CN103298985B

CN103298985B - Elastic polyurethane thread and manufacturing method thereof

Info

Publication number: CN103298985B
Application number: CN201180061006.4A
Authority: CN
Inventors: 铃木克哉; 上林达昭; 田中利宏
Original assignee: Toray Opelontex Co Ltd
Current assignee: Toray Opelontex Co Ltd
Priority date: 2010-10-19
Filing date: 2011-10-12
Publication date: 2015-05-06
Anticipated expiration: 2031-10-12
Also published as: WO2012053401A1; US20140033451A1; JPWO2012053401A1; MX2013004238A; US20140148537A1; CN103298985A; EP2631338A1; BR112013009233A2; HK1189248A1; TW201221713A; EP2631338A4; KR101851419B1; KR20130122622A; JP5870928B2; TWI553176B

Abstract

Disclosed is an elastic polyurethane thread with excellent antibacterial and deodorant properties and color fastness. The disclosed the elastic thread comprises a polyurethane with polymer diols and diisocyanate as starting materials and contains metal phosphates in a range of 0.5-10 mass%, wherein the emission amount of monoamine compounds with a molecular mass of 120 or less is 100 [mu]g/m2 or greater.

Description

Polyurethane elastic yarn and method for producing same

Technical Field

The present invention relates to a polyurethane elastic yarn having excellent antibacterial properties and deodorizing properties and excellent discoloration resistance, and relates to a polyurethane elastic yarn suitable for obtaining a fabric having antibacterial properties and deodorizing properties, and a method for producing the same.

Background

Elastic fibers are widely used for stretchable clothing such as socks, underwear, sportswear, sanitary applications (sanitary material applications) such as paper diapers and sanitary napkins, and industrial material applications because of their excellent stretch properties.

In recent years, in the course of requiring a more comfortable living environment, so-called "antibacterial commodities" such as antibacterial paints, antibacterial films, antibacterial threads, antibacterial cosmetic products, antibacterial kitchen supplies, antibacterial stationery, antibacterial sand, antibacterial discs, antibacterial fibers, antibacterial cosmetics, and the like have been widely appearing. Similarly, "deodorant products" such as clothes and bedding having a deodorizing function for aged smell have been emerging.

As antibacterial agents used for these products, inorganic antibacterial agents, particularly silver antibacterial agents, are widely used. Further, the deodorant may, for example, be activated carbon, silver-containing zeolite, zeolite or fine zinc oxide.

The inorganic antibacterial agent has excellent weather resistance, chemical resistance and acute oral toxicity lower than those of organic antibacterial agents. In addition, the heat resistance is significantly higher than that of organic antibacterial agents. Therefore, inorganic antibacterial agents have come to be added to synthetic resins and used in various fields. However, if the inorganic antibacterial agent is added to the synthetic resin and molded, the molded product is discolored by the action of the metal contained in the inorganic antibacterial agent and by the influence of heat during molding and light irradiated to the molded product, and a problem of a significant decrease in product value is likely to occur.

In view of the above, many techniques have been proposed for suppressing the thermochromic color of an antibacterial resin to which an inorganic antibacterial agent is added (patent document 1). However, although these techniques have confirmed certain performance in terms of antibacterial and deodorant properties, it is difficult to say that the yellowing resistance is completely solved because it is highly discolored under the influence of the environment and the passage of time.

Further, as an organic antibacterial agent, an antibacterial and deodorant polyurethane elastic fiber containing hinokitiol as a natural antibacterial agent and a metal oxide and/or a composite metal oxide containing at least one element selected from Zn, Si, Cu, Ni, Fe, Al and Mg has been proposed (patent document 2), and it has been confirmed that the polyurethane elastic fiber has a certain performance in terms of antibacterial properties and deodorant properties. However, since it is confirmed that the antimicrobial hinokitiol sublimates by the heat received in the dry spinning, it is necessary to previously contain a larger amount of the spinning dope. Further, since the residual amount of hinokitiol varies depending on the heat condition of spinning and the like, it is difficult to produce a polyurethane elastic yarn ensuring stable antibacterial property. In addition, hinokitiol, which is a natural antibacterial agent, is expensive, and thus has a problem in terms of cost.

Further, applications of organic synthetic antibacterial agents (patent document 3) and the like have been proposed. However, the organic synthetic antibacterial agents are not effective in deodorizing properties when used alone, and have a problem in terms of compatibility between antibacterial properties and deodorizing properties.

Documents of the prior art

Patent document

Patent document 1: japanese patent No. 4485871

Patent document 2: japanese laid-open patent publication No. 2002-105757

Patent document 3: japanese patent laid-open No. 2004-292471.

Disclosure of Invention

Problems to be solved by the invention

The purpose of the present invention is to provide a polyurethane elastic yarn having excellent antibacterial properties and deodorizing properties and excellent discoloration resistance, and a method for producing the same.

Means for solving the problems

The present invention for solving the above problems employs any of the following technical means.

(1) A polyurethane elastic yarn comprising polyurethane which is obtained by using polymer diol and diisocyanate as starting materials, wherein the elastic yarn contains metal phosphate and the emission amount of monoamine compound having a molecular weight of 120 or less is 100 [ mu ] g/m²The above.

(2) The polyurethane elastic yarn according to the item (1), wherein the content of the metal phosphate is 0.5 to 10 wt%.

(3) The elastic polyurethane yarn according to the above (1) or (2), wherein the metal phosphate has an average primary particle diameter of 3.0 μm or less.

(4) The elastic polyurethane wire according to any one of (1) to (3) above, wherein the metal phosphate is at least one selected from the group consisting of titanium phosphate, zirconium phosphate and aluminum dihydrogen tripolyphosphate.

(5) The polyurethane elastic yarn according to any one of (1) to (4) above, wherein the monoamine compound to be emitted is a secondary monoamine compound.

(6) The elastic polyurethane yarn according to any one of (1) to (5) above, further comprising a quaternary ammonium salt compound.

(7) The elastic polyurethane yarn according to the item (6), wherein the quaternary ammonium salt compound has the following structure:

[ solution 1]

Wherein,

r1 and R2 are hydrogen or alkyl with 1-3 carbon atoms, and may be the same or different;

r3 is an alkyl group having 10 to 22 carbon atoms;

r4 is an alkyl group having 1 to 22 carbon atoms, and may be the same as or different from R1, R2 or R3;

x-is an acidic counterion.

(8) The elastic polyurethane yarn according to the above (6) or (7), wherein the quaternary ammonium salt compound is contained in an amount of 0.1 to 5 wt%.

(9) A process for producing a polyurethane elastic yarn, which comprises mixing a metal phosphate with a spinning dope containing a polyurethane starting from a polymer diol and a diisocyanate, and simultaneously mixing a monoamine compound having a molecular weight of 120 or less so that the content of the monoamine compound is in the range of 0.01 to 0.5 wt.% based on the spinning dope, and dry-spinning the spinning dope.

(10) The method for producing a polyurethane elastic yarn according to the above (9), wherein the metal phosphate is mixed in the form of a dispersion in the spinning dope containing polyurethane starting from polymer diol and diisocyanate.

(11) The method for producing a polyurethane elastic yarn according to the above (9) or (10), wherein the metal phosphate is at least one selected from the group consisting of titanium phosphate, zirconium phosphate and aluminum dihydrogen tripolyphosphate.

(12) The method for producing a polyurethane elastic yarn according to any one of (9) to (11), wherein the monoamine compound having a molecular weight of 120 or less is a secondary amine compound.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a polyurethane elastic yarn can be obtained, whichIs an elastic yarn composed of polyurethane whose main constituent components are polymer diol and diisocyanate, the elastic yarn contains metal phosphate, and the emission amount of monoamine compound with molecular weight below 120 is 100 mug/m²This is because the composition is excellent in stretchability, deodorizing properties, antibacterial properties, and discoloration resistance. Therefore, the fabric using the polyurethane elastic yarn is excellent in stretchability, deodorizing properties, antibacterial properties, and discoloration resistance.

Drawings

Fig. 1 is a schematic diagram showing the dimensions of each part of the package.

Detailed Description

Hereinafter, the present invention will be described in more detail.

First, the polyurethane used in the present invention will be described.

The polyurethane used in the present invention is not particularly limited, as long as it is a polyurethane using a polymer diol and a diisocyanate as starting materials, and any polyurethane may be used. Further, the synthesis method is not particularly limited. That is, for example, a polyurethaneurea composed of a polymer diol, a diisocyanate, and a low molecular weight diamine, or a polyurethane urethane (polyurethane urethane) composed of a polymer diol, a diisocyanate, and a low molecular weight diol may be used. Further, a polyurethaneurea using a compound having a hydroxyl group and an amino group in the molecule as a chain extender is also possible. Polyfunctional glycols or isocyanates having a functionality of 3 or more are also preferably used within a range not to impair the effects of the present invention.

The polymer diol is preferably a polyether diol, a polyester diol, a polycarbonate diol, or the like. Further, polyether glycols are preferably used particularly from the viewpoint of imparting flexibility and elongation to the yarn.

As the polyether glycol, for example, polyethylene oxide, polyethylene glycol, a derivative of polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol (hereinafter abbreviated as PTMG), modified PTMG which is a copolymer of Tetrahydrofuran (THF) and 3-methyltetrahydrofuran (hereinafter abbreviated as 3M-PTMG), modified PTMG which is a copolymer of THF and 2, 3-dimethylthf, a polyol having side chains on both sides disclosed in japanese patent No. 2615131 and the like, a random copolymer in which THF and ethylene oxide and/or propylene oxide are irregularly arranged, and the like are preferably used. These polyether diols may be used in combination of one or more kinds thereof or may be used after copolymerization.

As the polyurethane elastic yarn, in view of obtaining abrasion resistance and light resistance, butylene adipate, polycaprolactone diol, polyester-based diol such as polyester polyol having a side chain disclosed in japanese patent laid-open publication No. 61-26612 and the like, polycarbonate diol disclosed in japanese patent laid-open publication No. 2-289516 and the like are preferably used.

The polymer diol may be used alone, or two or more of them may be used in combination or after copolymerization.

The molecular weight of the polymer diol is preferably 1000 or more and 8000 or less, more preferably 1500 or more and 6000 or less, from the viewpoint of obtaining elongation, strength, heat resistance and the like when the yarn is produced. By using the polyol having the molecular weight within this range, an elastic yarn excellent in elongation, strength, elastic recovery force, and heat resistance can be easily obtained.

Next, as the diisocyanate, aromatic diisocyanates such as diphenylmethane diisocyanate (hereinafter abbreviated as MDI), toluene diisocyanate, 1, 4-phenylene diisocyanate, xylylene diisocyanate, and 2, 6-naphthalene diisocyanate are particularly suitable for synthesizing a polyurethane having high heat resistance and strength. Further, as the alicyclic diisocyanate, for example, methylene bis (cyclohexyl isocyanate) (hereinafter referred to as H12MDI), isophorone diisocyanate, methylcyclohexane 2, 4-diisocyanate, methylcyclohexane 2, 6-diisocyanate, cyclohexane 1, 4-diisocyanate, hexahydroxylylene diisocyanate, hexahydrotoluene diisocyanate, octahydro 1, 5-naphthalene diisocyanate and the like are preferable. The aliphatic diisocyanate can be used particularly effectively in suppressing yellowing of the polyurethane elastic yarn. These diisocyanates may be used alone or in combination of two or more.

Next, as a chain extender used in synthesizing the polyurethane, at least one of a low-molecular-weight diamine and a low-molecular-weight diol is preferably used. The compound may have a hydroxyl group and an amino group in the molecule, such as ethanolamine.

Examples of the preferable low-molecular-weight diamine include ethylenediamine, 1, 2-propylenediamine, 1, 3-propylenediamine, hexamethylenediamine, p-phenylenediamine, p-xylylenediamine, m-xylylenediamine, p' -methylenedianiline, 1, 3-cyclohexanediamine, hexahydro-m-phenylenediamine, 2-methylpentamethylenediamine, and bis (4-aminophenyl) phosphine oxide. One or two or more thereof are preferably used. Ethylenediamine is particularly preferred. By using ethylenediamine, a yarn excellent in elongation, elastic recovery and heat resistance can be easily obtained. To these chain extenders, triamine compounds capable of forming a crosslinked structure, such as diethylenetriamine, may be added to such an extent that the effect is not lost.

Further, as the low molecular weight diol, ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, bishydroxyethoxybenzene, bishydroxyterephthalic acid ethylene glycol, 1-methyl-1, 2-ethanediol, and the like are representative. One or two or more thereof are preferably used. Ethylene glycol, 1, 3-propanediol, and 1, 4-butanediol are particularly preferable. When these low molecular weight diols are used, the heat resistance of the diol-extended polyurethane is further improved, and a yarn having higher strength can be obtained.

In the present invention, the molecular weight of the polyurethane is preferably in the range of 30000 or more and 150000 or less in terms of number average molecular weight from the viewpoint of obtaining a fiber having high durability and strength. The molecular weight was measured by GPC and converted to polystyrene.

It is also preferable to use one kind in combination in the polyurethaneOr two or more capping agents. The blocking agent is preferably a monoamine such as dimethylamine, diisopropylamine, ethylmethylamine, diethylamine, methylpropylamine, isopropylmethylamine, diisopropylamine, butylmethylamine, isobutylmethylamine, isopentylmethylamine, dibutylamine, and dipentylamine, a monoalcohol such as ethanol, propanol, butanol, isopropanol, allyl alcohol, and cyclopentanol, a monoisocyanate such as phenyl isocyanate, and the like. Wherein the amount of the monoamine compound having a molecular weight of 120 or less in the polyurethane elastic yarn under the condition of polyurethane polymerization is 100 [ mu ] g/m²From the viewpoint of the above, it is preferable to use a monoamine having a molecular weight of 120 or less as the blocking agent.

In the present invention, by incorporating a metal phosphate into a polyurethane elastic yarn made of polyurethane having the basic structure as described above, the deodorization performance with respect to ammonia gas can be improved without affecting the deodorization performance with respect to acetic acid gas, nonenal gas, and isovaleric acid gas which are inherently possessed by the polyurethane elastic yarn. Further, the amount of emissions from the elastic polyurethane yarn is 100 [ mu ] g/m by incorporating a monoamine compound having a molecular weight of 120 or less into the elastic polyurethane yarn²Above, preferably 100. mu.g/m²Above and 500. mu.g/m²Hereinafter, excellent antibacterial properties can be ensured.

From the viewpoint of deodorization, the metal phosphate of the present invention is preferably an acid phosphate of a 4-valent metal such as zirconium phosphate and titanium phosphate having a layered structure, aluminum dihydrogen tripolyphosphate, or the like. More preferably zirconium phosphate. These may be used alone or in combination of two or more.

The content of the metal phosphate is preferably in a range of 0.5 wt% or more and 10wt% or less with respect to the total weight of the polyurethane elastic yarn. If the content of the metal phosphate is less than 0.5% by weight, it is difficult to obtain sufficient ammonia gas deodorizing property when the fabric is produced, which is not preferable. More preferably 1.0% by weight or more. On the other hand, if the content is more than 10% by weight, it is not preferable in terms of deterioration of the stretching property and cost. More preferably 7.0 wt% or less. In view of the balance between the deodorization performance for ammonia gas and the physical properties and cost, the range of 1.5 wt% or more and 5.0 wt% or less is particularly preferable.

The metal phosphate preferably has an average primary particle diameter of 3.0 μm or less from the viewpoint of suppressing clogging of the spinning die with the dope. More preferably 1.5 μm or less. From the viewpoint of dispersibility, when the average primary particle size is less than 0.05 μm, the average primary particle size is preferably 0.05 μm or more because the coagulation force is high and it is difficult to make the average primary particle size uniform in the dope. More preferably 0.15 μm or more.

On the other hand, in order to obtain an emission amount of the monoamine compound having a molecular weight of 120 or less, emitted from the polyurethane elastic yarn, of 100. mu.g/m²As described above, for example, it is preferable to spin a spinning dope containing polyurethane containing a monoamine compound in a range of 0.01 wt% to 0.5 wt%. When the content of the monoamine compound in the spinning dope is less than 0.01 wt%, the monoamine is not sufficiently contained in the polyurethane elastic yarn obtained by spinning, and as a result, sufficient antibacterial properties cannot be obtained. On the other hand, if the monoamine compound is contained in an amount of 0.5 wt% or more in the dope, the resulting elastic polyurethane yarn will be inferior in quality such as yellowing.

Further, even when a monoamine having a molecular weight of 120 or less is used as a terminal-blocking agent in the synthesis of polyurethane without adding a monoamine after polymerization, the amount of the monoamine compound to be emitted in the elastic polyurethane yarn can be 100. mu.g/m²The above. Specifically, when the isocyanate group and the amino group are reacted, a chain extender such as a diamine compound and the monoamine compound are preferably mixed and used in advance. In this case, the ratio of the amino group in the chain extender to the amino group in the monoamine compound is preferably in the range of 5:1 to 25: 1. More preferably 5:1 to 20: 1. The amount of the chain extender used in the reaction with the mixture of monoamine compounds is preferably such that the molar ratio of the isocyanate group concentration to the amino end group concentration in the reaction is 1:1.04 to 1: 1.15. Thereby, a polymer solution containing more amino groups than in the conventional polymerization can be prepared, and the emission of the monoamine in the spun yarn can be ensuredThe amount is also 100. mu.g/m²The above.

Examples of the monoamine mixture having a molecular weight of 120 or less include secondary amine compounds such as diethylamine, dimethylamine, diisopropylamine, ethylmethylamine, N-methylpropylamine, isopropylmethylamine, N-butylmethylamine and N-methylisobutylamine, and primary amine compounds such as ethylamine, N-propylamine, isopropylamine, N-butylamine and cyclohexylamine. From the viewpoint of stability of the polyurethane spinning dope, a secondary amine compound is preferable.

In order to further improve the antibacterial property, the polyurethane elastic yarn preferably contains a quaternary ammonium salt compound. The quaternary ammonium salt-based compound differs in antibacterial effectiveness depending on the chain length of the alkyl group in the ammonium ion, and if the chain length of the alkyl group is long, the antibacterial effectiveness tends to be high. Further, if the chain length is too short, it is easily volatilized or deteriorated by heat at the time of spinning. On the other hand, if the chain length of the alkyl group is too long, the operability is poor. Therefore, the kind and chain length of the chain such as alkyl group are preferably selected to obtain desired characteristics.

Particularly preferred ammonium ions from the viewpoint of antibacterial efficacy are stearyl trimethylammonium ion, cetyl trimethylammonium ion, didecyl dimethylammonium ion, oleyltrimethylammonium ion, and the like. They generally have a structure supplied in the form of an organic acid salt such as a sulfonate or a phosphate, or a salt such as a chloride, a bromide, or an iodide. Among them, sulfonate is preferable from the viewpoint of stability such as discoloration and heat resistance.

[ solution 2]

Wherein,

r3 is an alkyl group having 10 to 22 carbon atoms;

x-is an acidic counterion.

As specific examples of the salt having the above structure, didecyl dimethyl ammonium trifluoride methanesulfonate, di-n-decyl dimethyl ammonium trifluoromethanesulfonate, di-n-decyl dimethyl ammonium pentafluoroethanesulfonate, n-hexadecyl trimethyl ammonium trifluoromethanesulfonate and benzyl dimethyl cocoalkyl ammonium pentafluoroethanesulfonate are given.

The content of the quaternary ammonium salt compound is preferably in the range of 0.1 to 5 wt% based on the total weight of the polyurethane elastic yarn, and more preferably in the range of 0.2 to 2 wt% based on the total weight of the polyurethane elastic yarn, from the viewpoint of exhibiting a balance among antibacterial properties, discoloration properties, and stretch properties.

The polyurethane elastic yarn may further contain various stabilizers, pigments, and the like. For example, BHT, hindered phenol-based reagents such as "Sumilizer" (registered trademark) GA-80 manufactured by Sumitomo chemical industries, Ltd., benzotriazole-based and benzophenone-based reagents such as "Tinuvin" (registered trademark) manufactured by Ciba-Katsuba corporation (チバガイギー Co.), phosphorus-based reagents such as "Sumilizer" (registered trademark) P-16 manufactured by Sumitomo chemical industries, various hindered amine-based reagents, various pigments such as iron oxide and titanium oxide, inorganic substances such as zinc oxide, cerium oxide, magnesium oxide, calcium carbonate and carbon black, fluorine-based and silicone-based resin powder, metal soaps such as magnesium stearate, lubricants such as silicone and mineral oils, various antistatic agents such as cerium oxide, betaine and phosphoric acid-based agents, and the like are preferably contained in the light-resistant agent, the antioxidant, and the like, and they are preferably reacted with the polymer. Further, in order to further improve durability against light, various nitrogen oxides, and the like, in particular, it is preferable to use a nitrogen oxide scavenger such as HN-150 manufactured by Hydrazine corporation, a thermal oxidation stabilizer such as "Sumilizer" (registered trademark) GA-80 manufactured by Sumitomo chemical industries, and a light stabilizer such as "Sumisorb" (registered trademark) 300 ♯ 622 manufactured by Sumitomo chemical industries, for example.

Next, a method for producing the polyurethane elastic yarn of the present invention will be described in detail.

In the present invention, a polyurethane spinning dope obtained from a polymer diol and a diisocyanate as starting materials is spun by adding (i.e., by allowing to exist) a metal phosphate and a monoamine compound having a molecular weight of 120 or less. From the viewpoint of stabilizing polymerization, it is preferable to prepare a polyurethane solution in advance and add a metal phosphate dispersion and a monoamine compound having a molecular weight of 120 or less thereto. The "spinning dope" in the present invention refers to a liquid to be finally spun, and the polyurethane solution refers to a solution containing polyurethane, and may be a liquid in any state.

The method for producing a polyurethane solution or the method for producing a polyurethane as a solute of a solution may be any of melt polymerization methods and solution polymerization methods, or may be other methods. However, the solution polymerization method is more preferable. In the case of the solution polymerization method, the generation of foreign matters such as gel in polyurethane is small, spinning is easy, and a polyurethane elastic yarn with low fineness is easily obtained. Further, in the case of the solution polymerization method, there is an advantage that the operation of making a solution can be omitted.

The polyurethane can be polymerized using the above-mentioned polymer diol, diisocyanate, chain extender, and, if necessary, the above-mentioned blocking agent. A particularly preferred polyurethane is a polyurethane synthesized by using PTMG having a molecular weight of 1500 or more and 6000 or less as a polymer diol, MDI as a diisocyanate, and at least one of ethylenediamine, 1, 2-propylenediamine, 1, 3-propylenediamine, and hexamethylenediamine as a chain extender.

The polyurethane is obtained by, for example, synthesizing the above-mentioned starting materials in DMAc, DMF, DMSO, NMP, or the like or a solvent containing these as a main component. For example, as a particularly preferable method, a so-called one-shot method in which each raw material is put into the above-mentioned solvent and dissolved, and heated to an appropriate temperature to cause reaction, thereby producing polyurethane, or a method in which a polymer diol and a diisocyanate are first melt-reacted, and then the reaction product is dissolved in a solvent, thereby producing polyurethane by reacting with the above-mentioned chain extender, may be employed.

When a diol is used as the chain extender, the melting point of the polyurethane on the high temperature side is preferably adjusted to a range of 200 ℃ to 260 ℃ from the viewpoint of obtaining a product excellent in heat resistance. As a representative method, it can be realized by controlling the kinds and the proportions of the polymer diol, MDI, diol. When the molecular weight of the polymer diol is low, a polyurethane having a high melting point at high temperature can be obtained by relatively increasing the proportion of MDI, and similarly, when the molecular weight of the diol is low, a polyurethane having a high melting point at high temperature can be obtained by relatively decreasing the proportion of the polymer diol.

When the molecular weight of the polymer diol is 1800 or more, the polymerization is preferably carried out in a ratio of (number of moles of MDI)/(number of moles of polymer diol) =1.5 or more so that the melting point on the high temperature side becomes 200 ℃ or more.

In the synthesis of the polyurethane, it is also preferable to use one or a mixture of two or more of catalysts such as amine-based catalysts and organometallic catalysts.

Examples of the amine catalyst include N, N-dimethylcyclohexylamine, N, N-dimethylbenzylamine, triethylamine, N-methylmorpholine, N-ethylmorpholine, N, N, N ', N ' -tetramethylethylenediamine, N, N, N ', N ' -tetramethyl-1, 3-propanediamine, N, N, N ', N ' -tetramethylhexamethylenediamine, bis-2-dimethylaminoethyl ether, N, N, N ', N ', N ' -pentamethyldiethylenetriamine, tetramethylguanidine, triethylenediamine, N, N ' -dimethylpiperazine, N-methyl-N ' -dimethylaminoethylpiperazine, N- (2-dimethylaminoethyl) morpholine, 1-methylimidazole, 1, 2-dimethylimidazole, N, n-dimethylaminoethanol, N, N, N '-trimethylaminoethylethanolamine, N-methyl-N' - (2-hydroxyethyl) piperazine, 2,4, 6-tris (dimethylaminomethyl) phenol, N, N-dimethylaminohexanol, triethanolamine and the like.

Further, as the organic metal catalyst, tin octylate, dibutyltin dilaurate, lead dibutyloctylate, and the like may be mentioned.

In the present invention, it is preferable to add a metal phosphate and a monoamine compound having a molecular weight of 120 or less to the polyurethane solution to prepare a spinning dope. As a method of adding the metal phosphate and the monoamine compound to the polyurethane solution, any method can be adopted. As representative methods thereof, various methods such as a method using a static mixer, a method using stirring, a method using a homomixer, and a method using a twin-screw extruder can be employed.

The metal phosphate and the monoamine compound may be added to the polyurethane solution separately or may be added to the polyurethane solution after being mixed in advance. From the viewpoint of exhibiting the deodorizing property against ammonia gas, it is preferable to mix them in advance to prepare a dispersion and add the dispersion to the polyurethane solution.

In order to improve the deodorization with respect to ammonia gas, it is preferable that the metal phosphate is contained in the polyurethane elastic yarn in a range of 0.5 wt% to 10 wt%. Therefore, it is necessary to disperse the metal phosphate in the polyurethane spinning dope before spinning in a range of 0.5 wt% to 10wt% of the spinning dope without unevenness, and it is preferable to obtain the spinning dope by adding the metal phosphate to a polyurethane solution using N, N-dimethylformamide, N-dimethylacetamide, or the like as a solvent, stirring and mixing the mixture to disperse the metal phosphate without unevenness. Specifically, it is preferable to disperse a metal phosphate in a solvent such as N, N-dimethylformamide or N, N-dimethylacetamide in advance to prepare a metal phosphate dispersion, and mix the dispersion with a polyurethane solution. Here, from the viewpoint of being uniformly added to the polyurethane solution, it is preferable to use the same solvent as the polyurethane solution as the solvent of the metal phosphate dispersion to be added. When the metal phosphate is added to the polyurethane solution, the above-mentioned agents such as a light-resistant agent and an antioxidant, and a pigment may be added at the same time.

In the present invention, the monoamine compound may be present in the spinning dope finally used for spinning by using the monoamine having a molecular weight of 120 or less as a terminal-blocking agent in the synthesis of the polyurethane, without adding the monoamine to the solution containing the polyurethane after the polymerization of the polyurethane.

In the present invention, the metal phosphate and the monoamine having a molecular weight of 120 or less are present in the dope together with the polyurethane as described above, but in order to improve the antibacterial activity against various bacteria, it is preferable to contain the monoamine having a molecular weight of 120 or less in the range of 0.01 to 0.5% by weight in the dope.

The concentration of the polyurethane in the polyurethane spinning solution is preferably in the range of 30 wt% to 80 wt%.

In the present invention, it is also preferable to contain a quaternary ammonium salt compound in order to improve the antibacterial activity against various bacteria. Therefore, the polyurethane spinning solution before spinning is spun while containing the quaternary ammonium salt compound. The quaternary ammonium salt compound may be contained in the spinning dope by itself or may be mixed in advance in the metal phosphate dispersion.

The polyurethane elastic yarn of the present invention can be obtained by, for example, dry spinning, wet spinning, or melt spinning the dope configured as described above and winding the dope. Among them, dry spinning is preferable from the viewpoint that stable spinning can be performed with any fineness from fine to coarse.

The fineness, the cross-sectional shape, and the like of the polyurethane elastic yarn of the present invention are not particularly limited. For example, the cross-sectional shape of the wire may be either circular or flat.

The dry spinning method is not particularly limited, and spinning can be performed by appropriately selecting spinning conditions and the like according to desired characteristics and spinning equipment.

For example, the permanent strain rate and the stress relaxation rate of the polyurethane elastic yarn of the present invention are particularly easily affected by the speed ratio of the godet roller and the winder, and therefore are preferably determined appropriately according to the purpose of use of the yarn. That is, from the viewpoint of obtaining a polyurethane elastic yarn having a desired permanent strain rate and stress relaxation rate, it is preferable to perform winding in a range where the speed ratio of the godet and the winder is 1.10 or more and 1.65 or less.

Further, the spinning speed is preferably 250 m/min or more from the viewpoint of improving the strength of the resulting polyurethane elastic yarn.

Examples

The present invention will be described in more detail with reference to examples.

[ Strength, stress relaxation Rate, permanent Strain Rate, elongation of polyurethane elastic yarn ]

The strength, stress relaxation rate, permanent strain rate, and elongation of the polyurethane elastic yarn were measured by subjecting a sample yarn to a tensile test using an Instron model 4502 tensile tester.

They are defined as follows.

That is, a sample of 5cm (L1) was stretched at a stretching rate of 50 cm/min by 300%, and the process was repeated 5 times. The stress at the 5 th time was designated as (G1). Then, the 300% stretch was maintained for 30 seconds. The stress after 30 seconds of holding was recorded as (G2). Subsequently, the elongation was recovered, and the length of the sample wire at which the stress reached 0 was recorded as (L2). Then, at the 6 th pass, the sample filaments were drawn until they broke. The stress at the time of breakage was designated as (G3), and the length of the sample wire at the time of breakage was designated as (L3).

Hereinafter, the above characteristics are known by the following formula.

Intensity [ cN ] = (G3)

Stress relaxation rate [% ] =100 × ((G1) - (G2))/(G1)

Permanent strain rate [% ] =100 × ((L2) - (L1))/(L1)

Elongation [% ] =100 × ((L3) - (L1))/(L1)

The tensile test was performed 3 times and the average value was obtained.

[ production of a knitted Fabric for evaluation of deodorant Property and antibacterial Properties ]

A22 dtex elastic polyurethane yarn was drawn 3 times, and a sheath yarn of a polyamide processed yarn (33 dtex 26 monofilament yarn made by Kyuupu, Toray corporation (Chinese imperial ceramics レ)) was covered with the yarn at a twist number of 800T/m to prepare a Single Covered Yarn (SCY) having S-twist and Z-twist.

Then, the S twist SCY was supplied to the yarn feeding ports 1 and 3 and the Z twist SCY was supplied to the yarn feeding ports 2 and 4 of a pantyhose knitting machine (manufactured by Rona emperor (ロナティ Co., Ltd.), with a knitting tension of 1.0g, and the number of stitches was 400, and a knitted fabric was knitted. The content of the polyurethane elastic yarn in the knitted fabric was 16%.

Next, the knitted fabric was dyed as described below to obtain a pantyhose knitted fabric.

(1) Presetting: using a vacuum drier at 90 ℃ for 10 minutes

(2) Dyeing: the dye "Lanaset" (registered trademark) Black B produced by Ciba concentrates (チバ, seeds スペシャルティ, seeds ケミカルズ) was treated at 90 ℃ for 60 minutes to dye Black at 2.0 owf%. The pH adjustment during dyeing was carried out with acetic acid and ammonium sulfate.

(3) Finally, the fabric was softened and finished by a setting process (using a pantyhose setting machine, setting: 115 ℃ C.. times.10 seconds, drying: 120 ℃ C.. times.30 seconds).

[ washing method ]

A manual of a washing method prepared by the society for evaluating new functions of textile products was used as a standard (JIS L0217:1995, attached Table 1, washing method 103). Specifically, 40 ml of JAFET standard detergent (manufactured by the society for evaluating the New function of fiber products) was dissolved in 3L of water at 40 ℃ to prepare a washing solution using a household electric washer specified in Table 1 of JIS L0217:1995 and washing method 103, and 1kg of the object to be washed as a sample was added to the washing solution. Washing for 5 minutes, dehydrating, rinsing for 2 minutes, dehydrating, and washing with the above-mentioned procedure as 1 time.

[ deodorizing Property ]

The deodorizing test was conducted by the following instrument test to evaluate the deodorizing ability of the odor component based on the deodorizing processed fiber product certification standard (the producer: the product certification department of the society of Law fiber evaluation technical Association, the production date: the average 14 years (2002) 9 months and 1 days). In addition, the acceptance criteria for the evaluation of the "deodorizing effect" as the reduction rate of each odor component in the instrumental analysis test, which was established by the society law fiber evaluation technical agreement, are shown in table 1.

(test tube method)

1. The sample (10 cm. times.10 cm) was placed in a sampling bag (Tedlar bag).

2. A predetermined amount of the test gas shown in Table 1 was injected, and the residual gas concentration (ppm) after 2 hours was measured using a detector tube (manufactured by Gastech corporation, ガステック) corresponding to the component. The gas filling rate was 3L, and the diluent gas was dry air or nitrogen.

[ Table 1]

Gas (es)	Initial concentration (ppm)	Qualification standard	Specification of
				Ammonia	100	Over 70 percent	JAFET
Acetic acid	50	Over 80 percent	JAFET
				Nonenal	14	Over 75 percent	JAFET

3. The same evaluation was performed without using a sample as a blank test.

4. In the evaluation, the reduction rate of the residual gas concentration was calculated according to the following formula and referred to as a deodorization rate.

[ number 1]

The measurement value was obtained from the average value of n = 3.

[ antibacterial Properties ]

The antibacterial test was carried out based on the antibacterial test procedures (JIS L1902:2008, bacterial suspension absorption method) specified by the society of law for fiber evaluation. The antibacterial activity value was calculated from the following formula, with X as the viable cell count (number) of the non-processed sample after 18 hours of culture and Y as the viable cell count (number) of the test fabric after 18 hours of culture, to evaluate the antibacterial efficacy. The measurement value was obtained from the average value of n = 3.

[ number 2]

The value of the bacteriostatic activity is LogX-LogY

Further, according to the society of community law, the fiber evaluation technical council, when the bacteriostatic activity value of staphylococcus aureus is 2.2 or more, it is considered to be "effective" in terms of antibacterial property.

[ emission amount of monoamino compound ]

Pretreatment:

after the polyurethane elastic yarn was wound, it was stored at 35 ℃ C.. times.65% RH for 14 days. Then, the elastic polyurethane yarn was put into a bag with a bayonet (manufactured by Nippon corporation, J-4, 340 mm. times.240 mm. times.0.04 mm), and then, the bag was sealed immediately after injecting clean air, and stored at room temperature of 23 ℃ for 100 hours.

And (3) analysis:

the entire gas was trapped in the trap tube from the treated bayonet bag into which polyurethane elastic wire was placed. The collected organic components were removed from the collection tube by heating and introduced into a GC/MS for analysis. The measurement conditions are shown in Table 2.

[ Table 2]

The calibration curve for toluene was used quantitatively by the absolute calibration curve method based on the absolute area of total ions. The emission amount per unit area from the test was measured by the following formula, and the measured value was obtained from the average value of n =2 by measuring 2 points for the same level of sample.

[ number 3]

Amount of emission (. mu.g/m)²) Component amount (μ g)/exposed area of filament portion (cm)²)×10

Exposed area (cm) of silk part²)＝((A/2)²×3.14－(B/2)²×3.14)×2＋((C+D)/2)×A×3.14

Here A, B, C, D is as defined in fig. 1. In fig. 1, (a) is a plan view of the package, and (b) is a front view of the package.

[ NOx yellowing resistance ]

10g of polyurethane elastic wire was wound around a stainless steel plate to prepare a sample card. The sample was allowed to contain NO at a predetermined concentration (7ppm) in air using a Scott tester (Scottester)₂The resultant gas was exposed for 50 hours. Before and after the exposure treatment, "b" Color was measured using a Color manager (Color Master) (Signal Processor (D25 DP-9000)), and the degree of yellowing was evaluated from the difference "Δ b" between before and after the treatment. The measurement value was obtained from the average value of n = 3.

[ average Primary particle diameter ]

The inorganic particles were photographed by a field emission scanning electron microscope (FE-SEM) S-800 manufactured by Hitachi, Ltd, and analyzed by Image processing software Image-Pro version 4.0. The projected area circle equivalent diameter was measured, and the number of n =20 was averaged for each sample.

[ content of Metal phosphate ]

The polyurethane elastic yarn was analyzed by the base yarn absorptiometry to determine the concentration of metal phosphate. The measurement was performed for metals (Al, Zr, Ti) in the metal phosphate. The measured value was obtained from the average of n =3, and the content of the metal phosphate was obtained by the following equation.

[ number 4]

。

[ content of Quaternary ammonium salt ]

1g of a sample (polyurethane yarn) was weighed, added to 100ml of methanol, and the quaternary ammonium salt was extracted. The extract was quantified by liquid chromatography based on a previously prepared standard solution. The analysis conditions are as follows. The measurement was determined by averaging n = 2.

Column: LiChrospher 100 RP-18(5 μm), inner diameter 4.6mm, length 150mm, column temperature: 35 deg.C

And (3) detection: UV210nm

Mobile phase: methanol/water mixed solution (60/40 vol%), flow rate: 1 ml/min, injection amount: 2 μ l.

[ example 1]

PTMG having a molecular weight of 1800 and MDI were reacted at 90 ℃ for 2 hours at a molar ratio of 1:1.58 to prepare an isocyanate-terminated prepolymer, which was then dissolved in DMAc to obtain 35% by weight of a prepolymer solution. Further, ethylenediamine as a chain extender, 1, 2-propylenediamine, and diethylamine as a chain terminator (end capping agent) were mixed at a ratio of amino end group concentration of 10:2:1, and dissolved in DMAc so as to reach 35% by weight, to prepare an amine solution. The prepolymer solution and the amine solution were mixed with stirring under conditions that the molar ratio of the isocyanate terminal group to the amine terminal group was 1:1.02 to prepare a DMAC solution (concentration: 35 wt%) of the polyurethaneurea polymer. Next, a polyurethane solution ("Methacrol" (registered trademark) 2462 manufactured by dupont) and a polycondensate of cresol and divinylbenzene ("Methacrol" (registered trademark) 2390 manufactured by dupont) were mixed in a ratio of 2 to 1 (weight ratio) to prepare an antioxidant DMAc solution (concentration 35 wt%). A polymer solution A1 was prepared by mixing 96 parts by weight of the DMAc solution of the above polyurethaneurea polymer with 4 parts by weight of the antioxidant DMAc solution.

Next, NS-10 (average primary particle diameter: 0.9 μm), which is a zirconium phosphate deodorant "ケスモン" (registered trademark) from Tokya Synthesis Co., Ltd., was dispersed in DMAc with a homomixer to prepare a zirconium phosphate dispersion B1 (35% by weight).

Subsequently, 35 wt% of diethylamine (molecular weight: 73.14) was prepared in DMAc to prepare a monoamine solution C1.

The polymer solutions a1, B1, and C1 were uniformly mixed at 96.9 wt%, 3 wt%, and 0.1 wt% to prepare a dope D1. This was dry-spun at a speed of 720 m/min under a condition that the speed ratio of the godet to the winder was 1.3, to obtain a 200g filament package of 22dtex polyurethane filament with a 2-filament and a zirconium phosphate content of 3 wt%.

The obtained polyurethane elastic yarn was used as a knitted fabric for evaluation, and the deodorizing property and the antibacterial property were measured. The results are shown in tables 3, 4 and 5 together with the amount of monoamine compound emitted from the polyurethane elastic yarn itself and the NOx yellowing resistance.

[ example 2]

The polymer solutions a1, B1, and C1 were uniformly mixed at 97.98 wt%, 2 wt%, and 0.02 wt% to prepare a dope D2. This was dry-spun in the same manner as in example 1 to obtain a filament package of 200g of 22dtex polyurethane filament with 2 monofilaments and a zirconium phosphate content of 2 wt%.

The results of the various evaluations are shown in tables 3, 4 and 5.

[ example 3]

The synthesized titanium phosphate (average primary particle diameter 1.1 μm) was dispersed in DMAc with a homomixer to prepare a titanium phosphate dispersion B2 (35% by weight) in place of the zirconium phosphate dispersion B1.

The polymer solutions a1, B2, and C1 were uniformly mixed at 96.98 wt%, 3 wt%, and 0.02 wt% to prepare a spinning dope D3. This was dry-spun in the same manner as in example 1 to obtain a filament package of 200g of polyurethane filaments having a content of 22dtex and 2 filaments and a titanium phosphate content of 3 wt%.

The results of the various evaluations are shown in tables 3, 4 and 5.

[ example 4]

Ethylmethylamine (molecular weight 89.14) was adjusted to 35% by weight in DMAc to prepare a monoamine solution C2 (35% by weight) in place of monoamine solution C1.

The polymer solutions a1, B1, and C2 were uniformly mixed in amounts of 94.88 wt%, 5 wt%, and 0.12 wt%, to prepare a spinning dope D4. This was dry-spun in the same manner as in example 1 to obtain 200g of a spun polyurethane yarn having 22dtex, 2 filaments, and a zirconium phosphate content of 5 wt%.

The results of the various evaluations are shown in tables 3, 4 and 5.

[ example 5]

Diisopropylamine (molecular weight 101.19) was adjusted to 35 wt% in DMAc to prepare a monoamine solution C3(35 wt%) instead of monoamine solution C1.

The polymer solutions a1, B1, and C3 were uniformly mixed at 99.35 wt%, 0.5 wt%, and 0.15 wt% to prepare a spinning dope D5. This was dry-spun in the same manner as in example 1 to obtain 200g of a spun polyurethane yarn having 22dtex, 2 filaments, and a zirconium phosphate content of 0.5 wt%.

The results of the various evaluations are shown in tables 3, 4 and 5.

[ example 6]

Isopropyl methylamine (molecular weight 73.14) was adjusted to 35 wt% in DMAc to make a monoamine solution C4(35 wt%) instead of monoamine solution C1.

The polymer solutions a1, B1, and C4 were uniformly mixed in an amount of 89.5 wt%, 10.0 wt%, and 0.5 wt% to prepare a spinning dope D6. This was dry-spun in the same manner as in example 1 to obtain a spun yarn of polyurethane yarn of 22dtex and 2 filaments, the content of zirconium phosphate being 10% by weight, and 200g of a wound yarn. However, the yarn breakage, which is considered to be the clogging of the die, occurs during the spinning process, and the spinnability is not good.

The results of the various evaluations are shown in tables 3, 4 and 5.

[ example 7]

N-butylamine (molecular weight: 73.14) was prepared at 35% by weight in DMAc to prepare a monoamine solution C5 (35% by weight) in place of the monoamine solution C1.

The polymer solutions a1, B1, and C5 were uniformly mixed at 95.9 wt%, 4.0 wt%, and 0.1 wt% to prepare a dope D7. This was dry-spun in the same manner as in example 1 to obtain a spun yarn of polyurethane yarn of 22dtex and 2 filaments, the content of zirconium phosphate being 4% by weight, and 200g of a wound yarn.

The results of the various evaluations are shown in tables 3, 4 and 5.

[ example 8]

The polymer solutions a1, B2, and C1 were uniformly mixed at 92.9 wt%, 7.0 wt%, and 0.1 wt% to prepare a dope D8. This was dry-spun in the same manner as in example 1 to obtain a filament package of 200g of polyurethane filaments having a content of 22dtex, 2 filaments, and 7 wt% of titanium phosphate.

The results of the various evaluations are shown in tables 3 and 4.

[ example 9]

Separately synthesized zirconium phosphate (average primary particle diameter 3.5 μm) was dispersed in DMAc with a homomixer to prepare zirconium phosphate dispersion B3(35 wt%) instead of zirconium phosphate dispersion B1.

The polymer solutions a1, B3, and C1 were uniformly mixed at 97.4 wt%, 2.5 wt%, and 0.1 wt% to prepare a dope D9. This was dry-spun in the same manner as in example 1 to obtain a 50g filament package of 22dtex polyurethane filaments containing 2 filaments and 2.5 wt% of titanium phosphate. However, a large number of broken threads, which are considered to be the clogging of the die, occur during the spinning process, and the spinnability is poor.

The results of the various evaluations are shown in tables 3, 4 and 5.

[ example 10]

The polymer solutions a1, B1, and C1 were uniformly mixed at 93.9 wt%, 6 wt%, and 0.01 wt% to prepare a spinning dope D10. This was dry-spun in the same manner as in example 1 to obtain a spun yarn of polyurethane yarn of 22dtex and 2 filaments, the content of zirconium phosphate being 6 wt%, and 200g of a wound yarn.

The results of the various evaluations are shown in tables 3, 4 and 5.

[ example 11]

A DMAC solution (35 wt%) of a polyurethane urethane polymer composed of PTMG having a molecular weight of 2100, MDI, ethylene glycol, and 1-butanol as a capping agent was prepared. Next, a polyurethane solution ("Methacrol" (registered trademark) 2462 manufactured by dupont) and a polycondensate of cresol and divinylbenzene ("Methacrol" (registered trademark) 2390 manufactured by dupont) were mixed in a ratio of 2 to 1 (weight ratio) to prepare an antioxidant DMAc solution (concentration 35 wt%). 96 parts by weight of the DMAc solution of the polyurethane polymer and 4 parts by weight of the antioxidant DMAc solution were mixed to prepare a polymer solution A2.

A quaternary ammonium salt compound "BARQUAT" (registered trademark) MS-100 (benzyldimethyltetradecylammonium chloride) manufactured by Longsha Japan K.K. (ロンザジャパン Co., Ltd.) was adjusted to 35% by weight in DMAc to prepare an antibacterial agent solution C6.

The polymer solutions a2, B1, C1 and C6 were uniformly mixed at 96.8 wt%, 2.5 wt%, 0.2 wt% and 0.5 wt% to prepare a spinning dope D11. This was dry-spun in the same manner as in example 1 to obtain a 200g filament package of 22dtex polyurethane filaments with 2 filaments and a zirconium phosphate content of 2.5 wt%.

The results of the various evaluations are shown in tables 3, 4 and 5.

[ example 12]

An aluminum dihydrogen tripolyphosphate deodorant "K-FRESH" (registered trademark) #100P (average primary particle diameter 1.0 μm) manufactured by Imperial chemical Co., Ltd. (テイカ Co., Ltd.) was dispersed in DMAc with a homomixer to prepare an aluminum dihydrogen tripolyphosphate dispersion B4 (35% by weight) in place of the zirconium phosphate dispersion B1.

The polymer solutions a1, B4, and C1 were uniformly mixed at 94.8 wt%, 5 wt%, and 0.2 wt% to prepare a dope D12. This was dry-spun in the same manner as in example 1 to obtain 200g of a spun polyurethane yarn having a content of 22dtex, 2 filaments, and aluminum dihydrogen tripolyphosphate of 5 wt%.

The results of the various evaluations are shown in tables 3, 4 and 5.

[ example 13]

The polymer solutions a2, B1, and C1 were uniformly mixed at 96.9 wt%, 3 wt%, and 0.1 wt% to prepare a dope D13. This was dry-spun in the same manner as in example 1 to obtain a spun yarn of polyurethane yarn of 22dtex and 2 filaments, the content of zirconium phosphate being 3% by weight, and 200g of a wound yarn.

The results of the various evaluations are shown in tables 3, 4 and 5.

[ example 14]

PTMG having a molecular weight of 1800 and MDI were mixed at a molar ratio of 1:1.58, and reacted at 90 ℃ for 2 hours to prepare an isocyanate-terminated prepolymer, which was then dissolved in DMAc to make 35 wt% of the prepolymer solution. Further, ethylenediamine as a chain extender and diethylamine as a chain terminator were mixed at a ratio of 14:1 of the concentration of the amino end group, and dissolved in DMAc to 35% by weight to prepare an amine solution.

The prepolymer solution and the amine solution were mixed with stirring under conditions that the molar ratio of the isocyanate terminal group to the amine terminal group was 1:1.06 to prepare a DMAC solution (35 wt%) of a polyurethaneurea polymer. Next, a polyurethane solution ("Methacrol" (registered trademark) 2462 manufactured by dupont) and a polycondensate of cresol and divinylbenzene ("Methacrol" (registered trademark) 2390 manufactured by dupont) were mixed in a ratio of 2 to 1 (weight ratio) to prepare an antioxidant DMAc solution (concentration: 35 wt%), and 96 parts by weight of the above polyurethane polymer DMAc solution and 4 parts by weight of the antioxidant DMAc solution were mixed to prepare a polymer solution a 3.

The polymer solutions a3 and B1 were uniformly mixed at 97 wt% and 3 wt% to prepare a dope D14. This was dry-spun in the same manner as in example 1 to obtain a spun yarn of polyurethane yarn of 22dtex and 2 filaments, the content of zirconium phosphate being 3% by weight, and 200g of a wound yarn.

The results of the various evaluations are shown in tables 3, 4 and 5.

[ example 15]

An antibacterial agent solution C7 was prepared by adding 35% by weight of "Nissan Container" (registered trademark) EQ-01D, a quaternary ammonium salt compound manufactured by Nissan chemical Co., Ltd., to DMAc.

The polymer solutions a1, B1, C1 and C7 were uniformly mixed at 96.8 wt%, 2.5 wt%, 0.2 wt% and 0.5 wt% to prepare a spinning dope D15. This was dry-spun in the same manner as in example 1 to obtain a 200g filament package of 22dtex polyurethane filaments with 2 filaments and a zirconium phosphate content of 2.5 wt%.

The results of the various evaluations are shown in tables 3, 4 and 5.

[ example 16]

A quaternary ammonium salt compound "NeojaamiDFS" manufactured by Sanyo chemical Co., Ltd was prepared in DMAc to prepare a solution C8(35 wt%).

The polymer solutions a3, B1, and C8 were uniformly mixed at 96.5 wt%, 2.5 wt%, and 1 wt% to prepare a dope D16. This was dry-spun in the same manner as in example 1 to obtain a 200g filament package of 22dtex polyurethane filaments with 2 filaments and a zirconium phosphate content of 2.5 wt%.

The results of the various evaluations are shown in tables 3, 4 and 5.

[ example 17]

The polymer solutions a3, B1, and C8 were uniformly mixed at 97.4 wt%, 2.5 wt%, and 0.1 wt% to prepare a dope D17. This was dry-spun in the same manner as in example 1 to obtain a 200g filament package of 22dtex polyurethane filaments with 2 filaments and a zirconium phosphate content of 2.5 wt%.

The results of the various evaluations are shown in tables 3, 4 and 5.

Comparative example 1

The polymer solution a1 was dry-spun in the same manner as in example 1 to obtain a 22dtex, 2 monofilament polyurethane yarn in 200g package.

The results of the various evaluations are shown in tables 3, 4 and 5.

Comparative example 2

The polymer solutions a1 and B1 were uniformly mixed in an amount of 97.5 wt% and 2.5 wt% to prepare a dope D18. This was dry-spun in the same manner as in example 1 to obtain a 200g filament package of 22dtex polyurethane filaments with 2 filaments and a zirconium phosphate content of 2.5 wt%.

The results of the various evaluations are shown in tables 3, 4 and 5.

Comparative example 3

The polymer solutions a1 and C2 were uniformly mixed in an amount of 99.8 wt% and 0.2 wt% to prepare a dope D19. This was dry-spun in the same manner as in example 1 to obtain a 22dtex, 2 monofilament, 200g filament winding of polyurethane filaments.

The results of the various evaluations are shown in tables 3, 4 and 5.

Comparative example 4

Silver-containing zeolite "Zeomikku" (registered trademark) SW-10N (average primary particle diameter 1.0 μm), manufactured by Takawa Fuel Ltd. (シナネンゼオミック Co., Ltd.), was dispersed in DMAc with a homomixer to prepare a zeolite dispersion B3 (35% by weight) in place of the zirconium phosphate dispersion B1.

The polymer solutions a1 and B3 were uniformly mixed at 96 wt% and 4 wt% to prepare a dope D20. This was dry-spun in the same manner as in example 1 to obtain a 22dtex, 2-filament, 200g of a polyurethane filament with a silver-containing zeolite content of 4 wt%.

The results of the various evaluations are shown in tables 3, 4 and 5.

Comparative example 5

Diamylamine (molecular weight 157.3) was adjusted to 35% by weight in DMAc to prepare a monoamine solution C9 (35% by weight) in place of the monoamine solution C1.

The polymer solutions a1, B1, and C9 were uniformly mixed at 97.9 wt%, 2.0 wt%, and 0.1 wt% to prepare a dope D21. This was dry-spun in the same manner as in example 1 to obtain a filament package of 200g of 22dtex polyurethane filament with 2 monofilaments and a zirconium phosphate content of 2 wt%.

The results of the various evaluations are shown in tables 3, 4 and 5.

Comparative example 6

High-silica zeolite HSZ-980HOA (average primary particle size: 2.0 μm) manufactured by Tosoh corporation (manufactured by DONG' O ソー Co., Ltd.) was dispersed in DMAc by a homomixer to prepare a zeolite dispersion B5 (35% by weight) in place of the zirconium phosphate dispersion B1.

The polymer solutions a1, B5, and C1 were uniformly mixed at 96.8 wt%, 3 wt%, and 0.2 wt% to prepare a dope D22. This was dry-spun in the same manner as in example 1 to obtain 200g of a spun polyurethane yarn having 22dtex, 2 filaments, and a zeolite content of 3 wt%.

The results of the various evaluations are shown in tables 3, 4 and 5.

Comparative example 7

Ultramicroparticulate zinc oxide "FINEX" -25 (average primary particle diameter 0.04 μm) made by Sakai chemical corporation was dispersed in DMAc with a homomixer to prepare zinc oxide dispersion liquid B6 (35% by weight) in place of zirconium phosphate dispersion liquid B1.

The polymer solutions a1, B6, and C1 were uniformly mixed at 96.9 wt%, 3 wt%, and 0.1 wt% to prepare a dope D23. This was dry-spun in the same manner as in example 1 to obtain a filament package of 200g of polyurethane filaments having 22dtex and 2 filaments and a zinc oxide content of 3 wt%.

The results of the various evaluations are shown in tables 3, 4 and 5.

Comparative example 8

The natural antibacterial agent hinokitiol was adjusted to 35% by weight in DMAc to prepare a solution C10 (35% by weight) instead of the monoamine solution C1.

The polymer solutions a1, B6, and C10 were uniformly mixed at 96.9 wt%, 3 wt%, and 0.1 wt% to prepare a dope D24. This was dry-spun in the same manner as in example 1 to obtain a filament package of 200g of polyurethane filaments having 22dtex and 2 filaments and a zinc oxide content of 3 wt%.

The results of the various evaluations are shown in tables 3, 4 and 5.

Comparative example 9

The polymer solutions a1 and C8 were uniformly mixed at 99 wt% and 1 wt% to prepare a dope D25. This was dry-spun in the same manner as in example 1 to obtain a filament package of 200g of polyurethane filaments having 22dtex and 2 filaments and a zinc oxide content of 3 wt%.

The results of the various evaluations are shown in tables 3, 4 and 5.

Comparative example 10

A silver-containing antibacterial agent "NOVARON" (registered trademark) AGT330 (average primary particle diameter: 0.5 μm) manufactured by Toyo Seisaku-Sho K.K., was dispersed in DMAc with a homomixer to prepare an inorganic antibacterial agent dispersion C11 (35% by weight) in place of the monoamine solution C1. The polymer solutions a1, B1, B6 and C11 were uniformly mixed at 96.5 wt%, 1.5 wt%, 1.0 wt% and 1.0 wt% to prepare a spinning dope D26. This was dry-spun in the same manner as in example 1 to obtain a 200g filament package of 22dtex polyurethane filaments with 2 filaments and a zirconium phosphate content of 1.5 wt%.

The results of the various evaluations are shown in tables 3, 4 and 5.

Comparative example 11

The polymer solutions a2 and B1 were uniformly mixed in an amount of 97.5 wt% and 2.5 wt% to prepare a dope D27. This was dry-spun in the same manner as in example 1 to obtain a 200g filament package of 22dtex polyurethane filaments with 2 filaments and a zirconium phosphate content of 2.5 wt%.

The results of the various evaluations are shown in tables 3, 4 and 5.

[ Table 3]

[ Table 4]

[ Table 5]

Industrial applicability

Since the elastic polyurethane yarn of the present invention is excellent in stretchability, deodorant properties, antibacterial properties, and discoloration resistance, a fabric excellent in stretchability, deodorant properties, antibacterial properties, and discoloration resistance can be obtained by using the elastic polyurethane yarn.

Description of the symbols

Outer diameter of A pack

Outer diameter of B paper tube

Width of filament coil at outermost layer C

D width of innermost layer of wire coil

Claims

1. A polyurethane elastic yarn comprising polyurethane which is obtained by using polymer diol and diisocyanate as starting materials, wherein the elastic yarn contains metal phosphate and the emission amount of monoamine compound having a molecular weight of 120 or less is 100 [ mu ] g/m²In the above, when reacting an isocyanate group and an amino group, a chain extender and the monoamine compound are used in combination, the ratio of the amino group in the chain extender to the amino group in the monoamine compound is in the range of 5:1 to 25:1, and the molar ratio of the isocyanate group concentration to the amino end group concentration during the reaction is in the range of 1:1.04 to 1:1.15.

2. The polyurethane elastic yarn according to claim 1, wherein the metal phosphate is contained in an amount of 0.5 to 10 wt%.

3. The polyurethane elastic yarn according to claim 1 or 2, wherein the metal phosphate has an average primary particle diameter of 3.0 μm or less.

4. The polyurethane elastic wire as claimed in claim 1 or 2, wherein the metal phosphate is at least one selected from the group consisting of titanium phosphate, zirconium phosphate and aluminum dihydrogen tripolyphosphate.

5. The polyurethane elastic yarn according to claim 1 or 2, wherein the monoamine compound to be emitted is a secondary monoamine compound.

6. The polyurethane elastic yarn according to claim 1 or 2, further comprising a quaternary ammonium salt compound.

7. The polyurethane elastic yarn according to claim 6, wherein the quaternary ammonium salt-based compound has the following structure:

[ solution 1]

Wherein,

r3 is an alkyl group having 10 to 22 carbon atoms;

x-is an acidic counterion.

8. The polyurethane elastic yarn according to claim 6, wherein the quaternary ammonium salt compound is contained in an amount of 0.1 to 5 wt%.

9. A process for producing a polyurethane elastic yarn, which comprises mixing a metal phosphate with a spinning dope containing a polyurethane starting from a polymer diol and a diisocyanate, and simultaneously mixing a monoamine compound having a molecular weight of 120 or less so that the content of the monoamine compound is in the range of 0.01 to 0.5 wt.% relative to the spinning dope, and dry-spinning the spinning dope, wherein a chain extender and the monoamine compound are mixed for use when reacting an isocyanate group with an amino group, the ratio of the amino group in the chain extender to the amino group in the monoamine compound is in the range of 5:1 to 25:1, and the molar ratio of the isocyanate group concentration to the amino end group concentration during the reaction is in the range of 1:1.04 to 1: 1.15.

10. The method for manufacturing polyurethane elastic yarns according to claim 9, wherein the metal phosphate is mixed in the form of a dispersion in the spinning dope containing polyurethane starting from polymer diol and diisocyanate.

11. The method for manufacturing the polyurethane elastic wire according to claim 9 or 10, wherein the metal phosphate is at least one selected from the group consisting of titanium phosphate, zirconium phosphate, and aluminum dihydrogen tripolyphosphate.

12. The method for producing a polyurethane elastic yarn according to claim 9 or 10, wherein the monoamine compound having a molecular weight of 120 or less is a secondary amine compound.