TWI322838B - Spandex fibers containing partially dehydroxylated hydrotalcite - Google Patents

Description

IX. DESCRIPTION OF THE INVENTION: FIELD OF THE INVENTION The present invention relates to a spandex fiber containing partially dehydroxylated hydrotalcite having excellent fading resistance and chlorine resistance, and such spandex The inherent properties of the fiber. BACKGROUND OF THE INVENTION Spandex fibers have high rubber-like elasticity and excellent physical properties, such as high tension and restoring force, and are suitable for use in, for example, underwear, socks, and sportswear. Spandex fibers are mainly composed of polyurethanes, and their physical properties are deteriorated when exposed to vaporized water. For example, if a swimsuit made of warp-made spandex and polyamide is exposed to contain Swimming pool water from 0.5 ppm to 3 ppm active gas. Therefore, by adding an additive to the spandex fiber, many attempts have been made to improve its chlorine resistance. For example, U.S. Patent No. 4,340,527 discloses the use of zinc oxide; U.S. Patent No. 5,626,960 teaches the use of a mixture of a calcium-calcium-magnesium ore and hydromagnesite; and Korean Patent Publication No. 92-3250 proposes the use of a carbonated and cesium carbonate. a combination of Japanese Patent Application No. 6-81215, the use of a MgO/ZnO solid solution; Japanese Patent Application No. S59-133248, the use of magnesium oxide, magnesium hydroxide or hydrotalcite; and the early application of this application H59-292346 proposes the use of hydrotalcite treated with a higher fatty acid and a decane coupling agent. In particular, U.S. Patent No. 5,447,969 discloses the use of hydrotalcite coated with water of crystallization and trans- fatty acid to improve the dispersibility of the hydrotalcite and thus prevent the hydrotalcite during the preparation of the spandex. The cohesiveness thus lowers the discharge pressure and reduces the frequency of yarn breakage during spinning, reduces fading in the treatment of the acid solution, and reduces the swelling when immersed in the vaporized water. More specifically, in such a patent, the dry spinning process of a polyurethane solution is operated at a high temperature of 330 t to obtain a spandex yarn. However, 'the dry spinning process is operated at a temperature of __ or w25 (rc), and the use of hydrated water and a fatty acid coated hydrotalcite causes the spandex yarn to fade to a brownish color. U.S. Patent No. 6,692,828 discloses The use of hydrotalcite coated with a melamine-based compound having good heat resistance as an additive improves the gas resistance of the spandex fiber. However, the dry spinning is operated at or above 250 C. At the time, the spandex yarn was still faded.

The use of partially decarbonated hydrotalcites which have been ground to a mean particle size equal to or less than 丨μηι to improve the chlorine resistance of the polyurethane spandex is disclosed in U.S. Patent Application Publication No. 1 262 499 A1. The partially decarbonated hydrotalcite is obtained by decomposing a part of carbonate ions of hydrotalcite into carbon dioxide and oxygen. The carbonate ions of hydrotalcite are important for making a spandex fiber resistant to chlorine. Therefore, the resulting spandex has a hydrotalcite containing a low carbonate ion content and thus has an unsatisfactory chlorine resistance. Korean Patent Application Publication No. 2-68114 discloses a method for preparing a spandex fiber having good fading resistance and gas resistance. The method is coated with a trisamine gas. The main compound is 1322838 and does not contain hydrotalcite, and is not dehydroxylated or decarbonated. However, when the slurry of the dehydrated hydrotalcite and the mixture of the slurry and a polymer are produced in the production of spandex, because of the high hygroscopicity of the dehydrated hydrotalcite only, it tends to be converted to have The original form of crystal water, 5 therefore it should be handled carefully. Also, such a high hygroscopicity results in fading of the spandex yarn at the time of dry spinning at or above 250 °C. Despite its good chlorine resistance, such a faded spandex degrades the quality of a product and it is impossible to dye the spandex white. Therefore, it is necessary to improve both the fading resistance of a spandex fiber and the gas resistance of a spandex fiber. SUMMARY OF THE INVENTION Summary of the Invention A main object of the present invention is to provide a Spand 15 yarn which has excellent gas resistance without fading when spun at a temperature equal to or higher than 200 ° C. fiber. According to an aspect of the invention, there is provided a spandex fiber comprising a partially de-saturated hydrotalcite in an amount of from 0.1 wt% to 10 wt%. BRIEF DESCRIPTION OF THE DRAWINGS The above and other objects and features of the present invention will become more apparent from the following description of the <RTIgt; Fig. 2 is a 27A1 magic angle spin nuclear magnetic resonance (MAS NMR) spectrum of hydrotalcite (Mg8Al4(0H)24(C03)2-6H20) used in Preparation Example 2; 7 Fig. 3 is a preparation example 2 obtained 27A1 MAS NMR spectrum of partially dehydroxylated hydrotalcite (Mg8Al4(0H)1604(C03)2); Fig. 4 is a 27ai MAS NMR spectrum of a spandex obtained in Example 2; Figure 5 is a 27A1 MAS NMR spectrum of water % stone extracted from the spandex spinning of Example 2; Figure 6 is a hydrotalcite (Mg8Al4(OH)24(C) used in Preparation Example 2.红外线3) 2,6H2〇) infrared (IR) absorption spectrum; Figure 7 is an IR of partially dehydroxylated hydrotalcite (Mg8Al4(OH)i6〇4(C03)2) obtained in Preparation Example 2. The absorption spectrum; and Fig. 8 is the IR absorption spectrum of the hydrotalcite extracted from the spandex spinning of Example 2.

C. Application: J. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT The spandex fiber of the present invention has excellent gas resistance and does not discolor at a spinning process operating at or above 200 ° C, the spandex The fiber can be dehydrated and partially de-hydrogenated by heat-treating a hydrotalcite having crystal water at a temperature of 200 ° C to 39 ° C, and then adding the thus obtained partially dehydrogenated water to a polyurethane solution. The talc is prepared. Thus, according to the present invention, the hydrotalcite is partially dehydroxylated by heat treatment which is operated at a high temperature for a long period of time, which is disclosed in the Korean Patent Application No. 2006-5814. The time period, and it is not decarbonated to produce sufficient gas resistance, as used in the EP application No. 1 262 499 A1. The use of crystal water is disclosed in U.S. Patent No. 5,447,969. This hydrotalcite is effective in preventing the problem of fading in the treatment of tannic acid solution and the problem of swelling when it is poured into chlorinated water. These problems are found to be achievable through the use of this month. The partially dehydrated hydrotalcite of the crystal water is overcome. The spandex fiber according to the present invention is described in detail as follows. It should be understood that the term used herein is defined in consideration of the function of the present invention. And the meaning is changed according to the purpose of the technology in the technical field 'and does not limit the structure of the invention. The term used herein, spinning, or,, spinning process, does not mean melt spinning means Dry spinning. The term "spinning temperature" as used herein refers to the maximum temperature to which a spandex polymer is subjected during a spinning process, for example, a polymer pellet in a melt spinning process. The melting temperature, or the spinning channel temperature of a dry spinning process. The term, fading, means that a white fiber is discolored to yellow or brown. The hydrotalcite used in the present invention is a metal hydroxide, and its The structure consists of two octahedral units, an anion (Αη-) and a ruthenium molecule in the form of a bilayer, which has a divalent or trivalent ring surrounded by six hydroxide ions (0Η·). Price (Μ+2 Or Μ+3) a metal cation, and the anion (Αη_) and Ηβ molecules are used to balance the charged capacity between the two layers, as shown in Figure 1. Such a hydrotalcite can be Heat treated at a high temperature to remove H2 〇 molecules from between the two layers' and further heat treated at a higher temperature to cause dehydroxylation. If the hydrotalcite is above a dehydroxylation temperature Heat treated at higher temperatures can cause decarbonation (see Stanimirova et al., Clay 1322838)

Minerals, 39: 177-191, 2004). The term "partially dehydroxylated hydrotalcite" as used herein means a hydrotalcite obtained by heat-treating a hydrotalcite having crystal water at a high temperature to cause dehydration and dehydroxylation, which may be 20H· – H20 + 02 is shown in Table 5. The partially dehydroxylated hydrotalcite has both an octahedral and a tetrahedral site, the latter containing a metal cation surrounded by four hydroxyl groups in the bilayer structure (see Stanimirova et al, Clay Materials, 39: 177-191). , 2004). In the present invention, the partially dehydroxylated hydrotalcite can be represented by the chemical formula (1): Table 10: M2+, 2.yAly(OH)24-2z〇z(C〇3)y/2mH20 (I) wherein Μ is Mg, Ca or Zn, y is a value in the range of 2.4 &lt; y$4, z is a value in the range of 0 &lt; zS8, and m is 0 or a positive integer. Preferably, the partially dehydroxylated hydrotalcite is selected from the group consisting of Mg8Al4(OH)丨604(C〇3)2, Mg8Al4(0H)808(C03)2, Mg9Al3(OH) 18〇3(C〇3)i 5 , Mg9Al3(0H)1206(C03)15 ,

Mg9.6Al2.4(〇H)19.2〇2.4(C〇3)l.2 'Mg9.6Al2.4(OH)14.4〇4.8(C03)i.2 '

Mg8Al4(0H)1604(C03)26H20, Mg8Al4(0H)808(C03)2.7H20, Mg9Al3(0H)1803(C03)L5.7.5H20, Mg9Al3(OH)1206(C03)15 8H20 20 and one of these mixture. According to the invention, the starting hydrotalcite having water of crystallization is preferably heat treated at a temperature of from 200 ° C to 390 ° C in an anhydrous atmosphere of nitrogen, helium, oxygen, hydrogen or carbon dioxide, more preferably It is between 250 ° C and 300 ° C. If the hydrotalcite with crystal water is less than 2 Torr. At a temperature of 10, it is heat treated and the hydrotalcite may not be dehydroxylated. If the hydrotalcite is heat treated at a temperature above 39 ° C, the hydrotalcite can undergo dehydroxylation and further decarbonation, resulting in poor fluorine resistance. Therefore, the partially de-saturated hydrotalcite obtained by heat treatment at about 25 (TC to 3 〇〇t: is useful for improvement of chlorine resistance. The partially dehydroxylated hydrotalcite of the present invention can absorb air. Moisture's but most of the absorbed water is at about 100. (: is evaporated, and therefore this absorbed water is different from that in the hydrotalcite before heat treatment and at about 17 (TC to 22) (The crystal water evaporated under TC. Therefore, the partially dehydroxylated hydrotalcite is believed to have an effect on the fading of the spandex yarn at a ratio equal to or higher than 200. Because the water absorbed therein is about 1 〇〇. (: has been removed, and when the initial crystallization water in the hydrotalcite with crystal water is equal to or higher than 20 〇. The evaporation of the spandex during the process can cause fading of the spandex yarn. Similarly, the spandex fiber of the present invention obtained by adding the partially dehydroxylated hydrotalcite is prepared by adding hydrotalcite having crystal water. Pan Yi, Kesi fiber has better (four) gas, which is expected to be this part De-chemicalization, the double-layered hydroxide (tetra) of the hydrotalcite is altered to increase its effect on the capacity of water absorption and ion exchange. = Polyamines used in the preparation of spandex fibers according to the present invention are Known - conventional hydrazine preparation, such that an organic diisocyanate (tetra) and - two compound anti-heart drive through the product, dry # should produce - polyurethane front disk ~ make the far precursor dissolved in - organic solvent and allow / , ~Diamine and monoamine reaction ^ The solution of the present invention - the isocyanate includes diphenylmethane-4,4'-diisocyanate, hexamethylene diisocyanate, toluene-isocyanate, butyl diisocyanate ( Butylenediscocyanate) and hydrogenated diphenylmethane-4,4'-diisocyanate. Likewise, examples of the diol polymer which can be used in the present invention include polybutylene glycol, polypropylene glycol, polydicarbonate, and the like. The diamine serves as a chain extender and examples thereof are ethylenediamine, propylenediamine and hydrazine. A monoamine is used as a chain terminator, and the monoamine may be diethyldiamine, ethanolamine or dimethylamine. In the present invention, The polyurethane for preparing the spandex fiber may further comprise an organic additive comprising a hindered phenol-based compound 10, benz furanone, an amine urea, a benzotrisene, a double a hindered amine-based compound, and a polymeric tertiary amine stabilizer, such as a polyamine having a tertiary nitrogen atom and a polydialkyl aminoalkyl methacrylate, so as to prevent The spandex fiber is discolored and deteriorates in physical properties. Further, the spandex fiber of the present invention may further comprise an inorganic additive such as titanium oxide and stearic acid. The whiteness of the spandex fiber is desired. 'The one oxidation can be used in an amount of from 1 wt% to 5 wt%. To increase the unwinding properties of the spandex fibers, the magnesium stearate can be used in an amount of from 0.1% by weight to 2% by weight. 2〇 According to the present invention, the partially de-hydrophobized hydrotalcite may be used in an amount of from 0 Jwt% to 100% by weight based on the weight of the polyurethane to be used. When the amount is less than 0.1% by weight, the gas resistance of the spandex fiber is insufficient, and when the amount is more than 10% by weight, the strength, elongation and modulus of the spandex fiber are deteriorated. . In the preparation of spandex fibers according to the invention, the partially dehydroxylated hydrotalcite can be added to the polyurethane at any convenient time, for example, by mixing with an additive followed by a sanding or grinding process. Thereafter or after a matte or grinding process that lacks an additive. 5 In the present invention, the partially dehydroxylated hydrotalcite can be more advanced coated or uncoated by the coating agent conventionally used in the art, which does not affect the gas resistance and fading of the spandex. Examples of the coating agent include aliphatic alcohols, fatty acids, fatty acid salts, fatty acid esters, carboxylic acid esters, styrene-bake/maleic anhydride copolymers, and derivatives thereof, and decane-based couplings 10 , a titanate-based coupling agent, a polyorganisms, a polyoxo-polyorganohydrogen oxane, and a melamine-based compound. Among these examples, fatty acids, fatty acid salts and/or melamine-based compounds are preferred because the first two exhibit excellent coating efficiency when dehydrogenated by heat-treated hydrotalcite. And the last one can minimize fading. 15 The hydrotalcite coating process can be carried out by adding a coating agent (the coating agent is added in an amount of 0.1% by weight to 10% by weight based on the weight of the hydrotalcite), such as water, alcohol, ether Or a solvent of dioxane to obtain a coating agent solution, adding hydrotalcite thereto and stirring the resulting solution for a period of time at an elevated temperature of 50 ° C to 170 ° C (if necessary, using a high pressure reactor) It was operated for 2 minutes to 2 hours, then filtered and dried. Alternatively, the coating process can also be operated by hot melt a solvent free coating agent and mixing the molten coating agent with hydrotalcite in a high speed mixer. In particular, the coating process using a melamine-based compound in water should be carried out at atmospheric pressure at a temperature higher than or equal to 15 (TC 13 1322838) due to the melamine-based compound. High melting point. The coating process using the fatty acids or the fatty acid salts in water is preferably carried out at a temperature equal to or higher than 100 ° C. When the coating temperature is less than 10 ° C It is difficult to achieve a uniform coating and non-fading, and the amount of coating agent required is increased by, for example, at less than 100 ° C in terms of hydrotalcite in the coating process, or The amount of the fatty acid salt is about 3% by weight, and the amount used can be reduced to 1.5% by weight based on the hydrotalcite in the coating process at 100 ° C or higher. In the heat treatment of the hydrotalcite, such a The reduced amount of coating agent can reduce its fading effect. 10 The fatty acids used as a coating agent in the present invention are preferably selected from monohydroxy fatty acids or polyhydroxy fatty acids, monohydroxy fatty acids or polyhydroxy fatty acids. Is 3 to 40 carbon atoms a branched or branched hydrocarbon chain, for example, lauric acid, caproic acid, palmitic acid or stearic acid. The fatty acid salts used as a coating agent in the present invention are composed of 15 6 to 30 carbons. a monofunctional or difunctional and saturated or unsaturated fatty acid of an atom, and a metal selected from the group consisting of metals of Group I to Group III of the Periodic Table of the Elements and zinc. Examples of such fatty acid salts include oleic acid, palmitic acid or The lithium, magnesium, calcium or zinc salt of stearic acid is preferably magnesium stearate, calcium stearate and stearic acid, more preferably magnesium stearate. 20 Used in the present invention The melamine-based compound as a coating agent includes a melamine compound, a phosphorus-containing melamine compound, and a melamine cyanurate compound, optionally substituted by an organic compound having a carboxyl group, which may be used alone or in combination. Used. Examples of melamine compounds include methylene dimelamine, ethylene-14 bismelamine, trimethylene diglycolamine, tetramethylene diglycolamine, hexamethylene dimelamine, and tenth Base two three Cyanamide, dodecamethylene dimelamine, 1,3-cyclohexylidene dimelamine, p-phenylene dimelamine, p-xylene dimelamine, di-extension ethyl tri-melamine, tri- 5 ex-ethyl tetramelamine, four Ethyl pentamine, hexaethyl melamine and melamine formaldehyde. Examples of melamine-containing compounds include any of the above-mentioned melamine compounds linked to phosphoric acid or monophosphate, for example, melamine pyrophosphate, melamine a primary phosphate, a melamine secondary phosphorus 10-acid salt, a melamine polyphosphate, a bis-(neopentitol phosphate) melamine salt, etc. Examples of the cyanuric acid melamine compound include at least one selected from the group consisting of A melamine cyanurate compound substituted with a substituent of a phenyl group, a phenyl group, a carboxymethyl group, a 2-carboxyethyl group, a cyanoguanidinyl group or a 2-cyanoethyl group. Preferably, the above melamine-based compound is reacted with a compound having a fluorenyl group. Examples of the compound of the (four) having - county include aliphatic monoretinic acid (for example, caprylic acid, deca-acid, lauric acid, undecanoic acid + tetraacid, pentadecanoic acid, palmitic acid, heptadecanoic acid stearic acid) , 19 &amp;L -10 S夂, -dodecanoic acid), aliphatic diacyl acid (for example, malonic acid, succinic acid, glutaric acid, adipic acid 'pimelic acid, suberic acid , azelaic acid, —,·undecanedioic acid (7) azelaic acid (3) undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 113-tridecanedicarboxylic acid, and w-fourth dicarboxylic acid) , aromatic mononuclear (for example, benzoic acid, phenylacetic acid, &amp; naphthoic acid 'β_# formic acid, eynnamie _, p-amino hippuric acid and 4 (2·嗟15 oxazolidine)-phthalaninoic acid), Aromatic dicarboxylic acids (for example, terephthalic acid, isophthalic acid, and phthalic acid), aromatic tricarboxylic acids (for example, 'trimellitic acid, l53, 5-benzenetricarboxylic acid, and Cis(2-carboxyethyl)dimeric isocyanate), aromatic tetraacids (for example, pyromellitic acid and biphenyltetracarboxylic acid), aliphatic cyclic monocarboxylic acids (for example, cyclohexane carboxylate) Acid) and aliphatic Like dicarboxylic acids (for example 'Shu, cyclohexanedicarboxylic acid 2_). The coating agent increases the dispersibility of the hydrotalcite in a spandex polymer solution and maintains the spinnability of the spandex. However, 'although the hydrotalcite is not coated, it can exhibit an excellent spinnability of 10' which is substantially equivalent to the spinnability of the coated hydrotalcite when it is sanded or ground. 15 20 The sanding or grinding process can be operated by grinding with a conventional bead mill, the hydrotalcite, a small amount of polyamine, and a mixture or slurry. The small amount of polyurethane used increases the dispersibility of the hydrotalcite. Examples of solvents which can be used in the sanding or grinding process include a mixture of oxime, dimethylformamide, dimethyl sulfoxide and the like. When the hydrotalcite is ground or ground to have a small secondary particle equal to an average size of 15 tons, in the preparation of the Span: dimension, it can exhibit a function equivalent to being coated and The function of fiber or ground hydrotalcite. Broken sand is also 'in the present invention, the heat used for the hydrotalcite is used to produce various types of desiccant to produce about 2 〇 (rc to 39 〇 can be made, for example, for example, and is handled by the heart Those operating in convection, conduction, radiation, microfabrication. The invention will be further described in detail with reference to the embodiments. However, it should be understood that the invention is not Limitations. Preparation of the smoothed stone which was dehydroxylated in the examples. 5 Preparation Example 1 Stearic acid and hydrotalcite having the chemical formula Mg8Al4(OH)24(C〇3)2.6H2〇 were successively added to water. The amount of stearic acid was 2 wt/w produced by the mixture at 15 Torr. (: stirred for 20 minutes, filtered and dried) to obtain stearic acid coated hydrotalcite. The hydrotalcite coated with 10 was heat-treated at 250 ° C for 4 hours to obtain a stearic acid-coated hydrotalcite having the chemical formula Mg8Al4(0H)1604(C03) 2. Preparation Example 2 Stearic acid, melamine polyphosphoric acid Salt and hydrotalcite with the chemical formula Mg8Al4(OH)24(C〇3)2*6H2〇 are successively added Into the water. 15 The amounts of stearic acid and melamine polyphosphate were 2 wt% and 1 wt%, respectively, based on the weight of the hydrotalcite. The resulting mixture was mixed at 160 ° C for 30 minutes, filtered and It is dried to obtain hydrotalcite coated with stearic acid and melamine polyphosphate. The coated hydrotalcite is heat treated at 250 ° C for 4 hours to obtain a coating of stearic acid and melamine polysulphate. Covered hydrotalcite having a chemical formula of Mg8Al4(0H)1604(C03)2. Preparation Example 3 Except that hydrotalcite having the chemical formula Mg8Al4(0H)24(C03)2.6H20 was coated with 3 wt% of melamine polyphosphate The procedure in Preparation 2 was repeated to obtain a hydrotalcite coated with melamine polyphosphate having the formula 17 ''Mg8Al4(〇H)i6〇4(C〇3) 2. Then, the product was under humid air . exposed for 7 days to obtain melamine coated chemical formula

Mg8Al4(〇H) 1604(C〇3) 2.6H20 hydrotalcite. I. Preparation 4 Hydrotalcite having the chemical formula Mg8Al4(OH)24(C03)2.6H2〇 was heat-treated at 25 ° C for 4 hours to obtain hydrotalcite having the chemical formula Mg8Al4(0H)1604(C03)2. The product was immersed in water for 5 hours at room temperature and dried at 6 (TC for 48 hours to obtain a chemical formula).

Water talc of Mg8Al4(〇H)16〇4(C03)2.7H20. 1〇I Preparation Example 5 The procedure in Preparation Example 1 was repeated except that hydrotalcite having the chemical formula Mg9Al3(〇H)24(e〇3)i.5'7.5H20 was coated with 1.5 wt% of stearic acid. A hydrotalcite having a chemical formula of Mg9Al3(〇H)18〇3(c〇3)15 coated with stearic acid is obtained. *Reference 6 ® except the procedure of coating the hydrotalcite having the chemical formula Mg9Al3(0H)24(C03)15.7.5H20 with 1.5 wt% of stearic acid and 1 wt% of melamine polyphosphate. To obtain a water-slip 20 stone having the chemical formula Mg9Ai3(〇H)i8〇3(C〇3)i.5 coated with stearic acid and melamine polysalt. Preparation Side 7 The procedure in Preparation 2 was repeated except that a talc of the chemical formula Mg9Al3(〇H)24(c〇3)15_7.5H20 was coated with 3 wt% of melamine polyphosphate, to obtain melamine polyphosphate. Salt coated with the chemical formula 18 1322838

Water talc of MggAldOHkCMCOA.s. Then, the product was exposed to moisture for 7 days to obtain a hydrotalcite having a chemical formula of Mg9Al3(OH)1803(C03)15.7.5H20 coated with melamine polyphosphate. Production Example 8 5 Hydrotalcite having a chemical formula was heat-treated at 250 ° C for 4 hours to obtain a hydrotalcite having a chemical formula of Mg9Al3(0H)1803(C〇3)15. The product was immersed in water at room temperature for 5 hours and dried at 60 ° C for 48 hours to obtain hydrotalcite having the chemical formula Mg9Al3(〇H)i8〇3(C〇3)i.5.8H2〇. 10 Comparative Preparation Example 1 The coating procedure of Preparation Example 2 was repeated except that the hydrotalcite having the chemical formula Mg6Al2(0H)i6C03.5H20 was coated with 3 wt% of the stearic acid-substituted melamine polyphosphate. The product was heat-treated at 180 ° C for 4 hours to obtain a stearic acid-coated hydrotalcite having a chemical formula of 15 Mg6Al2(〇H)i6C〇3, which was substituted with melamine polyphosphate. Comparative Preparation Example 2 The coating procedure of Preparation 2 was repeated except that the hydrotalcite having the chemical formula Mg^XOHhCCVSHsO was coated with 3 wt% of the stearic acid-substituted melamine poly-salt. The product was heat treated at 1 ° C for a few hours to obtain a hydrotalcite of the formula Mg6Al2(0H)16C03.5H20 coated with stearic acid substituted with melamine polyphosphate. Comparative Preparation Example 3 except that the chemical formula MguAl/OH^COd.SH2 was coated with 3% by weight of melamine polyphosphate. Outside the hydrotalcite' repeat the preparation procedure of the preparation of Example 2, 13 1322838. Then, the product was dried at 100 C for 1 hour to obtain a hydrotalcite having a chemical formula of Mg4.5Al2(〇H)nC〇3_3 ·5Η2〇 coated with melamine polyphosphate. Comparative tray preparation example 4 5 stearic acid and hydrotalcite having the chemical formula Mg6Al2(〇H)i6C〇3.5H2〇 are successively added to water. The amount of stearic acid is 3 wt% 'by weight of the hydrotalcite and The resulting mixture was stirred at 95 ° C for 3 minutes, filtered and dried to obtain a stearic acid coated hydrotalcite. The coated hydrotalcite was heat-treated at 180 ° C for 4 hours to obtain a stearic acid-coated hydrotalcite having the chemical formula Mg6Al2(0H)16C03. Comparative Preparation Example 5 Hydrotalcite having the chemical formula Mg6Al2(OH)i6CCV5H2 is at 18 Torr. The crucible was heat treated for 4 hours to obtain a hydrotalcite having the chemical formula Mg6Al2(〇H)16C03. 15 Experimental Example 1: 27A1 Magic Angle Spin Nuclear Magnetic Reel of Hydrotalcite NMR) The hydrotalcite obtained by this method was examined by 27 Α 1 magic angle spin nuclear magnetic resonance (MAS NMR) analysis to examine partial de-chemicalization. . Specifically, 27A1 MAS NMR analysis was performed using a 400 MHz solid state 2 NMR spectrometer (Varian, USA) under the following conditions: Al2〇3 standard, 104·21 ΜΗζ emission frequency, 15 kHz rotation, number of scans: 512 (water) Talc powder) or 8192 (hydrotalcite-containing yarn) and a pulse having a wavelength of 2.3 gs. The resulting 27A1 MAS NMR results can be used to determine the structure around the A13 in the water slide 20 1322838. For example, the 27Ai j^AS NMR data from the initial hydrotalcite having the chemical formula Mg8Al4(OH)24(C〇3)2.6H2〇 used in Preparation Example 2 shows a peak of a13+ with respect to octahedral coordination, The data of the 5 hydrotalcite of Mg8Al4(〇H)1604(C03)2 obtained in Preparation Example 2 as shown in Fig. 2 shows both the octahedral coordinated Al3+ peak and the partial de-chemicalization. The result of the tetrahedral coordination of the Al3+ peak is shown in Figure 3. Therefore, the hydrotalcite obtained in Preparation Example 2 was found to be partially dehydroxylated, which was confirmed by the presence of a tetrahedral peak. Experimental Example 2: Infrared rays of hydrotalcite (iw) 10 The hydrotalcite obtained in Preparation Example 2 was also examined for partial dehydroxylation by IR spectroscopy. If the hydrotalcite is partially dehydroxylated, an IR absorption The spectrum shows a distinct peak at a wavenumber of about 1500 cm-1 to 1600 cm-1. Specifically, the IR analysis is operated according to ATR (attenuated total reflection method) using IFS 88 (Bruker, Germany) under the following conditions: Wavenumber region ' ^m·1 resolution, and number of scans: 16. The ir absorption spectrum of the initial hydrotalcite having the chemical formula Mg8Al4(OH)24(C〇3)2'6H2〇 used in Preparation Example 2 A sufficiently large absorption peak at a wavenumber of about 1300 cm1 to 1400 cm-1, as shown in Fig. 6, and having the chemical formula 20 MgsAl4(OH)i6〇4(C〇3)2 obtained in Preparation Example 2 The spectrum of the hydrotalcite shows a considerable absorption peak at a wave number of about 13 〇〇cm-i to 1400 cm·1 and about 1500 cm1 to 1600 cm·1 as shown in Fig. 7. Therefore, only in the preparation example The hydrotalcite obtained in 2 was found to be partially dehydroxylated and was a distinct peak at about 1500 cm·1 to 1600 cm·1. It was confirmed that there was 21 1322838. Example 1 -8 and specific 鲂 f Example 1-5 518 g of diphenylmethane-4,4,-diisocyanate and 2,328 g of polybutylene glycol (Mw 1,800) in a nitrogen atmosphere The reaction was stirred at 80 ° C for 9 minutes to produce a 5 polyurethane prepolymer having an isocyanate group at both end groups. After cooling the prepolymer to room temperature, 4,269 g of dimethylacetamide was added. A polyurethane prepolymer solution was obtained. Next, 34.4 g of ethylenediamine, 1.06 g of propylenediamine and 9.1 g of diethylamine were dissolved in 1,117 g of dimethylacetamide. The product solution was equal to or low. Adding to the prepolymer solution at 10 ° C to obtain a poly 10 amine ester solution. 1 wt% of ethylene-bis(oxyethylene) double based on the total weight of the solid portion of the polyurethane solution -(3-(5-t-butyl-4-hydroxy-m-tolyl)-propionate), 1 wt% of bis(N,N-dimethylindenyl-4-phenyl)methane, Poly (N,N-diethyl-2-amine ethyl methacrylate) of lwt 〇 /0, 5 5 wt% of titanium dioxygen pentoxide, 0.5 wt% of stearic acid money, 4 wt% of Preparation Examples 1-8 and Comparative Preparations 1-5 each obtained The hydrotalcite (dispersed and ground by dispersing and grinding in dimercaptoacetamide using Advantis V3 (Drais Mahnheim, Germany)) is mixed with the polyurethane solution to obtain a spinning solution of a polyurethane. The spinning solution of the polyurethane is then The spinning temperature of 250 ° C was defoamed and dried by spinning to obtain a 4-wire 40-denier spandex fiber. The following properties of the obtained spandex fibers were measured, and the results are shown in Table 1: (1) Gas resistance 22 1322838 Spandex spinning water subjected to 50% stretching (pH 4.2, 97-981 ) treated for 2 hours and cooled to room temperature. The spandex spinning was immersed in 45 liters of vaporized water (pH 7.5) containing 3.5 ppm of active gas for 24 hours, and its strength was at a punch moving rate of 300 mm/min using Instron 5 4301 (Instron Co) ·, USA) By applying a lkg cell to a 5 cm long sample, the intensity retention rate is calculated as follows: Strength retention rate (%) = (S/SG) xl 〇〇 (where S〇 is The strength before treatment, and S is the strength after treatment) (2) Foil resistance 10 Separately used a spandex in a needle knitting machine (KT-400, diameter 4 inches, 400 needles, Nagata Seiki Company, A circular knitted fabric was prepared on Japan, and a detergent, 2 g/L of UNITOL CT-81 (Shinyong Chemical, Korea), 3 g/L of UNITOL-SMS (Shinyong) was used at 90 °C.

A mixture of Chemical 'Korea) and 0.5 g/L of NaOH was washed in water for 15:30 minutes, and the weight of water was 40 times the weight of the fabric. The yellowing value "b" of the fabric being washed was measured using a color-view spectrophotometer (BKY-Gardener, USA) under the following conditions: instrument geometry (AS) geometry (instrument geometry pAS'O., luminescence Object/observer = D65/10〇, 11 mm sample port aperture ' and 3 repeated measurements. Lower b value than 2〇 means less fading. 23 C β ) 1322838 Table 1 Coating Agent (Amount a) Example 1 Example 2 Stearic acid (2 wt%) + S polyamine polyphosphate nwt%) Example 3 Example 4 Example 5 Example 6 Melamine polyphosphate _ (3 wt%) _ Stearic acid (.5wt%) + S melamine polyphosphate (lwt%)

Example 7 Example 8 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Melamine Polyphosphate_(3wt%)_ Stearic acid-substituted melamine polyphosphate_(3wt° /〇)_ melamine polyphosphate substituted by stearic acid (3wt ° / 〇) melamine cyanurate (3wt ° / 〇) stearic acid (3wt%): the amount of water of the coating agent based on the weight of hydrotalcite Talc Mg8Al4(〇H)|6〇4(C〇3)2 Mg8Al4(〇H)16〇4(C03)2 Mg8Al4(0H)1604(C03)2.6H20 Mg8Al4(0H)1604(CO3)2.7H20 Mg9Al3( OH)1803(C03)15 Mg9Al3(OH)l803(C03)15 Mg9Al3(OH)18〇3(C〇3)i.5-7.5H20 Mg9Al3(0H)1803(C03)is-8H20 Mg6Al2(0H)16C03 Mg6Al2(0H)16C03.5H20 Mg4.5Al2(0H)13C03-3_5H20 MgeAl2(0H)16C03 Mg6Al2(OH)i6CO^

As shown in Table 1, the spandex of Examples 1 to 8 contains partially dehydroxylated hydrotalcite, and therefore they do not spun at a temperature equal to or higher than 5 200 ° C. Fading and good gas resistance. In contrast, spandex fibers containing water of crystallization (Comparative Examples 2 and 3) showed both poor fading resistance at the time of spinning at a high temperature and poor gas resistance. Similarly, these spandex fibers containing hydrotalcite which is not partially dehydroxylated and lacking water of crystallization (Comparative Examples 1, 4 and 5) are more resistant to fading than spandex fibers containing hydrotalcite which crystallizes 10 water, but They are less resistant to fading and are also resistant to chlorine than the spandex fibers of these inventions. 24 1322838 Experimental Example 3: The spandex yarn θ SAw . obtained in Example 2 in the _ _ MAS NMR analysis, the 27A1 MAS NMR analysis in the procedure of Example 1, and the resignation from the e ^ D fruit in the first 4 - as shown in Fig. 4, the peak of the ai3+ of the octahedral coordination of the spandex of the embodiment shows the tetrahedral coordination of 匐3+,

MAS NMR analysis 10 The spandex yarn present in the partially dehydroxylated hydrotalcite obtained in Example 2 was evaluated.

5 shows that the spandex yarn of Example 2 was degreased by treatment with petroleum ether, which was dissolved in methyl acetamide to a concentration of less than or equal to 1.3%. The mercaptoamine contains less than or equal to 15 i〇〇ppm of water, and the solution is subjected to two centrifugation to extract hydrotalcite. The extracted hydrotalcite is at 60. (The lower layer was dried and analyzed by 27A1 MAS NMR in the procedure according to Experimental Example 1. The total fruit confirmed that the extracted hydrotalcite had both an octahedral structure and a tetrahedral structure, as shown in Fig. 5. to show.

The spandex extracted from the spandex obtained in Example 2 was also analyzed by IR spectroscopy in the procedure of Experimental Example 2. As a result, the IR absorption spectrum of the extracted hydrotalcite shows a considerable absorption peak at a wavenumber of about 1500 Å! 1-1 to 1600 (: 111-1 as shown in the figure of No. 25 1322838 8 As described above, the spandex fiber of the present invention has both high gas resistance and high fading resistance at a temperature equal to or higher than 200 ° C during spinning, and thus for underwear, Socks and especially sportswear such as swimwear 5 are useful.

While the invention has been described with respect to the specific embodiments, it is to be understood that modifications and variations of the invention are intended to be included within the scope of the invention As defined in the scope of patents.

10 [Simple description of the drawings: J Figure 1 is a diagram showing the structure of the hydrotalcite; Figure 2 is a hydrotalcite (Mg8Al4(OH)24(C〇3)2.6H2〇) used in Preparation Example 2 27Ai Magic Angle Spin NMR NMR Spectroscopy; 15 Figure 3 is the 27A1 MAS of the hydrotalcite (Mg8Al4(OH)16〇4(C03)2) obtained in Preparation Example 2 NMR light is strict. Fig. 4 is a ~MAS NMR spectrum of a spandex obtained in Example 2; Fig. 5 is a 27A1 of a 20 stone extracted from the spandex of Example 2. MAS NMR spectrum; 'month 6 is an infrared (ir) absorption light of the hydrotalcite (Mg8Al4(OH)24(C03)2.6H2〇) which is used in the preparation example 2, and the seventh The figure is an IR absorption spectrum of a partially dehydroxylated hydrotalcite (Mg8Al4(〇H)i6〇4(C03)2) obtained in Preparation Example 2; and 26 1322838. FIG. 8 is a Spandec from Example 2. IR absorption spectrum of hydrotalcite extracted from Sifang. [Main component symbol description] (none)

Claims (1)

1322838 Patent Application No. 96150515 Patent Application Revision 98jJ^月23曰 X. Application Patent Range: Positive Replacement Page 1· A spandex fiber containing one 〇.iwt. /. To the dehydroxylated hydrotalcite, wherein the partially dehydroxylated hydrotalcite is represented by the chemical formula (1): M, 2.yAly(〇H) 24.2z〇2(C〇3)y/2mH2〇(I) among them 15 Μ is Mg, Ca or Zn, y is a value in the range of 2.4 &lt; y$4, z is a value in the range of 〇 &lt; ζ $8 and m is zero or a positive number. 2. The spandex fiber according to claim 1, wherein the partially dehydroxylated hydrotalcite is selected from the group consisting of MgsAl4(〇H)丨6〇4(C〇 3) 2, Mg8Al4(〇H)8〇8(C03)2, Mg9Al3(OH)18〇3(C〇3), .5 'Mg9Al3(OH)12〇6(C〇3), .5 'Mg9 .6Al24(〇H)19.2〇2,4(C03)12,Mg96Al2.4(〇H)14 (7), Mg8Al4(0H)1604(C03)2-6H20,Mg8Al4(0H)808(C03) 2.7H20, Mg9Al3(OH)18〇3(C〇3)i.5 7.5H20, Mg9Al3(〇H)丨2〇6(C03)丨5·8Η20 and one of these mixtures. 3. The spandex fiber of claim 1 or 2, wherein the 20 parts of the dehydroxylated hydrotalcite are heat treated by hydrothermal treatment of hydrotalcite having crystal water at a temperature of from 200 ° C to 390 ° C. Prepared. 4. The spandex fiber according to claim 3, wherein the partially dehydroxylated hydrotalcite is prepared by heat-treating hydrotalcite having crystal water at a temperature of 300 ° C jL 300 ° C. of. 28 1322838 ff years (3⁄4 positive replacement page ___________ 5. For the spandex fibers of claim 1 or 2, their 27A1 magic angle spin nuclear magnetic resonance (MAS NMR) spectra are shown The peak of Al3+ with octahedral coordination shows the peak of tetrahedral coordination of Al3+. 6_Spandex fibers of the first or second patent application, their red 5 outer (IR) absorption spectrum Shows significant absorption at 1300 cm·1 to 1400 cm·1 and lSOOcnT1 to 1600 cm-1 wavenumber. 7. Spandex fiber according to claim 1 or 2, wherein the part is dehydroxylated water Talc has an average size of less than or equal to 15 μm Secondary particles. 29