TWI238206B - Polyurethane elastic fiber and preparation thereof, cloth and swimming suit - Google Patents

Abstract

The present invention is related to polyurethane elastic fiber which is characterized by consisting from polyurethane urea and polyurethane and preparation thereof. The polyurethane elastic fiber of present invention can be used for the usage of swimming suit by way of such excellent anti-chlorine brittle function and thermoset property.

Description

1238206 V. Description of the invention (1) [Detailed description of the invention] [Technical field to which the invention belongs] The present invention relates to a polyurethane elastic fiber, a method for manufacturing the same, a cloth, and a swimsuit. More specifically, it is a polyurethane elastic fiber having excellent chlorine resistance suitable for swimwear used in swimming pools and the like. [Previous Technology] Polyurethane elastic fibers are widely used in stockings, underwear, and sportswear because they have high rubber elasticity and excellent mechanical and thermal properties such as tensile stress and recoverability. However, if a clothing product using polyurethane elastic fibers is repeatedly immersed in a chlorine bleach and washed for a long time, there is a problem that the elastic function of the polyurethane elastic fibers is reduced. That is, if a swimwear using polyurethane elastic fibers is repeatedly impregnated with chlorine-containing sterilizing chlorine water having an active chlorine concentration of 0. 5 to 3 ppm, the elastic function of polyurethane elastic fibers will be significantly impaired. And disconnection occurs. In order to improve the chlorine resistance of polyurethane elastic fibers, polyester-based polyurethane elastic fibers using aliphatic polyester diols as raw materials have been disclosed, but their chlorine resistance is insufficient. In addition, because aliphatic polyesters are highly bioactive, polyester-based polyurethane elastic fibers have the disadvantage of being easily invaded by mold. The elasticity of swimwear during use or storage is reduced, and problems such as disconnection are easy to occur. Polyether urethane elastic fibers using polyether diols with very little biological activity as raw materials Although there is less concern about mold caused by mold 1238206 V. Description of the invention (2) Embrittlement, but it has chlorine resistance than polyester The problem is that the polyurethane elastic fiber is worse. In addition, since the polyether polyurethane elastic fiber lacks thermosetting properties, the heat fixation of the fiber cloth and thread containing the polyurethane elastic fiber is a problem. That is, since polyurethane elastic fibers have low thermosetting efficiency, a thread made of polyurethane elastic fibers must be heat-fixed for a long time and at a high temperature. In a fiber cloth containing nylon fibers and polyurethane elastic fibers, if the heat-fixing temperature is high, there is a problem that causes fiber unevenness. This type of thread has low breaking strength, and it is difficult to weave the thread into a fiber cloth. When wearing a clothing product made of such a thread, the clothing product may be damaged. Such concerns are particularly significant when using polyurethane elastic fibers with small deniers such as women's socks and swimwear. [Problems to be Solved by the Invention] An object of the present invention is to provide polyurethane elastic fibers and stabilizers suitable for swimwear applications having excellent chlorine resistance and thermosetting characteristics in view of such prior art problems. Method for manufacturing this polyurethane elastic fiber. [Means for solving problems] In order to solve the aforementioned problems, the present invention adopts the following solving means. That is, a polyurethane elastic fiber characterized by being formed of polyurethane urea and polyurethane. 1238206 V. Description of the invention (3) In addition, in order to understand and solve the aforementioned problems, the method for producing the polyurethane elastic fiber of the present invention adopts the following solutions. That is, a polyurethane elastic fiber characterized by using polyurethane urea and polyurethane as a solute solution and spinning them is characterized. [Embodiments of the Invention] Hereinafter, the present invention will be described in detail. The polyurethane elastic fiber of the present invention is formed of polyurethane urea and polyurethane. In the present invention, the polyurethane urea is preferably composed mainly of a polyol, a diisocyanate, and a diamine. Polyurethane urea is preferably a polyether diol, a polyester diol, a polycarbonate diol, or the like. When the polyurethane elastic fiber of the present invention is used particularly in swimwear, from the viewpoint of preventing embrittlement caused by mildew, for example, polyhydric alcohols include polyethylene glycol, polypropylene glycol, and polybutylene glycol (hereinafter, Briefly referred to as PTMG), modified PTMG (hereinafter, briefly referred to as 3M-PTMG) copolymer of THF and 3-MeTHF, modified PTMG, snow and copolymer of THF and 2,3-dimethylbutane ^ Polyether glycols such as polyhydric alcohols having side chains on both sides as disclosed in Japanese Patent Publication No. 2615131 and the like are preferred. These polyhydric alcohol diols can also be used by mixing one or more kinds or copolymerizing them. In addition, when the abrasion resistance and light resistance of polyurethane elastic fibers are particularly required, butadiene adipate, polybutyrolactone diol, JP 1238206 V. Description of the invention (4) 6 1- Polyester diols such as polyester polyols having side chains disclosed in 266 1 and the like, and polycarbonate diols disclosed in JP 2-2 8 9 5 16 and the like are preferable. . Such a polyhydric alcohol may be used alone, or two or more kinds may be mixed or copolymerized. From the viewpoint of obtaining polyurethane elastic fibers having excellent elongation, strength, elastic restoring force, and heat resistance, the number average molecular weight of the polyol used in the polyurethane urea of the present invention is 1,000 to 8,000. The range is preferably, and a range of 1800 to 6000 is more preferable. Secondly, the diisocyanates used in the polyurethane urea of the present invention are aromatic diisocyanates, aliphatic diisocyanates, cycloaliphatic diisocyanates, aromatic aliphatic diisocyanates, and modified bodies of their diisocyanates (carbodiimide Amine modifiers, urethane modifiers, uretdione modifiers, etc.) and mixtures of two or more of these are preferred. Specific examples of the aforementioned aromatic diisocyanate include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolyl diisocyanate, and 2,6-tolyl diisocyanate. Isocyanate, 2,4-diphenylmethane diisocyanate, 4,4, -diphenylmethane diisocyanate (hereinafter, abbreviated as MDI), 4,4'-diisocyanate biphenyl, 3,3: di Methyl-4,4'-monoisochlorobiphenyl, 3,3, -dimethyl-4,4, -diisocyanatobiphenylmethane, 1,5-naphthyl diisocyanate, 1, 4-Diisocyanate benzene, xylylene monoisocyanate, 2,6-naphthyl diisocyanate and the like are preferred. Specific examples of the aforementioned aliphatic diisocyanate include ethylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, and twelve diisocyanate 1238206. 5. Description of the invention (5) Ester , 2,2,4-trimethyldiisocyanate adipate, lysine diisocyanate, 2,6-diisocyanatomethyloctanoate, bis (2-isocyanatoethyl) carbonate And 2-isocyanatoethyl-2,6-diisocyanatohexanoate are preferred. Specific examples of the alicyclic diisocyanate include dicyclohexylmethane_4,4 · -diisocyanate, cyclohexyl diisocyanate, methylcyclohexyl diisocyanate, and bis (2-isocyanatoethyl) -4- Cyclohexyl-1,2-dicarboxylic acid ester, 2,5-orthobornane diisocyanate, 2,6-orthobornane diisocyanate, methylene bis (cyclohexyl isocyanate) (hereinafter referred to as H12MDI), Methylcyclohexane 2,4-diisocyanate, methylcyclohexane 2,6-diisocyanate, cyclohexane 1,4-diisocyanate, hexahydroxylene diisocyanate, hexahydroxylene diisocyanate, octahydro丨, 5-naphthalene diisocyanate and the like are preferred. Specific examples of the aromatic aliphatic diisocyanate include m-xylene diisocyanate, p-xylene diisocyanate, α, α, α ', α tetramethylxylene diisocyanate, and the like. Among them, in terms of improving the strength of the final product and obtaining excellent heat resistance and strength, aromatic diisocyanate is preferred, and MDI is particularly preferred. From the viewpoint of suppressing yellowing of the polyurethane line, an aliphatic diisocyanate is preferred. These diisocyanates may be used alone or in combination of two or more. The chain extender used in the polyurethane urea of the present invention is preferably a low molecular weight diamine or the like. Low molecular weight diamines are, for example, ethylenediamine, 1,2-propane 1238206 5. Explanation of the invention (6) Diamine, 1,3-propanediamine, hexamethylenediamine, 1,3-cyclohexyldiamine, hexahydrogen Phenylenediamine, 2-methylpentanediamine, bis (4-aminophenyl) phosphine oxide, etc. are preferred. In particular, ethylene diamine is preferred from the viewpoint of obtaining a material having excellent elongation, elastic restorability, and heat resistance. Alas, the chain extender is also preferably a substance having a warp group and an amine group in a molecule like ethanolamine. Triamine compounds that can form a cross-linked structure in this chain extender, such as diethylene triamine, are preferably used to the extent that the effect is not lost. In the present invention, the main constituents are preferably a polyol, a diisocyanate, and a diol. The polyol and diisocyanate used in the polyurethane are preferably the same as those used in the aforementioned polyurethane urea, and it is also preferable to use different ones from those used in the polyurethane urea. Among them, the polyhydric alcohol is particularly preferably polybutylene ether glycol having a number average molecular weight of 2500 to 5,000. The chain extender used in the present invention is preferably a low-molecular-weight glycol. The low-molecular-weight diol is preferably ethylene glycol, 1,3-propanediol, 1,4-butanediol, bishydroxyethoxybenzene, dihydroxyethylene terephthalate, or the like. It is also preferable to use one or two or more of these low molecular diols. The polyurethane elastic fiber of the present invention is formed of the aforementioned polyurethane urea and the aforementioned polyurethane. 1238206 V. Description of the invention (8), various fungicides, deodorants, or silicone oils, mineral oils, etc. containing silver and zinc and these compounds, barium sulfate, thorium oxide, betaine and phosphoric acid Electrostatic agents, etc., also make it better to react with polymers. In particular, from the viewpoint of further improving the durability of chlorine water, light, and various nitrogen oxides for sterilization, for example, zinc oxide, magnesium oxide, and aluminum oxide are selected from the group consisting of Mg, Zn, and A1 metal oxides, composite oxides, Hydroxide, solid solution and hydrotalcite compounds composed of two or more kinds selected from oxides and composite oxides of Mg, Zn, and A1 metals and hydroxide groups, Funteite, and hydromagnesite Anti-chlorine deterioration agents such as mineral mixtures, etc., for example, nitric oxide supplements such as HN-150 manufactured by Hydrozine Co., Ltd., and "Sumilyzer" GA-80, etc. manufactured by Sumitomo Chemical Industry Co., Ltd. A thermal oxidation stabilizer, for example, a light stabilizer such as "Sumisorb" 300 # 622 manufactured by Sumitomo Chemical Co., Ltd. is preferably used. In particular, when the polyurethane elastic fiber of the present invention is used in swimwear applications, a chlorine deterioration preventing agent is more preferably used. In the present invention, such a chlorine deterioration preventing agent is preferably used 1) selected from the group consisting of Mg, Zn, and A1 metal oxides, composite oxides, and hydroxides, 2) selected from the group consisting of Mg, Zn, and A1 metal Two or more kinds of solid solutions selected from oxides, complex oxides, and hydroxide groups, and 3) at least one metal compound selected from the above 1) to 3) groups of hydrotalcite compounds. That is, 'using at least one selected from the group, 2) up to -10- 1238206, 5. Explanation of the invention (11) The method for producing ethyl acetate may be any method. That is, it may be either a melt polymerization method or a solution polymerization method. However, a solution polymerization method is more preferable. In the case of the solution polymerization method, there is less occurrence of foreign matter such as gel in polyurethane urea and polyurethane, and it is easy to obtain low-density polyurethane elastic fibers. Of course, in the case of the solution polymerization method, the effort of preparing a solution can be omitted, and it is also preferable from the viewpoint of production efficiency. Polyurethane urea used in the present invention can be made of polyhydric alcohols with a molecular weight of 1,000 to 8000, MDI, ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, hexamethylenediamine, At least one diamine selected from the group consisting of 1,3-cyclohexyldiamine and 2-methylpentanediamine for synthesis, and the melting point at the high temperature side is 2 50 ° C or more and 3 0 0 ° C or less Especially good. For the synthesis of polyurethane urea, for example, after the polyol and M DI are first melt-reacted, the reactants are dissolved in DMAc, DMF, DMSO, NMP, etc., and a solvent containing them as the main component, and the same as the above two The amine reaction is preferably a method for preparing a polyurethane urea solution. In addition, the melting point of the high-temperature side of polyurethane urea can be adjusted to 2 5 or more and 300 ° C or less, which can be achieved by controlling the types and ratios of polyol, M DI, and diamine. When the molecular weight of the polyol is high, a polyurethane urea having a high temperature and a high melting point can be obtained by relatively increasing the ratio of MDI. When the molecular weight of the polyol is 10,000 or more, from the viewpoint that the high-temperature side melting point of the polyurethane urea is made at 250 ° C or more, it is based on the NC group of the diisocyanate and the hydroxyl group of the polyol. The addition ratio of the molar number ratio ((based on the molar number of the NC0 group of the diisocyanate) / (based on -13-1238206 V. Description of the invention (12) the molar number of the hydroxyl group of the polyol)) is preferably 1.3 or more . Alas, in the synthesis of such polyurethane ureas, it is also preferable to use one or two or more kinds of amine catalysts and organometallic catalysts. Examples of the amine catalyst include N, N-dimethylcyclohexylamine, N, N-dimethylbenzylamine, triethylamine, N-methylmorpholine, N, N-ethylmorpholine, N, N , Nf, Nf-tetramethylethylenediamine, 1> 1,1 ^^-tetramethyl-1,3-propanediamine, ^] ^ ,, 1 ^ -tetramethylhexanediamine, bis-2 -Dimethylamino ether, N, N, N, Nf, N, pentamethyldiethylene triamine, tetramethylguanidine, triethylene diamine, N, Nf-dimethylpiperidine, N -Methyl-N'-dimethylaminoethyl-piperin, N- (2-dimethylaminoethyl) morpholine, 1-methylimidazole, 1,2-dimethylimidazole, N, N-dimethyl Aminoethanol, N, N, N'-triethylamineethylethanolamine, N-methyl-N '-(2-hydroxyethyl) piperin, 2,4,6-tris (dimethylamineethyl) Phenol, Ν, Ν · dimethylaminohexanol, triethanolamine and the like are preferred. The organometallic catalyst is preferably tin benzoate, dibutyltin dilaurate, dibutyl lead octoate, or the like. In the present invention, the concentration of the polyurethane urea solution is preferably within a range of 30% by weight to 80% by weight. The polyurethane used in the present invention may use at least one selected from the group consisting of polyols having a molecular weight of 1,000 to 8000, MDI, ethylene glycol, 1,3-propanediol, and 1,4-butanediol. Diol is synthesized, and the addition ratio of the NCO group mole number based on the diisocyanate and the _group mole number ratio of the polyol is particularly preferably 1.3 or more. In particular, the number average molecular weight is 2500 or more -14-1238206 below 5 000 5. Description of the invention (13) Polybutadiene glycol, and the addition ratio based on the ratio of the NCO-based molar number of the diisocyanate to the hydroxyl molar number of the polyol is 3 · 0 to 4.5 is more preferred. For the synthesis of such polyurethanes, for example, in DM Ac, DMF, MD SO, NMP, etc. and solvents containing them as the main component, each raw material is put in, dissolved, and heated and reacted at an appropriate temperature to obtain a polyamine. The so-called One Shot method of the ethyl formate solution, or the method of melting the reactant in the aforementioned solvent with a polyhydric alcohol and MDI first, and reacting with the aforementioned diol to obtain a polyurethane solution, etc. are good. Alas, in the synthesis of such polyurethanes, it is also better to use one or two or more kinds of amine catalysts and organometallic catalysts. Examples of the amine catalyst include N, N -dimethylcyclohexylamine, N, N -dimethylflatamine, triethylamine, N -methylmorpholine, N, N -ethylmorpholine, N, N , N ,, N, -tetramethylethylenediamine, N, N, N ', N'-tetramethyl-1,3-propanediamine, n, N, N ,, N, -tetramethylhexane Diamine, bis-2-dimethylaminoethyl ether, HN'N'N'-pentamethyldiethylenetriamine, tetramethylguanidine, triethylenediamine, n, n, dimethylamine D, N-methyl-N, dimethylamine ethyl-piperazine, n- (2-dimethylaminoethyl) morphine, 1-methyl flavor D, 1,2-dimethyl miso , N, N -dimethylaminoethanol, N, N, N '· triethylamine ethylethanolamine, N -methyl_n,-(2-hydroxyethyl) piperin, 2,4,6-tri (Dimethylaminoethyl) phenol, N, N-dimethylaminohexanol, triethanolamine and the like are preferred. Further, the organometallic catalyst is preferably tin octoate, dibutyltin dilaurate, dibutyl lead octoate, or the like. -15- 1238206 V. Description of the invention (16) Force is regarded as (G2). Secondly, the length of the sample yarn when the stress for recovering elongation is 0 is regarded as (L2). In the sixth round, the sample yarn was stretched until it was cut. The stress at break is regarded as (G3), and the length of the sample yarn at break is regarded as (L3). Hereinafter, the aforementioned characteristics are obtained by the following formula. Strength two (G3) Stress relaxation = l0 × ((Gl) — (G2)) / (G1) Fixability = l0 × ((L2)-(L1)) / (L1) Elongation = l〇 〇x ((L3) — (L1)) / (L1) [Chlorine embrittlement resistance] Polyurethane elastic yarn: Dilute sodium hypochlorite solution with ion-exchanged water to an effective chlorine concentration of 3 ppm and urea concentration of 3 ppm 5) Chlorine water adjusted to pH 7.2 with a sulfuric acid buffer solution. Add 5 g of negative mesh fabric to the sample yarn in a thermostatic bath whose temperature is adjusted to 28 ° C. The mesh fabric with a 50% elongation of the lateral force is added to the above. The polyurethane elastic yarn was immersed in a constant temperature bath of chlorine water, and the time until the polyurethane elastic yarn of the mesh fabric was observed to be broken was evaluated. [Thermosetting] The sample yarn is freely ordered to extend the sample yarn (length two L5) by 100% (length two 2x (L5)). This length is processed as it is at 180 ° C for 1 minute. It was left at room temperature for 1 day at the same length. Next, the elongation state of the sample yarn was released, and the length (L 6) was measured. Thermoset II 100x ((L6) — (L5)) / (L5) -18-1238206 V. Description of the invention (22) Ethyl ethyl urea, although it has high resistance to chlorine embrittlement and low thermosetting, it has poor recoverability And fixed). The combined results are shown in the table! . [Comparative Example 3] Using the polyurethane elastic fiber of Comparative Example 1, a double-knitted warp knitted fabric and a swimsuit were produced in the same manner as in Example 9. The resistance to chlorine embrittlement of the double-smoothed plain fabric after dyeing was as short as 86 hours, and a break in the polyurethane elastic yarn was also observed at 79 hours in the actual wearing test of the swimwear. -24- 1238206 V. Description of the invention (23) £ Thermosetting (%) Ό o rH rrH ^ sO in m to in Chlorine embrittlement resistance (time) m cn r— (〇〇m rH VO (NT— ( 〇r— (BU τ—Η τ · < mr * H om rH rH r * H ro rH Elongation (%) 455 458 T—H 470 465 455 460 451 479 472 1 Fixation (%) t—H ( N (N < N m (N Ύ--i (N (N (N o (T) stress relaxation (%) 〇 \ (N om 〇om τ-Η m ο m rH mo cn 00 (N cn cn strength ( cN) rH inch τ—Η inch inch 00 m metal compound zinc oxide zinc oxide zinc oxide zinc oxide zinc bisulfite MgO / ZnO Funtite / hydromagnesite zinc oxide zinc oxide A / B (wt ratio) rH 180/97 04 m rn τ—Η 180/97 180/97 180/97 8 o CQ PQ ▼ —H CQ (N fi PQ 1 < CQ rH r—H rH CQ 1 s < < rH < T-M < r ~ i < τ-Η < < i-H < rH <, i < 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparison Example 1 Comparative example 2

-25- 1238206 V. Description of the invention (24) [Effect of the invention] According to the present invention, it is possible to provide polyurethane elastic fibers suitable for swimwear applications having excellent chlorine embrittlement resistance and thermosetting properties. . In addition, by using the polyurethane elastic fiber of the present invention, it is possible to provide a mesh fabric and a swimwear which are excellent in suitability and touch, and which are less deteriorated by chlorine water such as a swimming pool, and are excellent in durability. -26-

Claims (1)

J 1238206 VI. Patent application scope No. 9 1 1 04 5 54 "Polyurethane elastic fiber and its manufacturing method, cloth and swimwear" patent case (Amended on December 3, 1993) Six patent application scope: 1. A polyurethane elastic fiber formed from polyurethane urea and polyurethane, which is characterized by: Contains 3% by weight to 97% by weight of polyurethane. In polyurethane, the addition ratio based on the ratio of the number of NCO-based moles of the diisocyanate to the number of hydroxyl moles of the polymer diol. 1.3 or more, in which polyurethane is a diol selected from the group consisting of ethylene glycol, 1,3-propanediol, and 1,4-butanediol, and polybutylene glycol, Polymeric diols selected from copolymers of tetrahydrofuran and 3-methyltetrahydrofuran, and modified polyether diols of polybutylene ether glycol, copolymers of tetrahydrofuran and 2,3-dimethyltetrahydrofuran, and Synthesized from diphenylmethane diisocyanate. 2 · If the polyurethane elastic fiber of item 1 of the scope of patent application, The sub-quantity is from 1,000 to 8000. 3. The polyurethane elastic fiber according to item 1 of the scope of the patent application, in which the polymer diol is polybutylene = ether glycol with a molecular weight of 2500 to 5,000, and is based on the NCO group mole number of the diisocyanate and The addition ratio based on the ratio of the hydroxyl mole number of the polymer diol is 3.0 or more and 4 _ 5 or less. 4. If the polyurethane elastic fiber in the first item of the scope of the patent application, _ is a 1-1238206 6. The scope of the patent application contains 1) selected from the group consisting of Mg, Zn, A1 metal oxides, composite oxides, and hydroxides Any of two kinds of materials, 2) selected from Mg, Zn, A1 metal oxides, composite oxides, and two or more solid solutions selected from the hydroxide group, 3) the above 1) hydrotalcite compounds ~ 3) At least one metal compound selected from the group. 5. The polyurethane elastic fiber according to item 4 of the application, wherein the metal compound contains 0.1 to 10% by weight. 6. The polyurethane elastic fiber according to item 1 of the scope of patent application, which is a mixture containing fangtite (Mg3Ca (C03) 4) and hydromagnesite. 7. The polyurethane elastic fiber according to item 6 of the patent application, wherein the mixture contains 0.1 to 10% by weight. 8. A kind of cloth, which contains polyurethane elastic fibers as described in the first item of the patent application scope. 9. A swimwear, which is made from a cloth such as the item No. 8 of the application for patent. The method for preparing polyurethane elastic fibers is characterized in that it contains polyurethane urea and polymer Polyurethane composed of urethane is spun with a solution containing 3% to 97% by weight of a solute. The polyurethane is selected from the group consisting of polybutylene ether glycol, tetrahydro Copolymer of sulfan and 3 -methyltetrahydrofuran, and polymer of the group of polybutylene ether ethylene monoether, tetrahydrofuran and 2,3-dimethyltetrahydrofuran-2,238,206 t, patent application scope , Diisocyanate and diol synthesized in polyurethane, the addition ratio based on the ratio of the NC0 group mole number of the diisocyanate to the polymer mole number of the hydroxyl group is 1.3 or more. . 1 1. The method for producing polyurethane elastic fibers according to item 10 of the application, which comprises adding a polyurethane solution to a polyurethane urea solution, followed by spinning. 12. The method for producing a polyurethane elastic fiber according to item 10 of the application, wherein the spinning method is a dry method. 1 3. The method for preparing polyurethane elastic fiber according to item 10 of the scope of patent application, wherein polyurethane can be composed of diol, high molecular diol having a molecular weight of 1,000 to 8000 and diisocyanate Acid diphenylmethane ester is synthesized in solution. 14. The method for preparing polyurethane elastic fiber according to item 10 of the scope of patent application, wherein polyurethane is a group consisting of ethylene glycol, 1,3-propanediol, and 1,4-butanediol It is synthesized by selecting at least one kind of diol and polybutadiene glycol with molecular weight of 2500 to 5000 and diphenylmethane diisocyanate, and according to the number of NCO group moles of diisocyanate and The addition ratio of the ratio of hydroxy moles is 3.0 or more and 4.5 or less. -3-