TWI276719B - A polyurethane elastic fiber having chlorine-resistance antistatic property and a method for producing the same - Google Patents

Abstract

The present invention relates to a polyurethane elastic fiber having excellent chlorine-resistance and antistatic property without affecting the original physical properties of polyurethane-polymers, and a method for producing the same. According to the present invention, the polyurethane-elastic fiber may have excellent chlorine-resistance and antistatic property by means of containing hydrotalcite coated with aliphatic alcohol.

Description

1276719 IX. Description of the Invention: [Technical Field of the Invention] [1] The present invention relates to a method for producing a P〇lyurethane elastic fiber having high chlorine resistance and high antistatic property, and the present invention It also relates to a method for producing a polyurethane elastic fiber produced by adding aliPhatic alcohol, which is high in chlorine resistance and high in antistatic property. [Prior Art] [2] Polyurethane elastic fibers generally have rubber-like high elastic properties and superior physical properties such as high tensile strength and restoring force, and thus have been used in underwear, socks, and sporting goods. However, if the polyurethane elastic fiber containing polyurethane as a main component is washed with a lotion such as bleach, sodium chloride or the like, the physical properties of the polyurethane may be severe. Degraded, the same, polyurethane and other synthetic fibers, such as polyamide and polyester woven swimsuit after contact with chlorine-containing water (active chlorine concentration of 0.5 to 3.5 ppm) The physical properties of polyazali elastic fibers are also degraded. [3] In order to solve the problem of quality degradation caused by chlorine, many research results have been devoted to the development of compounds containing high chlorine resistance, for example, the oxidation of U.S. Patent No. 4,340,527, and the carborite of U.S. Patent No. US 5,626,960 ( Huntite) and hydromagnesite mixture, calcium carbonate and barium 1276719 carbonate of Korean Patent No. 92-3250, magnesium oxide/zinc oxide (MgO/ZnO of Japanese Patent No. JPH6-81215) Solid, Japanese patent number jp S 59-133248, magnesium oxide, magnesium hydroxide or hydrotalcite, US Patent No. US 5,447,969, coated with stearic acid and its crystal water Hydrotalcite, U.S. Patent No. 5,969,028, which is a polyorganosiloxane compound coated with hydrotalcite, is used to prepare chlorine-resistant agents. [4] In general, magnesium aluminum carbonate compounds can effectively reduce the destructive properties of chlorine by capturing the characteristics of halogen compounds. U.S. Patent No. 5,447,96 is a magnesium aluminum carbonate coated with stearic acid and its crystal water. (hydrotalcite) and the hydrotalcite of the polyorganosiloxane compound in US Patent No. US 5,969,028 are used to avoid moisture absorption and enhance the distribution characteristics to improve the spinning. There is some degree of discharge pressure rise and wire breakage in the wire process, but the other non-gas resistance properties of the polyurethane elastic fiber cannot be improved. [5] Because the polyurethane elastic fiber has good adhesive properties, the electrostatic force generated by the polyurethane elastic fiber in the post-process stage (such as cylinder knitting, weaving) will entangle a large amount of polyurethane. Elastic fiber knitted fabric. The present inventors have found this problem and conducted research to try to improve the problem caused by this electrostatic force, and as a result, it has been confirmed that a polyurethane elastic fiber made of a hydroalcite which is covered with an aliphatic alcohol is used. It will be able to effectively improve the shortcomings of the electrostatic force caused by the conventional aluminum magnesium carbonate. 1276719 [6] The dispersion characteristics of hydrotalcite are well known in the art. The present invention relates to the addition of an aliphatic alcohol-coated hydrotalcite to a polyurethane polymer. Has excellent antistatic properties. [7] The present invention mainly relates to a method for producing a south gas-resistant and south antistatic polyurethane elastic fiber prepared by adding aluminum carbonate (hydrumtaleite) coated with an aliphatic alcohol . • [Description of the Invention] [8] Therefore, the main object of the present invention is to provide a method of polyurethane elastic fiber having excellent chlorine resistance and antistatic force without affecting the polyurethane polymer Some physical characteristics. [9] For this reason, the present invention mainly achieves the above objects and effects by the following technical means, and the present invention mainly relates to: 0. 1% to 1 which must contain the total weight of the polyurethane elastic fiber. 〇% of the fatty alcohol is coated with magnesium aluminum carbonate. [10] Thereby, the polyurethane elastic fiber is coated with aluminum carbonate by using a fatty alcohol, and has excellent chlorine resistance and antistatic force. [11] Next, a preferred embodiment will be further described, and the purpose and effect of the present invention will be further explained, so that the reviewing committee can have a more detailed understanding of the present invention and enable those skilled in the art to implement the following. The above description is only for the purpose of explaining the preferred embodiments, and is not intended to limit the scope of the present invention, and any changes or modifications of the present invention based on the spirit of the present invention will still belong to the present invention. The intention of protection _. [Embodiment] [12] In order to achieve the above object, the polyurethane elastic fiber may contain a fatty alcohol (aliphatic alc〇h〇1) and a hydrotalcite. [13] The added weight of magnesium sulphate (# (10) Shanru) is 10% 聚·1~1〇% of the polyaminan. [14] The weight percentage of aliphatic alcohol covered by hydrating talcite is 0·1 ～20〇/〇〇 of aluminum magnesium carbonate. [15] The molecular formula of magnesium aluminum carbonate is represented by (1) : M2+xA12 ( OH) y ( An-) z 0k-mH20 ( 1 ) M2+ represents magnesium ion (Mg2+), calcium ion (Ca2+) or reciprocal ion (Zn2+), and An- represents any An η-valent anion, X and y represent a number of 2 ® or more, Z represents a number of 3 or less, k represents 0 or any number equal to or less than 3, m represents 〇 or any positive number, and then An- represents OH_, F-, Cl-, Br·, N03_, S042-, CH3COO-, HP042-, 'oxalate ion, salicylate ion (saiiCyiate i〇n), silicate ion one of them. [16] Magnesium aluminum carbonate select at least one of the compounds (2) to (13) listed below: (2)

Mg4.5A12 (OH) 13C03-3.5H20 1276719

Mg6A12 (OH) 16C03 -5H20 ...- (3) Mg8A12 (OH) 20CO3 -6H20 ...- (4) Mg4A12 (OH) 12C03 -3H20 ---- (5) Mg4.5A12 ( OH) 13C03 -... (6) Mg6A12 ( OH) 16C03 ...- (7) Mg8A12 ( OH) 20CO3 - (8) Mg4A12 ( OH) 12C03 ... - (9) Mg4.5A12 (OH) 13 ( C03 ) 0.6 00.4 ...- (10) Mg6A12 (OH) 16 ( C03 ) 0.7 00.3 ...- (11) Mg4.5A12 (OH) 12.2 ( C03 ) 0.8 00.6 ...- (12) Mg4A12 ( OH) 12 ( C03 ) 0.6 00.4 ...- (13) (6) to (9) The molecular formula represents anhydrous aluminum magnesium carbonate, and the molecular formulas of (10) to (13) represent aluminum acid-destroying towns which have no crystal water and no C032- and OH-. [17] The fatty alcohol may comprise a monovalent or multivalent fatty alcohol or a linear or branched aliphatic alcohol containing from 3 to 40 carbons. The fatty alcohol compound may be selected from one or two of the following fatty alcohol compounds, including alkanol, cycloalkanol, n-hexanol, n-heptanol, n-octanol. ), 2-ethylhexanol, isooctyl alcohol, 2-octanol-2, methyl heptanol, decyl alcohol, isodecyl alcohol 1276719 (isodecyl alcohol), 2-capryl alcohol, lauryl alcohol, myristyl alcohol, palmitol alcohol, oleyl alcohol, benhenyl alcohol, Cetyl alcohol, stearyl alcohol, cyclohanxol, alkandiol, propylene glycol, trimethylene glycol, 1, 1,2-butylene glycol, 2,3-butylene glycol, 1,4-butylene glycol, 1,6_hex Glycol (1,6-haxanediol), pinacol, 1,2-pentanediol, 2 · 2-methyl-2,4-pentanediol, 1,3-butylene glycol, neopentyl glycol, 2- Ethyl-1,3-hexanediol (2-ethyM, 3-haxanediol), 2,4-pentanediol (2,4-pentanediol), 2,4·heptanediol (2,4_heptanediol), 2, 2,_Diethyl-1,3-propanediol (2.2-diethyl_l, 3_propanediol), 2-methyl-2-ethyl-1-butyl-l, 3-propanediol, 2-mercapto 2-methyl-2-butyM (3_propanediol), pentaerythritol, dipentaerythritol. The fatty alcohol compound may preferably be selected from the next to two compounds, including stearyl alcohol, lauryl alcohol, pentaerythritol, and dipentaerythritol. The method of coating the fatty alcohol compound may be carried out in water or a solvent, or a dry method may be used. 0 1276719 [18] The coating method of water or solvent may be carried out by dissolving aluminum magnesium carbonate in water or a solvent, and adding 0.1 to 20% by weight of the fatty alcohol to the solution, and heating and stirring to the melting point temperature of the fatty alcohol mixture, heating and stirring for 30 minutes, cooling the solution to room temperature for filtration, and then sloping the filtrate with electromagnetic waves. Aluminium magnesium carbonate surface. On the other hand, the dry type method can be carried out by placing 1·1 to 20% by weight of a fatty alcohol and magnesium aluminum carbonate together in a high-speed mixer, followed by heating and stirring to a melting point temperature of the fatty alcohol mixture. [20] In addition, if only aluminum magnesium carbonate is placed in a blender, the pre-formed fatty alcohol can be coated on the surface of the magnesium carbonate by electromagnetic waves. The electromagnetic waves that can be used include ultraviolet-visible rays (gamma). - gamma-rays, X-rays, microwaves, infrared rays, preferably microwave or infrared. Φ [21] If the fatty alcohol is not covered by electromagnetic waves, such as ultraviolet-visible rays, gamma-rays, X-rays, microwaves or Infrared rays cause problems in coating efficiency and poor polymer dispersion. The present invention finds that the electromagnetic wave coating method can improve the efficiency, and the method uses the method to add a fatty alcohol to the magnesium carbonate (hydrotalcite). ), and a polyurethane elastic fiber having high chlorine resistance and high antistatic property is obtained. 11 1276719 [22] The aluminum gallium malate coated with the fatty alcohol may have a particle size smaller than ι 〇 m, preferably less than 5 m. [23] The content of aluminum magnesium sulphate in the polyurethane elastic fiber coated with fatty alcohol is preferably 0.1% to 1% by weight of the total weight of the fiber, and if the content is less than 〇·1%, the polyurethane elastic fiber The chlorine resistance and antistatic property are too weak to be applied to industrial materials. However, if the content is higher than 丨〇%, even if the chlorine resistance and antistatic property of the fiber are improved, the fiber still contains an excessive amount of inorganic substances. Will result in a decrease in strength, ductility and modulus. [24] Aluminium magnesium carbonate coated with a fatty alcohol can be added in any process for producing polyurethane elastic fibers. For example, aluminum magnesium carbonate coated with a fatty alcohol can be added to a solution containing any additive or dispersion. It can also be added to a solution containing a polymer. [25] Polyurethane polymer used in the polyurethane elastic fiber of the present invention is well known in the art. According to the preparation method of polyurethane, organic diisocyanate is first used. The salt (diisocyanate) reacts with the polymer diol to obtain a precursor, and the precursor is dissolved in an organic solvent and reacted with a diamine or a/amine to obtain a poly(urethane) polymer. [26] The organic diisocyanate (〇rganic diisocyanate) of the present invention may comprise diphenylmethane-4,4'-diisocyanate or hexamethylenediamine. Isocyanate (hexamethylene isocyanate), toluene diisocyanate, butyl diisocyanate, p-methyl diisocyanate, and the like. The polymer diol 12 1276719 (Polymer diol ) may contain polytetramethylene ether glycol, polypropylene glycol, polycarbonate diol, and the like. [27] Monoamines as a chain terminator may include diethyl amine, mono-ethanol amine, dimethyl amine, and the like. • [28] The present invention relates to a compound which is necessary to prevent fading and deterioration of polyurethane elastic fibers caused by UV light, smoke, and heat treatment, and includes a phenol compound and a benzofuranone. , semi-carbazide, benzotriazol compound, amine compound, polymeric tertiary amine stabilizers (eg, polyurethane with tertiary nitrogen atom) Polyurethane and polydialkylaminoalkyl methacylate, and the like. The polyurethane elastic fiber according to the present invention may further contain additives such as titanium dioxide and magnesium stearate and the like. Depending on the color of the polyurethane elastic fiber, the titanium dioxide added to the polyurethane elastic fiber accounts for 0.1% to 5% by weight of the polyurethane elastic fiber, depending on the improved polyurethane elastic fiber unwinding. The characteristic is that magnesium stearate added to the polyurethane elastic fiber accounts for 0.1% to 2% by weight of the polyurethane elastic fiber. 13 1276719 [30] It is to be understood that the general description and details of the present invention are merely illustrative, and the claimed claims &lt;Gas resistance test&gt; [31] Test for strength retention in gas water: 50% stretch of polyurethane elastic fiber was treated with water (pH 4.2, 97 °C to 98 °C) for 2 hours at room temperature After cooling, the polyurethane elastic fiber was immersed in 45 liters of 3.5 ppm chlorine-containing chlorine water (pH 7.5) for 24 hours, and the strength retention rate of the polyurethane elastic fiber was analyzed by the following formula. * Strength retention rate (%) = S/SO X 100 SO: strength before treatment, S: strength after treatment [32] by Instron 4301 (Instron Co., USA ) Measurement intensity, sample length 5 cm, cross head rate 300 mm/min (1 kg cell) 〇 &lt;electrostatic force test&gt; [33] The cylindrical shaft for testing electrostatic force should be maintained at 20 ° C and 42 In the humidity environment for 24 hours, the test must be carried out in the same state as above. 1276719 [34] The electrostatic force test is carried out according to the method of r〇iHng, which is to fix the cylindrical bobbin to the creel, and unwind the unwinding roller with the connecting bobbin, and the unwinding rate is 150 m/min. The speed of the shaft is 200 m/min. 'The diameter of the take-up roller is the same as that of the unwinding roller. The distance between the two rollers is 1 meter away from the ground. [31] Place a steel bar on the take-up reel and the unwinding roll. Between the vehicles for the passage of the thick wire, the position of the electrostatic force is measured between the steel bar and the unwinding roller. The measurement is started 2 minutes after the unwinding, and the static electricity is measured by KSD_〇l〇3 (KASUGALTD·, Japan) instrument. force. <Preparation method of polyurethane polymer> [36] A method for preparing a polyisocyanate polymer having a diisocyanate functional group at both ends is as follows: 518 g of diphenylmethane 4,4'-diisocyanate (diphenylmethane_4,4_diisocyanate) and 2328 g of polytetramethyl ether glycol (molecular weight 1800), heated at 80 ° C under nitrogen for a reaction for 90 minutes to obtain a polyurethane prepolymer, which will be polymerized. The urethane prepolymer was cooled to room temperature, and then 4269 g of dimethylacetamide was added to obtain a polyurethane prepolymer solution containing 34.4 g of ethylene diamine and 10.6 g. A mixed solution of propylene diamine, 9.1 g of diethyl diamine, dinonylacetamide (1117 g), added to a solution containing a polyurethane prepolymer Polyurethaneurea solution. Based on the total weight of the polyurethane solution, 1.5% ethylene bis ( oxyethylene ) bis- 15 1276719 (3- ( 5_t-butyl_4_hydoroxy-m-toil) -propionate), 0.5 〇 / 〇 5,7-di-t-butyl-3_ (3,4-dimethyl phenyl ) -3H-benzofuran-2-one , 1% 1,1,Γ,Γ -tetramethyl_4_4' - (methylene-di-p-phenylene Addition of disemicarbazide, 1% poly(N, N_diethyl-2_aminoethyl methacrylate), 0.1% titanium dioxide (titanium dioxide) to the polyurethaneurea solution to prepare a polyurethane-urea solution for spinning applications. . [37] Prior to the addition of the additive, the Advantis V3 instrument manufactured by Drais Mannheim, Germany, was used to uniformly disperse the additive in the dimethylacetamide solvent and then added to the polymer solution. Examples 1-5 and Comparative Examples 1-4 [3 8] Adding the magnesium sulphate (example 1_5 and comparison 1-4) shown in Tables 1 and 2 to the polyurethane urea solution and mixing 'preparation for spinning use Polyurethane-urea solution. [39] After the defoaming of the polyurethane urea solution, the solution was prepared into a 40D/3f polyacetal urea (urea) elastic fiber by a dry spinning machine, and the temperature of the upper half of the body was controlled at 250 ° C. 3.5% of the finish oil TNU-604 (Sanyo Cooperate,

JaPan) is wound into a roll after processing.

16 1276719

[40] The physical properties of the obtained fibers are shown in Tables 1 and 2. Table 1

Ex.l Ex.2 Ex.3 Ex.4 Ex.5 Co.; Stearyl; Pentaerythritol; Lauryl; Caprylalcohol; Oleil; Am. 3 wt% 3 wt% 3 wt% 3 wt% 3 wt% For.; Mg4Al2( OH)i2 Mg4Al2(OH)i2 Mg4Al2(OH)12 Mg4Al2(OH)12 Mg4Al2(OH)12 Am. C03 *3H20; C03 ·3Η20; C03 ·3Η20; C03; (C03)〇.80〇.2; 4 Wt% 4 wt% 4 wt% 4 wt% 4 wt% SPR 88% 89% 87% 95% 86% SE 0.2 0.2 0.3 0.2 0.1 Note:

Co and Am: respectively represent the weight of the covering material and the coating percentage, and the covering material indicates the fatty alcohol, and the percentage by weight of the coating is based on the total weight of the magnesium aluminum carbonate.

For and Am: respectively represent the molecular weight formula of magnesium aluminum carbonate and the percentage by weight of aluminum magnesium carbonate, and the weight % of aluminum magnesium carbonate is based on the total weight of the fiber. S.P.R: indicates the percentage retention of the strength retention rate after 24 hours of gas water treatment.

17 1276719 S.E : indicates the electrostatic force value (unit: kV) Table 2

Com.l Com.2 Com.3 Com.4 Co·; Stearic acid Parmitic acid; No hydrotalcite No hydrotalcite Am. 3 wt% 3 wt% For.; Mg45Al2(OH)13 Mg6Al2(OH)i6 Mg4Al2(OH)12 Mg4Al2(OH)12 Am. C〇3*3.5H20; C03 *5H20; C03; (C03)〇.5 O〇.5; 4 wt% 4 wt% 4 wt% 4 wt% SPR 85% 83% 80% 72% SE 0.5 0.6 0.5 0.7 Notes:

Co and Am: respectively represent the percentage of the weight of the covering material and the coating, and the material of the coating indicates the fatty alcohol, and the percentage by weight of the coating is based on the total weight of the magnesium aluminum carbonate.

For and Am: respectively represent the molecular weight formula of magnesium aluminum carbonate and the percentage by weight of aluminum magnesium carbonate, and the weight % of aluminum magnesium carbonate is based on the total weight of the fiber. S.P.R: represents the percentage of strength retention after 24 hours of chlorine water treatment. 18 Ϊ276719 SE : indicates electrostatic force value (unit: kv) [41] As shown in Tables 1 and 2, the spinning produced according to Comparative Examples 3 and 4 is most often broken, and its physical properties are also better than those of other examples. The situation is poor.

[42] As shown in Tables 1 and 2, in the present invention, the polyurethane elastic fibers produced by coating the aluminum magnesium carbonate with a fatty alcohol have better chlorine resistance and have a strength retention rate of at least It is 86% or more of the other Comparative Examples 1 to 4, and the polyurethane elastic fibers of Examples} to 5 also have preferable antistatic force properties. [43] As shown in the above-mentioned details, in the technical position of manufacturing polyurethane elastic dimension, Benfa County has the advantage of superior (four) carbon-based superior dispersibility technology in polyester, in addition to this, Adding fatty alcohol-coated magnesium aluminum carbonate to polyurethane high score ': Polyurethane elastic fiber, imparting high antistatic property to the fiber [44] via the above system, by utilizing the present invention The creation of 'effectively solves the problem of ^, and advances the effect, so the invention fully complies with the provisions of the Patent Law. 2 The invention patent application is submitted to the Approved Review Committee.

Claims (1)

1276719 X. Patent application scope: 1. A polyurethane elastic fiber with excellent gas resistance and antistatic property, which must contain 0.1% to 10% of the total weight of polyurethane elastic fiber. Aluminium magnesium carbonate. 2. The polyurethane elastic fiber according to claim 1, wherein the fatty alcohol compound must contain at least a linear or branched monovalent or multivalent fatty alcohol having 3 to 40 carbons. 3. The polyurethane elastic fiber according to claim 1, wherein the fatty alcohol compound preferably comprises stearyl alcohol, lauryl alcohol, pentaerythritol, and Dipentaerythritol. 4. The polyurethane elastic fiber according to claim 1, wherein the molecular formula of the aluminum magnesium carbonate is represented by (1): M2+XA12(OH) y (An-) z Ok · mH20 ..... (1) M2+ represents magnesium ion (Mg2+), calcium ion (Ca2+) or zinc ion (Zn2+), An- represents any anion having n valence, X and y represent a number of 2 or more, and Ζ represents 3 or 3. The following numbers, k represents 0 or any number equal to or less than 3, m represents 0 or any positive number, and then An_ represents 〇H_, F-, Cl_, Br_, N03-, S042-, CH3COO-, HP042-, One of oxalate ion, salicylate ion, and silicate ion. 20 1276719 5. The polyurethane elastic fiber according to claim 1, wherein at least one of the following compounds (2) to (13) is selected: Mg4.5A12 (OH) 13C03-3.5H20 ...-(2) Mg6A12( OH) 16C03 -5H20 ---- (3 ) Mg8 A12 ( OH ) 20CO3 · 6H20 (4) Mg4A12( OH)12C03 -3H20 ...-( 5) Mg4.5A12( OH) 13C03 ...- (6) Mg6A12( OH)16C03 ...-(7) Mg8A12(OH)20CO3 ...- (8) Mg4A12 ( OH) 12C03 ...- (9) Mg4.5A12( OH) 13 (C03 ) 0.6 00.4 ... (10) Mg6A12(OH)16 (C03)0.7 00.3 ...· (11) Mg4.5A12( OH)12.2 (C03)0.8 00.6 ...· ( 12) Mg4A12( OH) 12 ( C03 0.6 00.4 (13) The molecular formulae of (6) to (9) represent anhydrous aluminum magnesium carbonate, and the molecular formulas of (10) to (13) represent crystal water without crystals and no C032- and OH-. 6. A method for producing an aluminum-containing magnesium carbonate polyurethane elastic fiber, comprising the steps of: 21 1276719 (A) preparing a polyurethane prepreg by reacting diisocyanate with a polymeric glycol Polymer. (B) Dissolving the polyurethane prepolymer in an organic solvent and reacting with a diamine or a monoamine. (C) Aluminium magnesium carbonate coated with a fatty alcohol is added together with an additive or separately to a polyurethane solution to prepare a polyurethane solution for spinning. 7. The method for producing an aluminum-containing magnesium carbonate polyurethane elastic fiber according to claim 6, wherein the method for covering the aliphatic alcohol with aluminum magnesium carbonate comprises ultraviolet-visible rays, gamma-rays ( Gamma-rays ), X-X-rays, microwaves or infrared rays. twenty two