. 7 is a graph of an infrared spectroscopy analysis of partially dehydrated hydrotalcite (Mg ₈ Al ₄ (OH) ₁₆ O ₄ (CO ₃ ) ₂ ) obtained in Preparation Example 2. FIG.

8 is a graph of hydrotalcite extracted from the spandex yarn prepared in Example 2 by infrared spectroscopy.

The present invention relates to spandex fibers containing partially dehydrated hydrotalcite. More specifically, the present invention relates to spandex fibers having excellent discoloration resistance and chlorine resistance while retaining the inherent physical properties of polyurethane-based polymers.

Spandex fibers are widely used in underwear, socks, sports clothes, and the like because they have excellent physical properties such as tensile stress and recoverability while maintaining high rubber elasticity. However, the polyurethane part, which is the main component of spandex fiber, is significantly degraded in physical properties when washing with chlorine bleach, and even in swimwear made by alternating spandex fiber and polyamide fiber, the amount of chlorine in the pool (active chlorine concentration 0.5 to 3.5 ppm) will degrade the physical properties of the spandex fibers.

In order to improve the resistance of spandex fibers to chlorine-induced degradation, many studies have been conducted. As a chlorine-resistant chlorine agent for spandex fibers, U.S. Patent No. 4,340,527 uses zinc oxide and U.S. Patent No. 5,626,960. Korean Patent Publication No. 92-3250 describes calcium carbonate and barium carbonate, and Japanese Patent Application Laid-Open No. Hei 6-81215 discloses a solid solution of MgO / ZnO. Korean Patent Laid-Open No. 59-133248 discloses magnesium oxide, magnesium hydroxide or hydrotalcite, and Japanese Patent Laid-Open No. 3-292364 disclose hydrotalcite treated with a higher fatty acid and a silane coupling agent, respectively. have.

U.S. Patent No. 5,447,969 uses hydrotalcite having crystal water and C ₁₀ to C ₃₀ fatty acid attached to thereby improve the dispersibility of the hydrotalcite to prevent the agglomeration of the hydrotalcite during the manufacturing process of the spandex fiber. In addition, the discharge pressure was increased during the spinning process and the yarn breakage was improved, and even when treated with tannin solution, the spandex fiber did not brown and swelled even when chlorine water was immersed. Specifically, U.S. Patent No. 5,447,969 discloses filament yarns by dry spinning a polyurethane polymer solution in 330 ° C hot air. However, the present inventors prepared a spandex polymer by adding hydrotalcite with C ₁₀ ~ C ₃₀ fatty acid attached to the crystal water as described in the US Patent Publication, and dry spinning in hot air at 250 ℃, spun yarn spun The phenomenon of discoloration to yellowish brown was found.

U. S. Patent No. 6,692, 828 discloses hydrotalcite coated with melamine-based compounds having excellent heat resistance as a chlorine resistant agent of spandex fiber, but even when such hydrotalcite is used, the degree is less than that of U.S. Patent No. 5,447,969. However, the phenomenon of discoloration of the spandex during dry spinning in hot air at 250 ° C. still remained.

European Patent Publication No. 1 262 499 A1 is intended to improve the chlorine resistance of spandex fibers using milling hydrotalcite as the chlorine resistant agent and having an average particle diameter of 1 micron or less. Specifically, looking at the structural formula of the hydrotalcite disclosed in EP 1 262 499 A1, unlike other prior art, partially decarbonized hydrotalum, in which some carbonate ions are decomposed into carbon dioxide and oxygen and oxygen remains. The structure of the site is shown. The carbonate content in the hydrotalcite plays an important role in imparting chlorine resistance to the spandex. When the hydrotalcite having a small content of carbonate is added to the spandex polymer, the chlorine resistance of the spandex is poor.

Korean Laid-Open Patent Publication No. 2006-5814 manufactures spandex having excellent discoloration resistance and chlorine resistance by using hydrotalcite coated with melamine-based compound and decrystallized water. The removed hydrotalcite has high hygroscopicity and is easy to return to hydrotalcite having the same number of crystals as the original state, and thus requires great care in handling. In addition, even in the case of hydrotalcite from which crystal water is removed, hydrotalcite absorbs moisture contained in the slurry or polymer during the slurry manufacturing process or the mixing process of the slurry and the polymer in the process of manufacturing spandex to hydrotalcite having crystal water. Because of the change, when the spandex polymer disclosed in Korean Laid-Open Patent Publication No. 2006-5814 at 250 ° C. or more, the degree of discoloration of yarns was lower than that of the conventional technology, but it was difficult to prevent discoloration completely.

No matter how good the chlorine resistance, the discolored spandex is deteriorated in the value of the commodity and may cause a problem that can not be dyed white in the subsequent processing process, it is necessary to improve such discoloration phenomenon.

Accordingly, an object of the present invention is to provide a chlorine resistant spandex fiber that does not discolor even when the spandex polymer containing hydrotalcite is spun at 200 占 폚 or higher.

The present invention provides a spandex fiber containing about 0.1 to 10% by weight relative to the total weight of the spandex fiber in order to achieve the above technical problem.

The present inventors heat-treated hydrotalcite having crystallized water at about 200 to 390 ° C. to remove the crystallized water and partially dehydrated hydrotalcite to the polyurethane polymer, so that discoloration does not occur even after spinning at 200 ° C. or higher. It was possible to produce spandex fibers having excellent chlorine resistance.

The present inventors partially dehydrated hydrotalcite by treating the hydrotalcite of the Korean Patent Publication No. 2006-5814 at a temperature higher than the heat treatment temperature and time and for a long time, and the European Patent Publication No. 1 262 499 A1. As it was not decarbonized, there was no loss of chlorine resistance.

In addition, U.S. Patent No. 5,447,969 describes that hydrotalcite having crystallized water must be used so that it does not discolor when treated with tannin solution and does not swell when immersed in chlorine treated water. When the polyurethane yarn was prepared by adding dehydrated hydrotalcite, it was found that it did not brown when treated with tannin solution and did not swell even when chlorine treated water was immersed.

Hereinafter, the spandex fiber which concerns on this invention is demonstrated concretely.

Terms defined in the description of the present invention are defined in consideration of the function of the present invention, which may vary according to the intention or practice of those skilled in the art, it is understood to limit the technical components of the present invention It should not be.

Spinning or spinning refers to both melt and dry spinning. Spinning temperature refers to the temperature at which the polymer chip melts for melt spinning and the temperature within the spinneret for dry spinning, which is the highest temperature the spandex polymer receives during the spinning process. In addition, discoloration means that the spandex fiber is changed to another color such as yellow or brown instead of white.

Hydrotalcite is a type of metal hydroxide, which has an octahedral structure in which a divalent or trivalent metal cation is located in the center and six hydroxide ions (OH ⁻ ) surround the metal cation. It has a double layer structure that forms two layers, and an anion and water molecules are positioned between the double layers to maintain an equilibrium of charge amount (see FIG. 1). Heat treatment of hydrotalcite at high temperature removes water molecules (ie, crystalline water) between the double layers, and heat treatment at higher temperatures results in dehydration, and decarbonization occurs at higher temperatures. See Stanimirova et al. Clay Minerals , 39: 177-191 (2004).

Partially dehydrated hydrotalcite is oxidized, dehydroxylation reaction by heating a hydrotalcite containing water of crystallization at a high temperature that the hydroxide ions contained in the hydrotalcite is decomposed with water and the oxide ion (2OH ^- → H ₂ O + O ^2- ) means the hydrotalcite occurred. Partially dehydrated hydrotalcite is converted into a tetrahedral structure in which four hydroxide ions surround a metal cation due to dehydration, which is converted into a tetrahedral structure in which four hydroxide ions surround a metal cation. The tetrahedron structure is mixed (see the same document).

In the present invention, the partially dehydroxylated hydrotalcite is preferably represented by the following formula (1):

M ^{2 +} _{12- y} Al _y (OH) _{24-2 z} O _z (CO ₃ ) _{y /} 2mH ₂ O

Wherein, M ^{2 +} is Mg ^{2 +,} Ca ^{2 +} or Zn ^{+ 2,} y is 2.4 and <y ≤ 4 is a positive value, z is in 0 <z ≤8 positive number, m is 0 or a positive number to be.

It is also preferred that the partially dehydrated hydrotalcite is at least one selected from compounds represented by the following structural formulas:

Mg ₈ Al ₄ (OH) ₁₆ O ₄ (CO ₃ ) ₂ , Mg ₈ Al ₄ (OH) ₈ O ₈ (CO ₃ ) ₂ , Mg ₉ Al ₃ (OH) ₁₈ O ₃ (CO ₃ ) _1.5 , Mg _{9 Al 3 (OH) 12 O 6} (CO 3) 1.5, Mg 9 .6 Al 2 .4 (OH) 19.2 O 2 .4 (CO 3) 1.2, Mg 9 .6 Al 2 .4 (OH) 14.4 O 4 _.8 (CO ₃ ) _1.2 , Mg ₈ Al ₄ (OH) ₁₆ O ₄ (CO ₃ ) ₂ · 6H ₂ O, Mg ₈ Al ₄ (OH) ₈ O ₈ (CO ₃ ) ₂ · 7H ₂ O, Mg _{9 Al 3 (OH) 18 O 3} (CO 3) 1.5 · 7.5H 2 O and _{Mg 9 Al 3 (OH) 12} O 6 (CO 3) 1.5 · 8H 2 O.

In the present invention, the partially dehydroxylated hydrotalcite is selected from the group consisting of hydrotalcite having crystalline water in an atmosphere containing no water such as nitrogen, helium, oxygen, hydrogen or carbon dioxide at about 200 to 390 ° C., preferably about It is prepared by heat treatment at 250 ~ 300 ℃.

When hydrotalcite with crystalline water is treated at a temperature below 200 ° C., the crystalline water is removed but dehydration may not proceed. In addition, the treatment of hydrotalcite having a grain constant at a temperature above 390 ° C., not only results in dehydration of the hydrotalcite but also decarboxylation, thereby lowering the chlorine resistance of the hydrotalcite. When using partially dehydrated hydrotalcite obtained by heat treatment at about 250 to 300 ° C., the chlorine resistance improvement effect of the spandex fiber is good.

Although partially dehydrated hydrotalcite resorbs moisture when it is left in the air, most of this water evaporates before and after about 100 ° C, which means that the number of crystals contained in hydrotalcite before the first heat treatment is about 170 It is distinguished from evaporating between ˜220 ° C. The water adsorbed on the hydrotalcite, which has been crystallized and partially dehydrated, does not affect the discoloration of the spandex yarn even if the polyurethane polymer is spun above 200 ° C. The exact reason for this has not yet been determined.However, when using hydrotalcite having crystalline water, the spandex yarn discolors due to evaporation of the initial crystallization water in a spinning process of 200 ° C. or higher, but using partially dehydrated hydrotalcite. Since the water adsorbed on the surface disappears by evaporation before and after about 100 ° C, discoloration of spandex yarn does not appear during the spinning process of 200 ° C or more.

In addition, in the present invention, the use of partially dehydrogenated hydrotalcite is superior to the chlorine resistance of the spandex fiber than the case of using hydrotalcite having crystal water before initial heat treatment. The reason for this is not clear, but the dehydration of the hydrotalcite due to the dehydration during the heat treatment causes the absorption capacity and the ion exchange capacity of the hydrotalcite to be improved.

Polyurethane polymers used in the preparation of the spandex fibers according to the present invention, as is known in the art, the reaction of organic diisocyanate and polymer diol to prepare a polyurethane precursor, which is dissolved in an organic solvent and then diamine and Prepared by reacting with monoamines. Organic diisocyanates used in the present invention include diphenylmethane-4,4'- diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, butylene diisocyanate, hydrogenated diphenylmethane-4,4'- diisocyanate, and the like. have. 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 and include, for example, ethylenediamine, propylenediamine, hydrazine and the like. On the other hand, monoamine is used as a chain terminator, for example, diethylamine, monoethanolamine, dimethylamine, and the like.

In order to prevent discoloration or a decrease in physical properties of the spandex fiber due to heat treatment during the processing of the spandex fiber or other ultraviolet rays, atmospheric smog, etc., a hindered phenol compound, a benzofuran-one compound, a semicarbazide system Compounds, benzotriazole compounds, hindered amine compounds, polymeric tertiary amine stabilizers (e.g., polyurethanes with tertiary nitrogen atoms, polydialkyl aminoalkyl methacrylates), etc., are added to the polyurethane polymer can do.

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

In the present invention, the addition amount of the partially dehydroxylated hydrotalcite is preferably about 0.1 to 10% by weight compared to the polyurethane polymer, but when less than 0.1% by weight, the property of imparting chlorine resistance to the spandex fiber is less than 10% by weight. Exceeding the% reduces the strength, elongation and modulus of the spandex fiber due to excessive inorganic content, which is not preferable.

In making the spandex fibers of the present invention, partially dehydrated hydrotalcite may be added to the polyurethane polymer at any convenient point in time. For example, partially dehydrated hydrotalcite may be added to the solution along with other additives and mixed with the polyurethane polymer after a sand grinding or milling process, and sand grinding in solvent separately from other additives. Or may be mixed with the polyurethane polymer after the milling process.

In the present invention, the partially dehydrated hydrotalcite may be coated or uncoated with a coating agent commonly used in the art, and the coating does not affect the discoloration resistance and the chlorine resistance of the spandex yarn. .

Coatings of partially dehydrated hydrotalcite include, for example, aliphatic alcohols, fatty acids, fatty acid salts, aliphatic esters, phosphate esters, styrene / maleic anhydride copolymers and derivatives thereof, silane coupling agents, titanate coupling agents. And polyorganosiloxanes, polyorganohydrogensiloxanes, and melamine 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 case of melamine-based compounds, discoloration occurs least in the heat treatment step of partially dehydrating hydrotalcite.

For coating of hydrotalcite, add an appropriate amount of coating agent to a solvent such as water, alcohol, ether, dioxane, etc. so that the amount of coating agent is about 0.1 to 10% by weight based on the weight of hydrotalcite, and then add uncoated hydrotalcite. Increasing the temperature, stirring for about 10 minutes to 2 hours at about 50 ~ 170 ℃ (using a high-pressure reactor, if necessary), and after the stirring is made through a filtering and drying process. 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 150 ° C or higher in water.

The inventors of the present invention has repeatedly studied the coating of fatty acids or fatty acid salts, when coating in water, 100 ℃ or more, the coating becomes more uniform than when coated in water, less than 100 ℃, heat-treated hydrotalcite after coating Also it was found that the discoloration of the coating agent is small. In addition, when the hydrotalcite is coated with a fatty acid or a fatty acid salt in water or 100 ° C. or more, the same coating effect can be obtained even if the amount of the coating agent is reduced compared to the coating in water or less than 100 ° C. For example, when a fatty acid or fatty acid salt is coated in water at less than 100 ° C., the amount of fatty acid or fatty acid salt required to obtain a coating effect is typically about 3% by weight relative to the weight of hydrotalcite, but is coated at 100 ° C. or more in water. In this case, the amount of the coating agent was reduced to about 1.5% by weight based on the hydrotalcite weight. When the coating agent is used in this way, there is an advantage in reducing the discoloration of the coating agent in the process of heat-treating the hydrotalcite after coating.

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- Nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid and 1,14 Tetradecanedicarboxylic acids, 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) -phthalaninoic acid (4- (2-thiazo (l) ylsulfamyl) -phthalaninoic acid), and aromatic dicarboxylic acids include terephthalic acid, Sophthalic acid and phthalic acid, aromatic tricarboxylic acids include trimellitic acid, 1,3,5-benzenetricarboxylic acid and tris (2-carboxyethyl) isocyanurate, and aromatic tetracarboxylic acids Pyromellitic acid and biphenyltetcarboxylic acid are cyclohexanecarboxylic acid as alicyclic monocarboxylic acid and 1,2-cyclohexane dicarboxylic acid as alicyclic dicarboxylic acid.

The coating agent increases the dispersibility of hydrotalcite in the spandex polymer to prevent radioactive deterioration of the spandex polymer.

However, even in the case of using uncoated hydrotalcite, sand grinding or milling of hydrotalcite shows almost the same radioactivity as using coated hydrotalcite.

The process of sand grinding or milling hydrotalcite may be achieved by mixing and milling hydrotalcite, solvents and small amounts of polyurethane polymers using conventional bead mills, or by using hydrotalcite, solvents, other additives and small amounts of The polyurethane polymer can be mixed to form a slurry and milled. Here, a small amount of polyurethane polymer serves to improve the dispersibility of hydrotalcite. As the solvent, one or more selected from dimethylacetamide, dimethylformamide and dimethyl sulfoxide are used.

Sand grinding or milling without coating the partially dehydrated hydrotalcite to make the secondary aggregated particle size below about 15 [mu] m on average will result in coating and sand grinding or milling of the partially dehydrated hydrotalcite. In comparison, there is no difference in the manufacturing process of the spandex fiber.

In the present invention, the apparatus for producing partially dehydrogenated hydrotalcite may be any type of convection, conduction, radiation, etc. as long as it is a dryer capable of heating hydrotalcite having crystal water at about 200 to 390 ° C. . Microwave drying or vacuum heating drying are also possible.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the present invention is not limited thereto.

Example

Preparation Example 1

The stearic acid was added to water so that 2% by weight of the hydrotalcite was added, hydrotalcite having the structural formula Mg ₈ Al ₄ (OH) ₂₄ (CO ₃ ) ₂ · 6H ₂ O was added thereto, followed by stirring at 150 ° C. for 20 minutes. After that, filtering and drying gave hydrotalcite coated with stearic acid. The coated hydrotalcite was then heat treated at 250 ° C. for 4 hours to prepare hydrotalcite of structural Mg ₈ Al ₄ (OH) ₁₆ O ₄ (CO ₃ ) ₂ coated with stearic acid.

Preparation Example 2

Compared to the weight of hydrotalcite, 2% by weight of stearic acid and 1% by weight of melamine polyphosphate were added to water, and hydrotalcite of Mg ₈ Al ₄ (OH) ₂₄ (CO ₃ ) ₂ .6H ₂ O was added. After addition, stirring at 160 ° C. for 30 minutes, followed by filtering and drying yielded hydrotalcite coated with stearic acid and melamine polyphosphate. Then, a hydrotalcite of Mg ₈ Al ₄ (OH) ₁₆ O ₄ (CO ₃ ) ₂ coated with stearic acid and melamine polyphosphate was prepared by heat treatment at 250 ° C. for 4 hours.

Preparation Example 3

Coating with melamine polyphosphate in the same manner as in Preparation Example 2, except that hydrotalcite of the structural formula Mg ₈ Al ₄ (OH) ₂₄ (CO ₃ ) ₂ .6H ₂ O was coated with 3% by weight of melamine polyphosphate. Hydrotalcite of the formula Mg ₈ Al ₄ (OH) ₁₆ O ₄ (CO ₃ ) ₂ was obtained. Then, hydrotalcite of structural Mg ₈ Al ₄ (OH) ₁₆ O ₄ (CO ₃ ) ₂ .6H ₂ O coated with melamine polyphosphate was prepared by standing in a moisture-containing atmosphere for one week.

Preparation Example 4

Hydrotalcite of Mg ₈ Al ₄ (OH) ₂₄ (CO ₃ ) ₂ · 6H ₂ O was heat treated at 250 ° C. for 4 hours to hydrotalcite of Mg ₈ Al ₄ (OH) ₁₆ O ₄ (CO ₃ ) ₂ After obtaining 5 hours of immersion in water at room temperature and dried for 48 hours at 60 ℃ to obtain a hydrotalcite of the structural formula Mg ₈ Al ₄ (OH) ₁₆ O ₄ (CO ₃ ) ₂ · 7H ₂ O.

Preparation Example 5

Strucic acid coated with stearic acid in the same manner as in Preparation Example 1, except that hydrotalcite of structural formula Mg ₉ Al ₃ (OH) ₂₄ (CO ₃ ) _1.5 · 7.5H ₂ O was coated with 1.5% by weight of stearic acid. Hydrotalcite of the structural formula Mg ₉ Al ₃ (OH) ₁₈ O ₃ (CO ₃ ) _1.5 was prepared.

Preparation Example 6

Structure same manner as _{Mg 9 Al 3 (OH) 24} (CO 3) 1.5 · 7.5H , except that the dihydro-coated hydrotalcite as stearic acid 1.5% by weight of melamine polyphosphate, and 1% by weight of the ₂ O Preparation 2 The hydrotalcite of Mg ₉ Al ₃ (OH) ₁₈ O ₃ (CO ₃ ) _1.5 coated with stearic acid and melamine polyphosphate was prepared.

Preparation Example 7

Structure as _{Mg 9 Al 3 (OH) 24} (CO 3) 1.5 · and a hydrotalcite of 7.5H ₂ O in the same manner as melamine polyphosphate, and is manufactured, except for a point coated with 3% by weight Example 2 Melamine polyphosphate A hydrotalcite having a coated structural formula Mg ₉ Al ₃ (OH) ₁₈ O ₃ (CO ₃ ) _1.5 was obtained, and then left in a moisture-containing atmosphere for 1 week to coat Mg ₉ Al ₃ (OH) coated with melamine polyphosphate. ) was prepared hydrotalcite of _{18 O 3 (CO 3) 1.5} · 7.5H 2 O.

Preparation Example 8

Formula _{Mg 9 Al 3 (OH) 24} (CO 3) 1.5 · 7.5H 2 O in the hydrotalcite to 250 ℃ 4 hour heat treatment of the formula Mg ₉ Al _{3 (OH) 18 O 3 (CO} 3) _1.5 hydrotalcite obtained a site, and then, to prepare a hydrotalcite of the after 5 hours immersion in water at room temperature and dried at 60 ℃ 48 sigan formula _{Mg 9 Al 3 (OH) 18} O 3 (CO 3) 1.5 · 8H 2 O.

Comparative Production Example 1

The hydrotalcite of the structural formula Mg ₆ Al ₂ (OH) ₁₆ CO ₃ · 5H ₂ O was coated in the same manner as in Preparation Example 2, except that 3% by weight of melamine polyphosphate substituted with stearic acid was coated. Then, hydrotalcite of the coated structural formula Mg ₆ Al ₂ (OH) ₁₆ CO ₃ was prepared by heat treatment at 180 ° C. for 4 hours.

Comparative Production Example 2

The hydrotalcite of the structural formula Mg ₆ Al ₂ (OH) ₁₆ CO ₃ · 5H ₂ O was coated in the same manner as in Preparation Example 2, except that 3% by weight of melamine polyphosphate substituted with stearic acid was coated. Then, the hydrotalcite of Mg ₆ Al ₂ (OH) ₁₆ CO ₃ · 5H ₂ O coated with melamine polyphosphate substituted with stearic acid was prepared by drying at 100 ° C. for 1 hour.

Comparative Production Example 3

The hydrotalcite of the structural formula Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ · 3.5H ₂ O was coated in the same manner as in Preparation Example 2, except that 3% by weight of melamine cyanurate was coated. Then, the hydrotalcite of Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ · 3.5H ₂ O coated with melamine cyanurate was prepared by drying at 100 ° C. for 1 hour.

Comparative Production Example 4

Stearic acid was added to water to 3% by weight of hydrotalcite, hydrotalcite of Mg ₆ Al ₂ (OH) ₁₆ CO ₃ · H ₂ O was added, followed by stirring at 95 ° C. for 30 minutes, followed by filtering. And dried to obtain hydrotalcite coated with stearic acid. Then, hydrotalcite of the structural formula Mg ₆ Al ₂ (OH) ₁₆ CO ₃ coated with stearic acid was prepared by heat treatment at 180 ° C. for 4 hours.

Comparative Production Example 5

Hydrotalcite of the structural formula Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .5H ₂ O was heat-treated at 180 ° C. for 4 hours to prepare hydrotalcite of the structural formula Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .

Hydrotalcite ²⁷ Al Magic Angle Spinning Nuclear Magnetic Resonance Analysis

In order to confirm whether the prepared hydrotalcite was partially dehydrated, a ²⁷ Al magic angle spinning nuclear magnetic resonance (MAS NMR) analysis was performed.

²⁷ Al MAS NMR analysis was carried out using a Varian 400 MHz soiled state NMR spectrometer (Varian, USA), and as experimental conditions, standard sample Al ₂ O ₃ was used, and the transmitter frequency The transmitter frequency is 104.21 MHz, the spinning rate is 15 kHz, the scan number is 512 (hydrotalcite powder) or 8192 (hydrotalcite-containing yarn), and the pulse length is Was a one pulse of 2.3 Hz.

²⁷ Al MAS NMR analysis ^reveals the surrounding environment surrounding Al ³⁺ in hydrotalcite. For example, the structural formula Mg ₈ Al ₄ (OH) having the crystal water used in Preparation Example 2 and not dehydrated is used. ₂₄ (CO _{3) 2} · 6H ₂ O is hydrotalcite of the dog 6 hydroxyl group Al ³⁺ Surrounding it to form a octahedral structure, ²⁷ Al MAS NMR analysis was also when the peak 2, and so on. In addition, the partially dehydrated hydrotalcite of the structural formula Mg ₈ Al ₄ (OH) ₁₆ O ₄ (CO ₃ ) ₂ obtained in Preparation Example 2 has 6 hydroxyl groups as Al ³⁺ due to dehydration. The surrounding octahedral structure and four hydroxyl groups make Al ³⁺ As the surrounding tetrahedral structure is mixed, as shown in FIG. 3, the peak due to octahedron and the tetrahedron were simultaneously observed in the ²⁷ Al MAS NMR analysis.

Thus, by checking the presence or absence of the tetrahedral peak in the ²⁷ Al MAS NMR analysis, it was determined whether the obtained hydrotalcite was partially dehydroxylated hydrotalcite.

Infrared Spectroscopy of Hydrotalcite

In order to confirm whether the obtained hydrotalcite was partially dehydrated, it was analyzed by infrared spectroscopy (IR spectroscopy). Hydrotalcite between teuneun when partial dehydroxylation as a peak in the infrared spectroscopy at about 1500 ~ 1600cm ^-1 appears.

Infrared spectroscopy is IFS 88 (Bruker (Bruker), Germany) were measured through the apparatus, the experimental conditions, in the infrared range 400 ~ 4000cm ^-1 scanning resolution (resolution) of 4cm ^-1 number (No. scan) Was measured by the ATR (attentuated total reflectance) method.

As a result of analyzing the hydrotalcite of the structural formula Mg ₈ Al ₄ (OH) ₂₄ (CO ₃ ) ₂ · 6H ₂ O with crystal water used in Preparation Example 2 by infrared spectroscopy, Peak only at 1300 ~ 1400cm ^-1 appear. However, as shown in FIG. 7, the partially dehydrogenated hydrotalcite of the structural formula Mg ₈ Al ₄ (OH) ₁₆ O ₄ (CO ₃ ) ₂ obtained in Preparation Example 2 is about 1500-1 except about 1300-1400 cm ⁻¹ . Peaks were also observed at 1600 cm ^-1 .

Thus, by checking whether the peak appears at about 1500 ~ 1600cm ^-1 through infrared spectroscopy analysis, it was determined whether the obtained hydrotalcite was partially dehydroxylated hydrotalcite.

Examples 1-8 and Comparative Examples 1-5

518 g of diphenylmethane-4,4'-diisocyanate and 2328 g of polytetramethylene ether glycol (molecular weight 1800) were reacted with stirring at 80 ° C. for 90 minutes in a stream of nitrogen gas to prepare a polyurethane prepolymer having isocyanate at both ends. It was. After cooling the prepolymer to room temperature, 4269 g of dimethylacetamide was added to obtain a polyurethane prepolymer solution. Subsequently, 34.4 g of ethylenediamine, 10.6 g of propylenediamine, and 9.1 g of diethylamine were dissolved in 1117 g of dimethylacetamide, and added to the prepolymer solution at 10 ° C. or lower to obtain a polyurethane solution.

1% by weight of ethylenebis (oxyethylene) bis- (3- (5- t -butyl-4-hydroxy- m -toyl) -propionate) based on solids as an additive to the polyurethane solution, 1, 1,1 ', 1'-tetramethyl-4,4'-(methylene-di- p -phenylene) dicemicarbazide 1% by weight, poly (N, N-diethyl-2-aminoethyl methacrylate ) 1% by weight, 0.5% by weight of titanium dioxide, 0.5% by weight of magnesium stearate and 4% by weight of hydrotalcite prepared in Production Examples 1 to 8 and Comparative Production Examples 1 to 5 were respectively added and mixed to prepare a polyurethane spinning solution. Obtained.

Before adding the additives to the polyurethane spinning stock, the additives are dispersed in a dimethylacetamide solvent and ground using an Advantis V3 device (Drais Mannheim, Germany) and added to the polyurethane spinning stock. It was.

After degassing the spinning stock solution, the spinning filament was spun into hot air at an upper temperature of 250 ° C. to prepare 4 filament 40 denier spandex fibers, and the physical properties thereof were summarized in Table 1 below.

1) Strong retention rate test in chlorine water (chlorine resistance test)

The spandex yarn was treated for 2 hours in water at pH 4.2, 97-98 ° C. under 50% elongation, cooled at room temperature, and then immersed in 45 L chlorine water with 3.5 ppm of active chlorine at pH 7.5 for 24 hours at room temperature. %) = S / S _o × 100 (S _o : strong before treatment, S: strong after treatment) to evaluate the strong retention. Instron 4301 (Instron, USA) was used for the robust evaluation, and the sample length was 5 cm and measured at a cross head speed of 300 mm / min using a 1 kg cell.

2) Color measurement of spandex yarn (discoloration resistance test)

The elastic yarn was knitted using a circular knitting machine (KT-400, 4 inches in diameter, 400 submerged, Nagaka Seiki, Japan), and then knit the spandex circular knitted fabric. After mixing 2 g / L, 3 g / L of UNITOL SMS (New Cinema, Korea), and 0.5 g / L of NaOH, it refine | purified in bath ratio 1:40, 90 degreeC, and 30 minutes. The refined circular knitted fabrics were each measured for the yellowing value "b" using a color-view spectrophotometer (BYK-Gardener, USA) (test conditions: Instrument Geometry ) = 45 ^0/0, the light emitting system / observation system (Illuminant / Observer) = D65 / 10 ^0, 11mm sample port hole (sample port aperture) used, measured 3 times). The smaller the b value, the less discoloration.

As shown in Table 1, the use of partially dehydrated hydrotalcite did not discolor the spandex during the spinning process at a high temperature of 200 ° C. or higher, and also showed excellent chlorine resistance (see Examples 1 to 8).

On the other hand, when hydrotalcite having crystalline water was used, discoloration was severe during hot spinning and poor chlorine resistance (see Comparative Examples 2 and 3). In addition, in the case of using hydrotalcite in which only crystallized water was removed and not partially dehydrogenated, discoloration during high temperature radiation was better than hydrotalcite having crystallized water, but it was more resistant than using partially dehydrogenated hydrotalcite. It was much less discolored and lacked chlorine resistance (see Comparative Examples 1, 4 and 5).

Of hydrotalcite in spandex fibers ²⁷ Al MAS NMR Analysis

As a result of analyzing the spandex yarn prepared in Example 2 by ²⁷ Al MAS NMR, as shown in FIG. 4, a tetrahedral peak surrounding Al ³⁺ in the partially dehydrated hydrotalcite appeared simultaneously with the octahedral peak.

Of hydrotalcite extracted from spandex fiber ²⁷ Al MAS NMR Analysis

In order to confirm that the spandex fiber prepared in the example contained hydrodesite hydrolyzed partially, hydrotalcite was extracted from the prepared spandex fiber and analyzed by ²⁷ Al MAS NMR.

In order to extract hydrotalcite from spandex fibers, (i) removing the emulsion from the fibers with petroleum ether, (ii) dissolving the fibers in excess dimethylacetamide with a water content of 100 ppm or less, wherein The content of the fiber in dimethylacetamide is 1.3% or less), (i) centrifugation of the dissolved fiber with a centrifuge, (i) centrifugation of the sample by dissolving again with dimethylacetamide and recentrifugation. Step, and (iii) drying the sample obtained in (iii) at 60 ℃ or less.

Example 2 extracted from a spandex yarn manufactured by analysis of the hydrotalcite by ²⁷ Al MAS NMR, as shown in Figure 5, the tetrahedral and octahedral peak peak around the Al ³⁺ as seen in a partial dehydroxylation as hydrotalcite Appeared simultaneously.

Infrared Spectroscopic Analysis of Hydrotalcite Extracted from Spandex Fiber

In order to confirm that the spandex fiber prepared in the example contained hydrotalcite partially dehydrated, hydrotalcite was extracted from the prepared spandex fiber and analyzed by infrared spectroscopy.

The method of extracting hydrotalcite from spandex yarn was the same as in ²⁷ Al MAS NMR analysis.

Example 2 is cut out from a spandex yarn manufactured by analysis of the hydrotalcite by infrared spectroscopy, as shown in Figure 8, about 1500 ~ 1600cm ^-1 peak appearing at the partial dehydration oxidized hydrotalcite as was observed.

While the invention has been described in connection with the specific embodiments described above, it should be understood that those skilled in the art may variously modify and change the invention within the scope of the invention as defined by the appended claims.

Spandex fiber according to the present invention does not discolor even when spun at 200 ℃ or more shows excellent chlorine resistance. In addition, the spandex fiber according to the present invention can be effectively used in sports clothing such as underwear or socks, especially swimwear because of excellent discoloration and chlorine resistance.

Claims (8)

Spandex fiber containing 0.1 to 10% by weight of the partially dehydrated hydrotalcite relative to the total weight of the spandex fiber. The method of claim 1, Partially dehydrated hydrotalcite is a spandex fiber, characterized in that <Formula 1> M ^{2 +} _{12- y} Al _y (OH) _{24-2 z} O _z (CO ₃ ) _{y /} 2mH ₂ O Wherein, M ^{2 +} is Mg ^{2 +,} Ca ^{2 +} or Zn ^{+ 2,} y is 2.4 and <y ≤ 4 is a positive value, z is in 0 <z ≤8 positive number, m is 0 or a positive number to be. The method of claim 2, The partially dehydroxylated hydrotalcite is Mg ₈ Al ₄ (OH) ₁₆ O ₄ (CO ₃ ) ₂ , Mg ₈ Al ₄ (OH) ₈ O ₈ (CO ₃ ) ₂ , Mg ₉ Al ₃ (OH) ₁₈ O ₃ (CO ₃ ) _1.5 , Mg ₉ Al ₃ (OH) ₁₂ O ₆ (CO ₃ ) _1.5 , Mg _9.6 Al _2.4 (OH) _19.2 O _2.4 (CO ₃ ) _1.2 , Mg _9.6 Al _2.4 (OH) _14.4 O _4.8 ( CO ₃ ) _1.2 , _{Mg 8 Al 4 (OH) 16} O 4 (CO 3) 2 · 6H 2 O, Mg 8 Al 4 (OH) 8 O 8 (CO 3) 2 · 7H 2 O, Mg 9 Al 3 (OH) 18 O 3 (CO ₃ ) Spandex fibers, characterized in that at least one selected from the group consisting of _1.5 · 7.5H ₂ O and Mg ₉ Al ₃ (OH) ₁₂ O ₆ (CO ₃ ) _1.5 · 8H ₂ O. The method according to any one of claims 1 to 3, Partially dehydrated hydrotalcite is a spandex fiber, characterized in that the hydrotalcite containing crystalline water produced by heat treatment at 200 ~ 390 ℃. The method of claim 4, wherein Partially dehydrated hydrotalcite is a spandex fiber, characterized in that the hydrotalcite containing crystalline water produced by heat treatment at 250 ~ 300 ℃. The method according to any one of claims 1 to 3, Partially dewatering the oxidized hydrotalcite are ²⁷ Al magic angle spinning nuclear magnetic resonance (MAS NMR: magic angle spinning nuclear magnetic resonance) analysis when a peak indicating Al ³⁺ containing octahedral Al ^{3 +} and containing tetrahedral structure is observed at the same time Spandex fiber, characterized in that. The method according to any one of claims 1 to 3, Partially dehydrated hydrotalcite is a spandex fiber, characterized in that the peak is observed in the 1300 ~ 1400cm ^-1 region and 1500 ~ 1600cm ^-1 region, respectively, when analyzed by IR spectroscopy. The method according to any one of claims 1 to 3, Spandex fiber, characterized in that the secondary aggregated particle size of the partially dehydrated hydrotalcite is 15 μm or less.

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