EP2021537B1 - Fibres spandex contenant de l'hydrotalcite partiellement déshydroxylée - Google Patents

Fibres spandex contenant de l'hydrotalcite partiellement déshydroxylée Download PDF

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Publication number
EP2021537B1
EP2021537B1 EP07708702A EP07708702A EP2021537B1 EP 2021537 B1 EP2021537 B1 EP 2021537B1 EP 07708702 A EP07708702 A EP 07708702A EP 07708702 A EP07708702 A EP 07708702A EP 2021537 B1 EP2021537 B1 EP 2021537B1
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EP
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Prior art keywords
hydrotalcite
acid
spandex
spandex fiber
partially dehydroxylated
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German (de)
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EP2021537A1 (fr
EP2021537A4 (fr
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Byung Su Song
Seung Won Seo
Byung Ha Yoo
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Hyosung Corp
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Hyosung Corp
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/10—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyurethanes
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/06—Load-responsive characteristics
    • D10B2401/061—Load-responsive characteristics elastic

Definitions

  • the present invention relates to a spandex fiber containing a partially dehydroxylated hydrotalcite which has excellent discoloration-resistance and chlorine-resistance as well as the intrinsic properties of spandex fiber.
  • Spandex fibers have high rubber-like elasticity and excellent physical properties such as high tensile force and restoration force suitable for use in, e.g., underwears, socks and sports wears.
  • Spandex fibers consist predominantly of polyurethane, whose physical properties deteriorate when exposed to chlorinated water, e.g., if a swimming wear manufactured by warp-knitting spandex and polyamide is exposed to swimming-pool water containing from 0.5 to 3 ppm of active chlorine.
  • US Patent No. 4,340,527 suggests the use of zinc oxide; US Patent No. 5,626,960 , a mixture of huntite and hydromagnesite; Korean Patent Publication No. 92-3250 , a combination of calcium carbonate and barium carbonate; JP Application Laid-Open No. H6-81215 , an MgO/ZnO solid solution; JP Application Laid-Open No. S59-133248 , magnesium oxide, magnesium hydroxide or hydrotalcite; and JP Application Laid-Open No. H3-292364 , hydrotalcite treated with a higher fatty acid and a silane coupling agent.
  • US Patent No. 5,447,969 discloses the use of hydrotalcite having crystallized water and being coated with a C 10-30 fatty acid, to improve the dispersability of the hydrotalcite and thus prevent the hydrotalcite aggregation during the course of preparing spandex, thereby reducing the rise of discharge pressure and the frequency of yarn breakage while spinning, the discoloration during tannin solution-treatment, and the swelling when immersed in chlorinated water. More specifically, in such patent, the dry spinning process of a polyurethane solution is conducted at a high temperature condition of 330 °C to obtain spandex yarn. However, the use of hydrotalcite having crystallized water and being coated with a C 10-30 fatty acid causes the spandex yarn discoloration to yellow-brown during the dry spinning process conducted at a temperature of 250 °C or higher.
  • US Patent No. 6,692,828 discloses the use of hydrotalcite coated with a melamin-based compound having good heat-resistance as an additive to improve the chlorine-resistance of spandex fibers.
  • the spandex yarn still undergoes discoloration during dry spinning conducted at 250 °C or higher.
  • EP Application Publication No. 1 262 499 A1 discloses the use of partially decarbonated hydrotalcite milled to an average grain size of 1 ⁇ m or less for improving the chlorine-resistance of polyurethane spandex.
  • the partially decarbonated hydrotalcite is obtained by decomposing a part of carbonic ion moieties of hydrotalcite into carbon dioxide and oxygen.
  • the carbonic ion of hydrotalcite is important for imparting the chlorine-resistance to a spandex fiber. Accordingly, the resultant spandex has the hydrotalcite containing a low carbonic ion content, thereby having unsatisfactory chlorine-resistance.
  • Korean Patent Application Publication No. 2006-5814 discloses a method for preparing a spandex fiber having good discoloration-resistance and chlorine-resistance by using hydrotalcite which is coated with a melamine-based compound and free of crystallized water, without dehydroxylation- or decarbonation-treatment.
  • said hydrotalcite only dehydrated should be carefully handled since it is high hygroscopic and tends to convert to the original form having crystallized water, during making its slurry or a mixture of the slurry and a polymer in spandex production. Also, such a high hygroscopicity still leads to the discoloration of the spandex yarn during dry spinning at 250 °C or higher.
  • a spandex fiber comprising a partially dehydroxylated hydrotalcite in an amount of 0.1 to 10 % by weight as defined in claim 1.
  • the spandex fiber of the present invention has excellent chlorine-resistance and does not undergo discoloration during spinning process conducted at 200 °C or higher, which may be prepared by heat-treating a hydrotalcite having crystallized water at a temperature of 200 to 390 °C to induce dehydration and partial dehydroxylation and then adding a partially dehydroxylated hydrotalcite thus obtained to a polyurethane solution.
  • hydrotalcite is partially dehydroxylated by heat-treatment conducted at a high temperature for a long period beyond those disclosed in Korean Patent Application Publication No. 2006-5814 , and it is not decarbonated to give sufficient chlorine-resistance, other than that used in EP Application Publication No. 1 262 499 A1 .
  • the spandex fiber according to the present invention is described in detail as follows.
  • spinning or “spinning process” used herein means either melt-spinning or dry-spinning.
  • spinning temperature used herein means the maximum temperature to which a spandex polymer is subjected during a spinning process, e.g., the melting temperature of a polymer chip in a melt-spinning process, or the spinning chamber temperature of a dry-spinning process.
  • discoloration means that a white fiber gets colored as yellow or brown.
  • the hydrotalcite used in the present invention is a type of metal hydroxide whose structure consist of two octahedral units having metal cation of 2 or 3 valences (M +2 or M +3 ) surrounded by six hydroxide ions (OH - ) in the form of double layers, anions (A n- ) and H 2 O molecules for balancing the charged capacity between the double layers, as shown in FIG. 1 .
  • Such a hydrotalcite can be heat-treated at a high temperature to remove H 2 O molecules from between the double layers and further heat-treated at a higher temperature to induce dehydroxylation. If the hydrotalcite is heat-treated at a higher temperature than the dehydroxylation temperature, decarbonation may be induced ( see Stanimirova et al., Clay Minerals, 39: 177-191, 2004 ).
  • partially dehydroxylated hydrotalcite used herein means a hydrotalcite obtained by heat-treating a hydrotalcite having crystallized water at a high temperature to induce dehydration and dehydroxylation which may be represented by 20H - ⁇ H 2 O + O 2- .
  • the partially dehydroxylated hydrotalcite has both octahedral and tetrahedral sites, the latter containing a metal cation surrounded by four hydroxyl groups within the double-layered structure ( see Stanimirova et al., Clay Minerals, 39: 177-191, 2004 ).
  • the partially dehydroxylated hydrotalcite is represented by formula (I): M 2+ 12-y Al y (OH) 24-2z O z (CO 3 ) y/2 ⁇ mH 2 O (I) wherein, M is Mg, Ca or Zn, y is a value in the range of 2.4 ⁇ y ⁇ 4, z is a value in the range of 0 ⁇ z ⁇ 8, and m is zero or a positive number.
  • the partially dehydroxylated hydrotalcite is selected from the group consisting of compounds of 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, Mg 9 Al 3 (OH) 12 O 6 (CO 3 ) 1.5 ⁇ 8H 2 O, and a mixture thereof.
  • the starting hydrotalcite having crystallized water is preferably heat-treated at a temperature of 200 to 390 °C, more preferably 250 to 300 °C under a moisture-free atmosphere of nitrogen, helium, oxygen, hydrogen or carbon dioxide.
  • the hydrotalcite having crystallized water is heat-treated at a temperature less than 200 °C, the hydrotalcite may not be dehydroxylated. If the hydrotalcite having crystallized water is heat-treated at a temperature higher than 390 °C, the hydrotalcite may undergo dehydroxylation and further decarbonation, leading to deteriorated chlorine-resistance. Accordingly, the partially dehydroxylated hydrotalcite obtained from the heat-treatment at about 250 to 300 °C is useful for the improvement of chlorine-resistance.
  • the partially dehydroxylated hydrotalcite of the present invention may adsorb moisture in air, but most of the moisture adsorbed is vaporized at about 100 °C, and thus such adsorbed moisture is different from crystallized water which is present in the hydrotalcite before heat-treatment and vaporizes at about 170 to 220 °C. Accordingly, the partially dehydroxylated hydrotalcite is believed to give no affection on the discoloration of the spandex yarn during a spinning process at 200 °C or higher since the moisture adsorbed therein is already removed at about 100 °C, while the hydrotalcite having crystallized water may induce the discoloration of the spandex yarn as the initial crystallized water thereof vaporizes during a spinning process at 200 °C or higher.
  • the inventive spandex fiber prepared by adding the partially dehydroxylated hydrotalcite has superior chlorine-resistance than that prepared by adding hydrotalcite having crystallized water, which is considered as a result that the layered double hydroxide system of the partially dehydroxylated hydrotalcite is changed to enhance its capacity for water absorption and ion-exchange.
  • the polyurethane used in the preparation of the spandex fiber according to the present invention may be prepared by a conventional method known in the art, e.g., by reacting an organic diisocyanate and a diol polymer to produce a polyurethane precursor, dissolving the precursor in an organic solvent and allowing the resulting solution to react with a diamine and monoamine.
  • the organic diisocyanate which may be used in the present invention includes diphenylmethane-4,4'-diisocyanate, hexamethylenediisocyanate, toluenediisocyanate, butylenediisocyanate and hydrogenated diphenylmethane-4,4'-diisocyanate.
  • examples of the diol polymer which may be used in the present invention include polytetramethylene ether glycol, polypropylene glycol, polycarbonate diol, etc.
  • the diamine is used as a chain extender and examples thereof are ethylenediamine, propylenediamine and hydrazine.
  • the monoamine is used as a chain terminator and it may be diethyldiamine, monoethanolamine or dimethylamine.
  • the polyurethane for preparing the spandex fiber may further comprise organic additives including hindered phenol-based compounds, benzofuranons, semicarbazides, benzotriazoles, hindered amine-based compounds, and polymeric tertiary amine stabilizers such as a tertiary nitrogen atom-containing polyurethane and polydialkyl aminoalkyl methacrylate, so as to prevent the spandex fiber from discoloration and deterioration in physical properties.
  • organic additives including hindered phenol-based compounds, benzofuranons, semicarbazides, benzotriazoles, hindered amine-based compounds, and polymeric tertiary amine stabilizers such as a tertiary nitrogen atom-containing polyurethane and polydialkyl aminoalkyl methacrylate, so as to prevent the spandex fiber from discoloration and deterioration in physical properties.
  • the spandex fiber of the present invention may further comprise inorganic additives such as titanium dioxide and magnesium stearate.
  • the titanium dioxide may be used in an amount of 0.1 to 5 % by weight according to the whiteness of the spandex fiber desired.
  • the magnesium stearate may be used in an amount of 0.1 to 2 % by weight to enhance the unwinding property of the spandex fiber.
  • the partially dehydroxylated hydrotalcite is used in an amount of 0.1 to 10 % by weight based on the weight of the polyurethane used.
  • the amount is less than 0.1 % by weight, the chlorine-resistance of the spandex fiber may be insufficient, and when the amount is higher than 10 % by weight, the strength, elongation and modulus of the spandex fiber deteriorate.
  • the partially dehydroxylated hydrotalcite may be added to the polyurethane at any convenient time, e.g., after mixing with an additive followed by a sand-grinding or milling process, or after a sand-grinding or milling process in the absence of an additive.
  • the partially dehydroxylated hydrotalcite may be further coated or not coated with a coating agent conventionally used in the art, which does not affect the chlorine-resistance and discoloration of the spandex yarn.
  • a coating agent conventionally used in the art, which does not affect the chlorine-resistance and discoloration of the spandex yarn.
  • the coating agent include aliphatic alcohols, fatty acids, fatty acid salts, fatty acid esters, phosphoric acid esters, styrene/maleic acid anhydride copolymers and derivatives thereof, silane-based coupling agents, titanate-based coupling agents, polyorganosiloxanes, polyorganohydrogensiloxanes and melamine-based compounds.
  • fatty acids, fatty acid salts and/or melamine-based compounds are preferred since said two formers exhibit excellent coating efficiency and the latter can minimize discoloration upon the dehydroxylation of hydrotalcite by heat-treatment.
  • the coating process for hydrotalcite may be conducted by adding a coating agent to a solvent such as water, alcohol, ether or dioxane in an amount of 0.1 to 10 % by weight based on the weight of hydrotalcite to obtain a coating agent solution, adding hydrotalcite thereto and stirring the resulting solution at an elevated temperature of 50 to 170 °C (if necessary, using a high-pressure reactor) for 10 minutes to 2 hours, followed by filtering and drying.
  • the coating process may be conducted by heat-melting a coating agent without solvent and mixing the melted coating agent with hydrotalcite in a high-speed mixer.
  • the coating process using the melamine-based compounds in water should be conducted at a temperature of 150 °C or higher under pressure, due to a high melting point of the melamine-based compound.
  • the coating process using the fatty acids or fatty acid salts in water is preferably carried out at a temperature of 100 °C or higher.
  • the coating temperature is less than 100 °C, it is difficult to achieve uniform coating and non-discoloration, and the amount of the coating agent required increases.
  • the fatty acids or fatty acid salts is used in an amount of about 3 % by weight based on the hydrotalcite in the coating process at less than 100 °C, while its amount may be reduced to 1.5 % by weight based on the hydrotalcite in the coating process at 100 °C or higher.
  • Such a reduced amount of the coating agent can reduce its discoloration during heat-treating of the hydrotalcite.
  • the fatty acids which may be used as a coating agent in the present invention are preferably selected from mono- or poly-hydroxy fatty acids having linear or branched hydrocarbon chains of 3 to 40 carbon atoms, e.g., lauric acid, carproic acid, palmitic acid and stearic acid.
  • the fatty acid salts which may be used as a coating agent in the present invention are formed from mono- or di-functional and saturated or unsaturated fatty acid having 6 to 30 carbon atoms, and a metal selected from metals of Groups I to III of Elementary Periodic Table and zinc.
  • the fatty acid salts include lithium, magnesium, calcium, aluminum or zinc salts of oleic acid, palmitic acid or stearic acid, preferably magnesium stearate, calcium stearate and aluminum stearate, more preferably magnesium stearate.
  • the melamine-based compounds which may be used as a coating agent in the present invention include melamine compounds, phosphor-containing melamine compounds and melamine cyanurate compounds, optionally substituted with an organic compound having a carboxyl group, which may be used alone or in combination.
  • melamine compounds examples include methylene dimelamine, ethylene dimelamine, trimethylene dimelamine, tetramethylene dimelamine, hexamethylene dimelamine, decamethylene dimelamine, dodecamethylene dimelamine, 1,3-cyclohexylene dimelamine, p -phenylene dimelamine, p -xylene dimelamine, diethylene trimelamine, triethylene tetramelamine, tetraethylene pentamelamine, hexaethylene heptamelamine and melamine formaldehyde.
  • Examples of phosphor-containing melamine compounds include any of the above-mentioned melamine compounds coupled with phosphoric acid or a phosphate, e.g., dimelamine pyrophosphate, melamine primary phosphate, melamine secondary phosphate, melamine polyphosphate and melamine salt of bis-(pentaerythritol phosphate) phosphoric acid, etc.
  • a phosphate e.g., dimelamine pyrophosphate, melamine primary phosphate, melamine secondary phosphate, melamine polyphosphate and melamine salt of bis-(pentaerythritol phosphate) phosphoric acid, etc.
  • melamine cyanurate compounds include melamine cyanurates substituted with at least one substituent selected from methyl, phenyl, carboxymethyl, 2-carboxyethyl, cyanomethyl and 2-cyanoethyl.
  • the above melamine-based compounds are reacted with an organic compound having a carboxyl group.
  • the organic compound having a carboxyl group include aliphatic monocarboxylic acids (e.g., 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); aliphatic dicarboxylic acids (e.g., malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebasic acid, 1,9-nonanedicarboylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid,
  • a coating agent enhances the dispersibility of the hydrotalcite in a spandex polymer solution and maintain the spinnability of the spandex.
  • hydrotalcite is not coated, it can exhibit excellent spinnability substantially equivalent to that of the coated hydrotalcite when sand-grinded or milled.
  • the sand-grinding or milling process may be conducted by milling a mixture or slurry of the hydrotalcite, a small amount of polyurethane and a solvent using a conventional bead mill.
  • the small amount of polyurethane used can enhance the dispersibility of the hydrotalcite.
  • the solvent which may be used in the sand-grinding or milling process include dimethylacetamide, dimethylformamide, dimethylsulfoxide and a mixture thereof.
  • the hydrotalcite when sand-grinded or milled to have secondary particles of an average size of about 15 ⁇ m or less, it can exhibit functions substantially equivalent to those of the hydrotalcite coated and sand-grinded or milled, during the preparation of the spandex fiber.
  • the heat-treatment for dehydroxylation of the hydrotalcite may be conducted using various types of dryers to give heat of about 200 to 390 °C, e.g., those operated in a convection, conduction, radiation, microwaves or vacuum heating process.
  • Stearic acid and hydrotalcite of formula Mg 8 Al 4 (OH) 24 (CO 3 ) 2 ⁇ 6H 2 O were successively added to water.
  • the amount of stearic acid was 2 wt% based on the weight of the hydrotalcite.
  • the resulting mixture was stirred at 150 °C for 20 minutes, filtered and dried, to obtain hydrotalcite coated with stearic acid.
  • the coated hydrotalcite was heat-treated at 250 °C for 4 hours, to obtain hydrotalcite of formula Mg 8 Al 4 (OH) 16 O 4 (CO 3 ) 2 coated with stearic acid.
  • Stearic acid, melamine polyphosphate and hydrotalcite of formula Mg 8 Al 4 (OH) 24 (CO 3 ) 2 ⁇ 6H 2 O were successively added to water.
  • 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 stirred at 160 °C for 30 minutes, filtered and dried, to obtain the hydrotalcite coated with stearic acid and melamine polyphosphate.
  • the coated hydrotalcite was heat-treated at 250 °C for 4 hours, to obtain hydrotalcite of formula Mg 8 Al 4 (OH) 16 O 4 (CO 3 ) 2 coated with stearic acid and melamine polyphosphate.
  • Hydrotalcite of formula Mg 8 Al 4 (OH) 24 (CO 3 ) 2 ⁇ 6H 2 O was heat-treated at 250 °C for 4 hours, to obtain hydrotalcite of formula Mg 8 Al 4 (OH) 16 O 4 (CO 3 ) 2 .
  • the resultant was immersed in water at room temperature for 5 hours and dried at 60 °C for 48 hours, to obtain hydrotalcite of formula Mg 8 Al 4 (OH) 16 O 4 (CO 3 ) 2 ⁇ 7H 2 O.
  • Hydrotalcite of formula Mg 9 Al 3 (OH) 24 (CO 3 ) 1.5 ⁇ 7.5H 2 O was heat-treated at 250°C for 4 hours, to obtain hydrotalcite of formula Mg 9 Al 3 (OH) 18 O 3 (CO 3 ) 1.5 .
  • the resultant was immersed in water at room temperature for 5 hours and dried at 60 °C for 48 hours, to obtain hydrotalcite of formula Mg 9 Al 3 (OH) 18 O 3 (CO 3 ) 1.5 ⁇ 8H 2 O.
  • Stearic acid and hydrotalcite of formula Mg 6 Al 2 (OH) 16 CO 3 ⁇ 5H 2 O were successively added to water.
  • the amount of stearic acid was 3 wt% based on the weight of the hydrotalcite, and the resulting mixture was stirred at 95 °C for 30 minutes, filtered and dried, to obtain hydrotalcite coated with stearic acid.
  • the coated hydrotalcite was heat-treated at 180°C for 4 hours, to obtain hydrotalcite of formula Mg 6 Al 2 (OH) 16 CO 3 coated with stearic acid.
  • Hydrotalcite of formula Mg 6 Al 2 (OH) 16 CO 3 ⁇ 5H 2 O was heat-treated at 180°C for 4 hours, to obtain hydrotalcite of formula Mg 6 Al 2 (OH) 16 CO 3 .
  • the hydrotalcite obtained was analyzed by 27 Al magic angle spinning nuclear magnetic resonance (MAS NMR) to examine the partial dehydroxylation thereof.
  • 27 Al MAS NMR analysis was performed using a 400 MHz solid state NMR spectrometer (Varian, USA) under the conditions of: Al 2 O 3 standard, 104.21 MHz transmitter frequency, 15 kHz spinning rate, scan numbers of times: 512 (hydrotalcite powder) or 8192 (hydrotalcite-contained yarn) and one pulse having 2.3 ⁇ s of pulse length.
  • the 27 Al MAS NMR result obtained can be used to determine the structure surrounding Al 3+ within the hydrotalcite.
  • the data from 27 Al MAS NMR for the initial hydrotalcite of Mg 8 Al 4 (OH) 24 (CO 3 ) 2 ⁇ 6H 2 O used in Preparation 2 shows a peak for octahedrally coordinated Al 3+ as shown in FIG. 2
  • the data for the hydrotalcite of Mg 8 Al 4 (OH) 16 O 4 (CO 3 ) 2 obtained in Preparation 2 shows peaks for both octahedrally coordinated Al 3+ and tetrahedrally coordinated Al 3+ as a result of partial dehydroxylation, as shown in FIG. 3 .
  • the hydrotalcite obtained in Preparation 2 was also analyzed by IR spectroscopy to examine the partial dehydroxylation thereof. If the hydrotalcite is partially dehydroxylated, an IR absorption spectrum shows a distinct peak at wave numbers of about 1500 to 1600 cm -1 .
  • IR analysis was performed using IFS 88 (Bruker, German) according to ATR (attenuated total reflectance) under the conditions of: 400 to 4000 cm -1 wave number area, 4cm -1 resolution and scan numbers: 16.
  • the IR absorption spectrum of the initial hydrotalcite of formula Mg 8 Al 4 (OH) 24 (CO 3 ) 2 ⁇ 6H 2 O, used in Preparation 2 shows a significant absorption peak at wave numbers of about 1300 to 1400 cm -1 as shown in FIG. 6
  • the spectrum for the hydrotalcite of formula Mg 8 Al 4 (OH) 16 O 4 (CO 3 ) 2 obtained in Preparation 2 shows significant absorption peaks at wave numbers of about 1300 to 1400 cm -1 and about 1500 to 1600 cm -1 as shown in FIG. 7 .
  • the polyurethane spinning solution was then defoamed and dry-spinned at a spinning temperature of 250 °C, to obtain a 4-filament 40-denier spandex fiber.
  • the spandex fibers obtained were measured for the following properties, and the results are shown in Table 1.
  • the spandex yarn subjected to 50% stretching was treated with water (pH 4.2, 97 to 98 °C) for 2 hours and cooled to at room temperature.
  • the spandex yarn was dipped in 45 l of chlorinated water (pH 7.5) containing 3.5 ppm of active chlorine for 24 hours, and its strength was measured with Instron 4301 (Instron Co., USA) by applying 1 kg cell to a sample piece of 5 cm long, at 300 mm/min of cross head speed, to calculate the strength preservation rate as follows:
  • Strength preservation rate % S / S 0 x 100 (wherein, S 0 is strength before treatment, and S is strength after treatment)
  • Tubular knitted fabric was prepared using a spandex alone with a tubular knitting machine (KT-400, 4 inches of diameter, 400 needles, Nagata Seiki Company, Japan), and scoured in water whose weight was 40 times as much as the weight of the fabric using a mixture of scouring agents, 2 g/L of UNITOL CT-81 (Shinyoung Chemical, Korea), 3 g/L of UNITOL-SMS (Shinyoung Chemical, Korea) and 0.5g/L of NaOH at 90 °C for 30 minutes.
  • a mixture of scouring agents 2 g/L of UNITOL CT-81 (Shinyoung Chemical, Korea), 3 g/L of UNITOL-SMS (Shinyoung Chemical, Korea) and 0.5g/L of NaOH at 90 °C for 30 minutes.
  • Stearic acid (2 wt%) Mg 8 Al 4 (OH) 16 O 4 (CO 3 ) 2 94% -1.5
  • the spandex fibers of Examples 1 to 8 contain the partially dehydroxylated hydrotalcite and thus they did not discolor during spinning at a temperature of 200 °C or higher and were also good resistant to anti-chlorine.
  • the spandex fibers containing hydrotalcites having crystallized water (Comparative Examples 2 and 3) exhibited poor resistant to both discoloration during spinning at a high temperature and chlorine.
  • spandex fibers containing hydrotalcites which is not partially dehydroxylated and the absence of crystallized water were more resistant to discoloration than those containing hydrotalcites having crystallized water, however, they were less resistant to discoloration and also to chlorine, as compared with the inventive spandex fibers.
  • the spandex yarn obtained in Example 2 was analyzed by 27 Al MAS NMR by the procedure of Experimental Example 1, and the result is shown in FIG. 4 .
  • the data for the spandex fiber of Example shows peaks for both octahedrally coordinated Al 3+ and tetrahedrally coordinated Al 3+ .
  • the spandex yarn obtained in Example 2 was evaluated for the presence of partially dehydroxylated hydrotalcite.
  • the spandex yarn of Example 2 was de-oiled by petroleum-ether treatment, the oil-free yarn was dissolved in dimethylacetamide having 100 ppm or less of moisture to a concentration of 1.3% or less, and the solution was subjected to centrifugation twice to extract hydrotalcite.
  • the exracted hydrotalcite was dried at 60 °C and analyzed by 27 Al MAS NMR according to the procedure of Experimental Example 1.
  • the hydrotalcite extracted from the spandex fiber obtained in Example 2 was also analyzed by IR spectroscopy according to the procedure of Experimental Example 2.
  • the IR absorption spectrum for the exracted hydrotalcite shows a significant absorption peak at wave numbers of about 1500 to 1600 cm -1 as shown in FIG. 8 .
  • the spandex fiber of the present invention has high resistance to both chlorine and discoloration during spinning at a temperature of 200 °C or higher, and is therefore useful for underwear, socks, and particularly, sports apparel such as swimsuit.

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  • Artificial Filaments (AREA)

Abstract

La présente invention concerne une fibre spandex contenant de l'hydrotalcite partiellement déshydroxylée en une quantité de 0,1 à 10% en poids, présentant une excellente résistance à la décoloration et au chlore ainsi que des propriétés intrinsèques de fibre spandex, et peut donc être avantageusement utilisée dans la fabrication de sous-vêtements, de chaussettes, et de vêtements de sport.

Claims (7)

  1. Fibre d'élasthanne comprenant une hydrotalcite partiellement déshydroxylée en une quantité de 0,1 à 10 % en poids,
    l'hydrotalcite partiellement déshydroxylée étant représentée par la formule (I) :

            M12-yAly(OH)24-2zOz(CO3)y/2•mH2O     (I)

    dans laquelle
    M est Mg, Ca ou Zn,
    y est une valeur située dans la plage 2,4 ≤ y ≤ 4,
    z est une valeur située dans la plage 0 < z ≤ 8, et
    m vaut zéro ou est un nombre positif.
  2. Fibre d'élasthanne selon la revendication 1, l'hydrotalcite partiellement déshydroxylée étant choisie dans l'ensemble constitué par les composés de Mg8Al4(OH)16O4(CO3)2, Mg8Al4(OH)8O8(CO3)2, Mg9Al3(OH)18O3(CO3)1,5, Mg9Al3(OH)12O6(CO3)1,5, Mg9,6Al2,4(OH)19,2O2,4(CO3)1,2, Mg9,6Al2,4(OH)14,4O4,8(CO3)1,2, Mg8Al4(OH)16O4(CO3)2•6H2O, Mg8Al4(OH)8O8(CO3)2•7H2O, Mg9Al3(OH)18O3(CO3)1,5•7,5H2O, Mg9Al3(OH)12O6(CO3)1,5•8H2O et leurs mélanges.
  3. Fibre d'élasthanne selon la revendication 1 ou 2, l'hydrotalcite partiellement déshydroxylée étant préparée par traitement à la chaleur d'une hydrotalcite ayant de l'eau cristallisée à une température située dans la plage allant de 200 à 390°C.
  4. Fibre d'élasthanne selon la revendication 3, dans laquelle l'hydrotalcite partiellement déshydroxylée est préparée par traitement thermique d'une hydrotalcite ayant de l'eau cristallisée à une température située dans la plage allant de 250 à 300°C.
  5. Fibre d'élasthanne selon la revendication 1 ou 2, dont le spectre de résonance magnétique nucléaire par rotation à l'angle magique du 27Al (RMN RAM) montre des pics tant pour Al3+ coordonné de manière octaédrique que pour Al3+ coordonné de manière tétraédrique.
  6. Fibre d'élasthanne selon la revendication 1 ou 2, dont le spectre d'absorption des infrarouges (IR) montre des pics d'absorption significatifs aux nombres d'onde de 1300 à 1400 cm-1 et de 1500 à 1600 cm-1.
  7. Fibre d'élasthanne selon la revendication 1 ou 2, dans laquelle l'hydrotalcite partiellement déshydroxylée a des particules secondaires ayant une taille moyenne de 15 µm ou moins.
EP07708702A 2006-05-09 2007-02-01 Fibres spandex contenant de l'hydrotalcite partiellement déshydroxylée Active EP2021537B1 (fr)

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KR1020060041407A KR100762548B1 (ko) 2006-05-09 2006-05-09 부분적으로 탈수산화된 하이드로탈사이트를 함유하는스판덱스 섬유
PCT/KR2007/000551 WO2007129807A1 (fr) 2006-05-09 2007-02-01 Fibres spandex contenant de l'hydrotalcite partiellement déshydroxylée

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KR101007888B1 (ko) * 2006-12-07 2011-01-14 주식회사 두본 산화물 형태의 하이드로탈사이트 및 그의 제조방법
KR100870533B1 (ko) 2007-06-28 2008-11-26 주식회사 효성 열처리된 헌타이트-하이드로마그네사이트 혼합 광물을함유하는 스판덱스 섬유
KR101130282B1 (ko) * 2009-10-26 2012-03-26 이화여자대학교 산학협력단 층상형 금속 이중층 수산화물 변이체 세피오사이트 화합물 및 그의 제조방법
KR101054809B1 (ko) 2010-12-22 2011-08-05 (주)세창 하이드로탈사이트를 포함하는 합성섬유 조성물
KR101186818B1 (ko) 2012-02-17 2012-09-28 (주)우진고분자 표면처리된 히드로탈사이트 및 이를 포함하는 조성물
KR102412143B1 (ko) 2022-01-17 2022-06-22 ㈜쿨베어스 극피동물 유래 다공성 물질을 포함하는 항염소 스판덱스 및 그 제조방법

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CN1089821C (zh) * 1997-02-13 2002-08-28 旭化成株式会社 弹性聚氨基甲酸乙酯纤维及其生产方法
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JP2000290836A (ja) * 1999-04-05 2000-10-17 Asahi Chem Ind Co Ltd ポリウレタンウレア弾性繊維
JP3922680B2 (ja) * 2000-10-11 2007-05-30 株式会社海水化学研究所 塩素系殺菌剤の中和剤およびその製造方法
ITMI20011144A1 (it) * 2001-05-30 2002-12-02 Fillattice S P A Composizione di fibra elastica in grado di resistere alle acque contenenti cloro
KR100438005B1 (ko) 2002-04-04 2004-06-30 주식회사 두본 내염소성 폴리우레탄 탄성사의 제조방법 및 그 탄성사
KR100437988B1 (ko) 2002-04-29 2004-06-30 주식회사 두본 내염소성 및 내열성이 우수한 스판덱스 섬유 및 그제조방법
KR100548645B1 (ko) * 2004-07-14 2006-02-02 주식회사 효성 내변색성 및 내염소성 스판덱스 섬유 및 그 제조방법
KR100575374B1 (ko) 2004-10-22 2006-05-02 주식회사 효성 내염소성 및 정전기 방지 특성이 우수한 폴리우레탄 탄성섬유 및 그 제조방법

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KR20060066689A (ko) 2006-06-16
JP2009536274A (ja) 2009-10-08
TW200742777A (en) 2007-11-16
BRPI0711341A2 (pt) 2011-08-30
WO2007129807A1 (fr) 2007-11-15
JP4728425B2 (ja) 2011-07-20
EP2021537A1 (fr) 2009-02-11
KR100762548B1 (ko) 2007-10-04
EP2021537A4 (fr) 2009-12-09
BRPI0711341B1 (pt) 2017-08-01
CN101528993B (zh) 2011-07-13
CN101528993A (zh) 2009-09-09
TWI322838B (en) 2010-04-01

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