TWI553176B - Polyurethane elastic yarn and method for producing the same - Google Patents

Description

Polyurethane elastic yarn and manufacturing method thereof

The present invention relates to a polyurethane elastic yarn which is excellent in antibacterial property and deodorizing property and excellent in color solidity, and is suitable for obtaining an antimicrobial property with respect to a polyurethane elastic yarn. Deodorant fabric; and its manufacturing method.

Because of its excellent stretch characteristics, the elastic fiber is widely used for stretchable clothing applications such as leg clothing, underwear, and sportswear, sanitary applications such as disposable diapers and sanitary napkins (use of sanitary materials), and industrial materials.

In recent years, under the demand of a more comfortable living environment, antibacterial coatings, antibacterial film ‧ tablets, antibacterial monofilament, antibacterial cosmetics, antibacterial kitchen supplies, antibacterial stationery, antibacterial sand, antibacterial toilet paper, antibacterial So-called "antibacterial products" such as fibers and antibacterial cosmetics are gradually appearing in the market. In addition, similarly, "deodorant products" such as clothing and bedding having a deodorizing function such as age-related odor are listed.

As an antibacterial agent used for such products, in particular, an inorganic antibacterial agent can be seen as a silver-based antibacterial agent. Further, examples of the deodorant include activated carbon, silver-containing zeolite, zeolite, and fine particle zinc oxide.

The inorganic antibacterial agent has excellent weather resistance, chemical resistance, and excellent acute oral toxicity as compared with the organic antibacterial agent. In addition, the heat resistance is significantly higher than that of the organic antibacterial agent. Therefore, an inorganic antibacterial agent is added to a synthetic resin and used in many fields. However, when an inorganic antibacterial agent is added to the synthetic resin and molded, the effect of the metal contained in the inorganic antibacterial agent, the heat during molding or the light that is irradiated onto the molded article, tends to cause discoloration of the molded article, and the value of the product. Significantly reduced problems.

Therefore, many techniques for suppressing thermal discoloration of an antibacterial resin to which an inorganic antibacterial agent is added have been proposed (Patent Document 1). However, although these techniques can achieve certain performance in antibacterial and deodorizing properties, it is difficult to say that the fading resistance greatly distorts with the environment or time.

In addition, there has been proposed an antibacterial deodorizing polyurethane elastic fiber containing ceramyl alcohol as a natural antibacterial agent for an organic antibacterial agent and containing a compound selected from the group consisting of Zn, Si, Cu, Ni, Fe, Al, and Mg. The metal oxide and/or the composite metal oxide of at least one element (Patent Document 2) is considered to have a certain effect on the antibacterial property and deodorizing property of the polyurethane elastic yarn. However, the antibacterial agent of eucalyptus is considered to be sublimated by the heat in the dry spinning, and therefore it is necessary to contain a large amount in the spinning stock solution in advance. In addition, since the residual amount of eucalyptus varies depending on the heat condition of the spinning, etc., it is difficult to produce a polyurethane elastic yarn which retains stable antibacterial properties. In addition, since the natural antibacterial agent of eucalyptus is expensive, there is a problem in terms of cost.

Further, there is also a proposal to use an organic synthetic antibacterial agent (Patent Document 3). When it is used alone, it does not have the effect of deodorizing property, and there is a problem in the aspect of achieving both antibacterial property and deodorizing property.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 4485871

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2002-105757

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2004-292471

An object of the present invention is to provide a polyurethane elastic yarn which is excellent in antibacterial property and deodorant property and excellent in color solidity; and a method for producing the same.

In order to solve the above problems, the present invention employs any of the following means.

(1) A polyurethane elastic yarn comprising an elastic yarn of a polyurethane containing a polymer diol and a diisocyanate as a starting material, which contains a metal phosphate and has a molecular weight of 120 or less. The amount of the monoamine compound released is 100 μg/m ² or more.

(2) The polyurethane elastic yarn according to the above (1), wherein the metal phosphate content is 0.5% by weight or more and 10% by weight.

(3) The polyurethane elastic 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 polyurethane elastic yarn according to any one of (1) to (3), wherein the metal phosphate is selected from the group consisting of titanium phosphate, zirconium phosphate, and aluminum dihydrogen phosphate. At least one of the constituent groups.

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

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

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

Further, R1 and R2 are hydrogen or an alkyl group having 1 to 3 carbon atoms (which may be the same or different), R3 is an alkyl group having 10 to 22 carbon atoms, and R4 is an alkyl group having 1 to 22 carbon atoms (which may be combined with R1). R2, R3 are the same or different), X- is an acidic relative ion

(8) The polyurethane elastic yarn according to the above (6) or (7), wherein the content of the quaternary ammonium salt compound is in the range of 0.1% by weight to 5% by weight.

(9) A method for producing a polyurethane elastic yarn by mixing a metal phosphate in a spinning stock solution containing a polyurethane having a polymer diol and a diisocyanate as a starting material, and simultaneously A monoamine compound having a molecular weight of 120 or less is mixed, and the content thereof is in a range of 0.01% by weight or more and 0.5% by weight or less based on the spinning stock solution, and the spinning stock solution is dry-spun.

(10) The method for producing a polyurethane elastic yarn according to the above (9), wherein the spinning stock solution containing the polyglycolate containing the polymer diol and the diisocyanate as a starting material Mixing the metal phosphate as a dispersion.

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

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

According to the present invention, since the main constituent component contains the elastic yarn of the polymer diol and the polyisocyanate of the diisocyanate, and contains the metal phosphate, the amount of the monoamine compound having a molecular weight of 120 or less is 100 μg/m ² or more. Therefore, a polyurethane elastic yarn excellent in stretchability, deodorant property, antibacterial property, and color stability can be obtained. Therefore, the fabric using the polyurethane elastic yarn is excellent in stretchability, deodorant property, antibacterial property, and color stability.

[Formation of the Invention]

The invention is further described in detail below.

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 polymer diol and a diisocyanate as a starting material. Further, the synthesis method is not particularly limited. That is, for example, it may be a polyurethane containing a polymer diol, a diisocyanate, and a low molecular weight diamine, or may be a polyurethane containing a polymer diol, a diisocyanate, and a low molecular weight diol. Carbamate. Further, it may be a polyurethane urethane which uses a compound having a hydroxyl group and an amine group in the molecule as a chain extender. A trifunctional or higher polyfunctional glycol or an isocyanate is preferably used insofar as it does not impair the effects of the present invention.

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

As the polyether diol, for example, polyethylene oxide, polyethylene glycol, a derivative of polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol (hereinafter abbreviated as PTMG), and tetrahydrofuran (THF) are preferably used. And denatured PTMG of a copolymer of 3-methyltetrahydrofuran (hereinafter abbreviated as 3M-PTMG); denatured PTMG of a copolymer of THF and 2,3-dimethyl THF, both sides disclosed in Japanese Patent No. 2615131 A polyol having a side chain; a random copolymer of THF and ethylene oxide and/or propylene oxide irregularly arranged, and the like. One type or a mixture of two or more kinds of the above polyether diols may be used in combination or copolymerization.

From the viewpoint of obtaining abrasion resistance or light resistance, it is preferable to use butylene adipate, polycaprolactone diol, JP-A-61-26612, etc. as the polyurethane elastic yarn. A polyester diol such as a polyester polyol having a side chain, a polycarbonate diol disclosed in JP-A No. 2-289516, and the like.

These polymer diols may be used singly or in combination of two or more kinds thereof or copolymerized.

The molecular weight of the polymer diol is preferably from 1,000 or more and 8,000 or less, more preferably from 1,500 to 6,000, from the viewpoint of the elongation, strength, heat resistance and the like at the time of obtaining the yarn. By using a polyol having a molecular weight within this range, an elastic yarn excellent in elongation, strength, elastic recovery, and heat resistance can be easily obtained.

Next, as the diisocyanate, an aromatic diisocyanate such as diphenylmethane diisocyanate (hereinafter abbreviated as MDI), toluene diisocyanate, 1,4-diisocyanate benzene, decyl diisocyanate or 2,6-naphthalene diisocyanate is particularly suitable. For the synthesis of high heat resistance and high strength polyurethane. Further, as the alicyclic diisocyanate, for example, methylene bis(cyclohexyl isocyanate) (hereinafter referred to as H12MDI), isophorone diisocyanate, methylcyclohexane 2,4-diisocyanate, methyl ring is preferable. Hexane 2,6-diisocyanate, cyclohexane 1,4-diisocyanate, hexahydroindole diisocyanate, hexahydrotoluene diisocyanate, octahydro 1,5-naphthalene diisocyanate, and the like. Aliphatic diisocyanates are particularly effective for inhibiting the fading of polyurethane elastomer yarns. Further, these diisocyanates may be used singly or in combination of two or more.

Next, it is preferred to use at least one of a low molecular weight diamine and a low molecular weight diol in the chain extender used in the synthesis of the polyurethane. Further, it may be a group having a hydroxyl group and an amine group in the molecule like ethanolamine.

Preferred examples of the low molecular weight diamine include ethylenediamine, 1,2-propylenediamine, 1,3-propanediamine, hexamethylenediamine, p-phenylenediamine, p-nonanediamine, and methylene diamine. Amine, p,p'-methylenediphenylamine, 1,3-cyclohexanediamine, hexahydroisophthalamide, 2-methylpentamethylenediamine, bis(4-aminophenyl) oxidation Phosphine and the like. It is preferable to use one or two or more of these. Particularly preferred is ethylenediamine. By using ethylenediamine, it is possible to easily obtain a yarn having excellent elongation and elastic recovery and further excellent heat resistance. In the chain extender, a triamine compound which can form a crosslinked structure, such as diethylenetriamine or the like, can be added to the extent that the effect is not lost.

Further, as the low molecular weight diol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, bishydroxyethoxybenzene, bishydroxyethylene terephthalate, 1-methyl-1 , 2-ethylene glycol and the like are representative. One or two or more of these are preferably used. Particularly preferred are ethylene glycol, 1,3-propanediol, and 1,4-butanediol. When these are used, the urethane-extended polyurethane has high heat resistance, and a yarn having high strength can be obtained.

The molecular weight of the polyurethane in the present invention is preferably in the range of 30,000 or more and 150,000 or less as the number average molecular weight from the viewpoint of obtaining fibers having high durability and strength. Further, the molecular weight is measured by GPC and converted by polystyrene.

In the polyurethane, it is also preferred to use one type of terminal mounting agent or a mixture of two or more types. As the terminal mounting agent, preferred are dimethylamine, diisopropylamine, ethylmethylamine, diethylamine, methylpropylamine, isopropylmethylamine, diisopropylamine, butylmethylamine, isobutylmethylamine, isopentyl. A monoamine such as methylamine, dibutylamine or dipentylamine, a monoalcohol such as ethanol, propanol, butanol, isopropanol, allyl alcohol or cyclopentanol, or a monoisocyanate such as phenyl isocyanate. In the case where the polyurethane is polymerized under the conditions that the amount of the monoamine compound having a molecular weight of 120 or less in the polyurethane elastic yarn is 100 μg/m ² , the molecular weight is preferably used. A monoamine of 120 or less is used as the terminal mounting agent.

In the present invention, the polyurethane elastic yarn containing the polyurethane having the above-described basic constitution does not interfere with the original possession of the polyurethane elastic yarn because it contains a metal phosphate. The deodorizing property of the acetic acid gas, the terpene gas, and the isoxalic acid gas can also improve the deodorizing property against ammonia gas. Further, the polyurethane elastic yarn is simultaneously contained with a monoamine compound having a molecular weight of 120 or less, and the release amount of the elastic polyurethane yarn is 100 μg/m ² or more, preferably 100 μg/ When m ² or more and 500 μg/m ² or less, excellent antibacterial properties can be maintained.

The metal phosphate in the present invention is preferably an acid phosphate of a tetravalent metal such as zirconium phosphate or titanium phosphate having a layer structure, and aluminum dihydrogenphosphate or the like. More preferably, it is zirconium phosphate. These may be used alone or in combination of two or more.

The content of the metal phosphate is preferably in the range of 0.5% by weight or more and 10% by weight or less based on the total weight of the polyurethane elastomer yarn. When the content of the metal phosphate is less than 0.5% by weight, it is difficult to obtain sufficient ammonia deodorizing property when the fabric is formed, which is not preferable. More preferably, it is 1.0% by weight or more. On the other hand, when the content exceeds 10% by weight, the stretchability is deteriorated and the cost is not good. More preferably, it is 7.0% by weight or less. In consideration of the balance between the deodorizing property and the physical properties of ammonia gas and the cost, it is particularly preferably in the range of 1.5% by weight or more and 5.0% by weight or less.

From the viewpoint of suppressing the spinning stock solution from blocking the spinning metal spun, the metal phosphate is preferably one having an average primary particle diameter of 3.0 μm or less. More preferably, it is 1.5 μm or less. Further, from the viewpoint of dispersibility, when the average primary particle diameter is smaller than 0.05 μm, the cohesive force is increased, and it becomes difficult to uniformly mix in the spinning stock solution, and the average primary particle diameter is 0.05 μm or more. good. More preferably, it is 0.15 μm or more.

On the other hand, in order to reduce the amount of the monoamine compound having a molecular weight of 120 or less from the polyurethane elastic yarn to 100 μg/m ² or more, for example, it is preferred to contain the polyalkate-containing spinning stock solution to 0.01. Spinning of a monoamine compound in a range of wt% or more and 0.5 wt% or less. The content of the monoamine compound in the spinning dope is less than 0.01% by weight, which means that the polyurethane elastic yarn after spinning does not contain sufficient monoamine, and as a result, sufficient antibacterial property cannot be obtained. On the other hand, when the monoamine compound contained in the spinning stock solution is 0.5% by weight or more, the obtained polyurethane elastic yarn is deteriorated in quality such as fading property.

In addition, even if a monoamine is not added after the polymerization, and a monoamine having a molecular weight of 120 or less is used as a terminal mounting agent in synthesizing the polyurethane, the monoamine compound in the elastic polyester yarn can also be obtained. The amount of elution is 100 μg/m ² or more. Specifically, when the isocyanate group is reacted with an amine group, it is preferred to use a chain extender such as a diamine compound in advance and the monoamine compound. The ratio of the amine group in the chain extender to the amine group of the monoamine compound at this time is preferably in the range of 5:1 to 25:1. More preferably, it is in the range of 5:1 to 20:1. The amount of the mixture of the chain extender and the monoamine compound used in the reaction is preferably such that the molar ratio of the isocyanate group concentration to the amine terminal group concentration in the reaction is in the range of 1:1.04 to 1:1.15. Thereby, a polymer solution containing more amine groups than in the usual polymerization can be produced, and the release amount of the monoamine of the yarn after spinning can be ensured to be 100 μg/m ² or more.

Examples of the monoamine compound having a molecular weight of 120 or less include diethylamine, dimethylamine, diisopropylamine, ethylmethylamine, N-methylpropylamine, isopropylmethylamine, N-butylmethylamine, and N-methyl. A secondary amine compound such as isobutylamine or a primary amine compound such as ethylamine, N-propylamine, isopropylamine, N-butylamine or cyclohexylmonoamine. From the viewpoint of the stability of the polyurethane spinning stock solution, a secondary amine compound is preferred.

In order to further improve the antibacterial property of the above-mentioned polyurethane elastic yarn, it is preferred to further contain a 4-grade ammonium salt compound. The fourth-order ammonium salt compound differs in the antimicrobial strength depending on the alkyl chain length in the ammonium ion. If the chain length of the alkyl group is long, the antimicrobial activity is likely to be high. Further, if the chain length is too short, it is liable to volatilize or deteriorate due to heat during spinning. On the other hand, if the chain length of the alkyl group is too long, the usability is deteriorated. Therefore, it is preferred to select a chain type such as an alkyl group and a chain length in order to obtain desired characteristics.

From the viewpoint of antibacterial power, particularly preferred ammonium ions are stearin trimethylammonium ion, cetyltrimethylammonium ion, dimercaptodimethylammonium ion, oil sulfhydryltrimethylammonium ion, and the like. These generally have a structure which can be supplied by an organic acid salt of a sulfonate, a phosphate or the like or a salt of a chloride, a bromide, an iodide or the like. Among them, a sulfonate is preferred from the viewpoint of stability of discoloration and heat resistance.

In addition,

R1 and R2 are hydrogen or an alkyl group having 1 to 3 carbon atoms (which 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 (which may be the same as or different from R1, R2, and R3).

X- is an acidic relative ion

Specific examples of the salt having the above configuration include dimercaptodimethylammonium 3 fluorinated methylsulfonate, di-n-decyldimethylammonium trifluoromethanesulfonate, and di-n-decyldimethylammonium salt. Pentafluoroethane sulfonate, n-hexadecyltrimethylammonium triflate, and benzyldimethylcocoalkylammonium pentafluoroethane sulfonate.

From the viewpoint of exhibiting an antibacterial property and maintaining a balance between discoloration and stretching characteristics, the quaternary ammonium salt compound preferably contains a range of 0.1% by weight or more and 5% by weight or less based on the total weight of the polyurethane conjugated elastic yarn. Further, it is more preferably in the range of 0.2% by weight or more and 2% by weight or less.

Further, various stabilizers, pigments, and the like may be further contained in the polyurethane elastic yarn. It is also preferable to contain, for example, a light-resistant agent, an antioxidant, a hindered phenol-based drug such as "Sumilizer" (registered trademark) GA-80 manufactured by Sumitomo Chemical Co., Ltd., and "TINUVIN" manufactured by Ciba-Geigy Co., Ltd. A benzotriazole-based or diphenyl ketone-based pharmaceutical agent such as a registered trademark), a phosphorus-based agent such as "Sumilizer" (registered trademark) P-16 manufactured by Sumitomo Chemical Co., Ltd., various hindered amine-based agents, and iron oxide. Various pigments such as titanium oxide, inorganic materials such as zinc oxide, cerium oxide, magnesium oxide, calcium carbonate, and carbon black; metal soaps such as fluorine-based or polyoxynized resin powders; magnesium stearate; A slip agent such as oxygen or mineral oil, various antistatic agents such as cerium oxide, betaine or phosphoric acid, and the like, and it is preferred to react with the polymer. In particular, in order to further improve the durability against light or various kinds of nitrogen oxides, etc., it is also preferable to use, for example, a nitrogen oxide supplement such as HN-150 manufactured by Nippon Bismuth Co., Ltd., "Sumilizer" manufactured by Sumitomo Chemical Co., Ltd. "Thermal stabilizer for "Sumisoap" (registered trademark) 30.0#622, manufactured by Sumitomo Chemical Co., Ltd., is a thermal oxidation stabilizer such as (registered trademark) GA-80.

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

In the present invention, a polymer diol and a diisocyanate are used as a starting material, and a spinning solution of the polyurethane obtained from the above contains (i.e., exists) a metal phosphate and has a molecular weight of 120. Spinning with the following monoamine compound. From the viewpoint of stabilizing the polymerization, it is preferred to prepare a polyurethane solution in advance, and to add a metal phosphate dispersion liquid and a monoamine compound having a molecular weight of 120 or less. Further, the "spinning stock solution" in the present invention means a liquid which is finally used for spinning, and on the other hand, a polyurethane solution means a solution containing a polyurethane, which can be in any state. liquid.

The method for producing the polyurethane solution and the method for preparing the solute urethane in the solution may be either a melt polymerization method or a solution polymerization method, or may be other methods. However, a solution polymerization method is preferred. In the case of the solution polymerization method, a small amount of foreign matter such as a colloid generated in the polyurethane is easy to be spun, and a low-density polyurethane elastic yarn can be easily obtained. Also in the case of solution polymerization, of course, the advantage of the operation of making the solution can be omitted.

The polyurethane may be a polymer diol, a diisocyanate or a chain extender as described above, and may be polymerized as needed using an end mounting agent as described above. As a particularly suitable polyurethane, PTMG having a molecular weight of 1500 or more and 6000 or less as a polymer diol, MDI as a diisocyanate, ethylenediamine as a chain extender, and 1,2-propane II can be used. At least one of an amine, a 1,3-propanediamine, and a hexamethylenediamine is synthesized.

The polyurethane is obtained by, for example, DMAc, DMF, DMSO, NMP, or the like, or a solvent containing the above-mentioned raw materials. As a particularly suitable method, for example, each raw material can be put into such a solvent and dissolved, and heated to a moderate temperature to cause a reaction to form a polyurethane, which is a so-called single-plug method (one- In addition, there is a method of first reacting a polymer diol with a diisocyanate, then dissolving the reactant in a solvent, and reacting with the aforementioned chain extender to prepare a polyurethane.

When a diol is used as a chain extender, from the viewpoint of obtaining excellent heat resistance, it is preferred to adjust the melting point of the high temperature side of the polyurethane to a range of from 200 ° C to 260 ° C. A representative method can be achieved by controlling the type and ratio of polymer diol, MDI, diol. When the molecular weight of the polymer diol is low, by increasing the ratio of MDI relatively, a high-melting-point polyurethane can be obtained, and similarly, when the molecular weight of the diol is low, it is relatively reduced. The ratio of the polymer diol can give a polyurethane having a high melting point on the high temperature side.

When the molecular weight of the polymer diol is 1800 or more, in order to make the melting point of the high temperature side 200 ° C or more, it is preferable to carry out (the molar number of MDI) / (the number of moles of the polymer diol) = 1.5 or more. polymerization.

Further, in the synthesis of the polyurethane, it is preferred to use one or a mixture of two or more kinds of catalysts such as an amine catalyst or an organic metal catalyst.

Examples of the amine-based catalyst include N,N-dimethylcyclohexylamine, N,N-dimethylbenzylamine, triethylamine, and N-methyl. Porphyrin, N-ethyl Porphyrin, 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'-dimethylperazine , N-methyl-N'-dimethylamine ethylpipe , N-(2-dimethylaminoethyl) Porphyrin, 1-methylimidazole, 1,2-dimethylimidazole, N,N-dimethylaminoethanol, N,N,N'-trimethylamine ethylethanolamine, N-methyl-N' -(2-hydroxyethyl) piperidine 2,4,6-gin(dimethylaminomethyl)phenol, N,N-dimethylaminohexanol, triethanolamine, and the like.

Further, examples of the organic metal catalyst include tin octylate, dibutyltin dilaurate, and dibutyl lead octoate.

In the present invention, a metal phosphate and a monoamine compound having a molecular weight of 120 or less are preferably added to the polyurethane solution to prepare a spinning dope.

The method of adding the metal phosphate and the monoamine compound in the polyurethane solution may be any method. As a representative method, various means such as a method using a static stirrer, a method of 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 separately added to the polyurethane solution, or may be added to the polyurethane solution after premixing. From the viewpoint of exhibiting deodorizing properties against ammonia gas, it is preferred to add these to the polyurethane solution after mixing them in advance to prepare a dispersion.

In order to improve the deodorizing property to ammonia gas, the polyurethane elastic yarn preferably contains a metal phosphate in a range of 0.5% by weight or more and 10% by weight or less. Therefore, it is necessary to uniformly disperse the metal phosphate in the range of 0.5% by weight or more and 10% by weight or less of the spinning dope in the pre-spinning spinning stock solution, preferably in N, N- a metal urethane solution in which a solvent such as dimethylformamide or N,N-dimethylacetamide is added to the solution, and the mixture is stirred and mixed to uniformly disperse it to obtain a spun. Yarn stock solution.

Specifically, it is preferred to disperse a metal phosphate in a solvent such as N,N-dimethylformamide or N,N-dimethylacetamide to prepare a metal phosphate dispersion. The dispersion was mixed into a polyurethane solution. Here, from the viewpoint of uniformly adding to the polyurethane solution, the solvent of the metal phosphate dispersion to be added is preferably the same solvent as the polyurethane solution. Further, when a metal phosphate is added to the polyurethane solution, the aforementioned chemicals such as a light stabilizer, an antioxidant, or the like may be simultaneously added.

Further, in the present invention, after the polymerization of the polyurethane, the monoamine is added to the solution containing the polyurethane, and a monoamine having a molecular weight of 120 or less can be used in a large amount as the synthetic polyaminocarboxylic acid. The terminal mounting agent in the case of ethyl ester, and the monoamine compound is present in the spinning stock solution finally supplied to the spinning.

In the present invention, as described above, the metal phosphate and the monoamine having a molecular weight of 120 or less are present in the spinning dope together with the polyurethane, and in order to improve the antibacterial property against various bacteria, it is preferred to spin. The monoamine compound having a molecular weight of 120 or less is contained in the stock solution in a range of 0.01% by weight or more and 0.5% by weight or less.

Further, the concentration of the polyurethane in the polyurethane spinning stock solution is usually preferably in the range of 30% by weight or more and 80% by weight or less.

Further, in the present invention, in order to improve the antibacterial property against various bacteria, it is preferred to contain a quaternary ammonium salt compound. Therefore, the pre-spinning polyurethane spinning dope contains the above-described quaternary ammonium salt compound as described above and is spun. The method of containing the fourth-order ammonium salt compound in the spinning stock solution may be mixed with the polyurethane solution alone or may be mixed with the metal phosphate dispersion liquid in advance.

The spinning dope composed as described above is, for example, dry-spun, wet-spun, or melt-spun, and wound, to obtain the polyurethane elastic yarn of the present invention. Among them, from the viewpoint of stable spinning from fine to coarse various fineness, dry spinning is preferred.

The fineness, 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 yarn may be circular, and may be flat.

Further, the dry spinning method is not particularly limited, and it is only necessary to appropriately select a spun yarn corresponding to a desired property or a spinning condition of a spinning device.

For example, the permanent strain rate and the stress relaxation rate of the polyurethane elastic yarn of the present invention are particularly susceptible to the speed ratio of the guide roller and the winder, and therefore it is preferable to appropriately determine 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 preferred that the speed ratio of the guide roller to the coiler is in the range of 1.10 or more and 1.65 or less. Wrap around.

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

[Examples]

The invention will be described in further detail by way of examples.

[Strength, Stress Relaxation Rate, Permanent Strain Rate, and Elongation of Polyurethane Elastic Yarn]

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

These are defined by the following.

That is, a 5 cm (L1) sample was stretched 300% at a stretching speed of 50 cm/min five times. This fifth stress is defined as (G1). Next, this 300% elongation state was maintained for 30 seconds. The stress after 30 seconds is maintained as (G2). Then, the elongation is recovered, and when the stress is 0, the length of the sample yarn is set to (L2). The sample yarn was further stretched to break at the sixth time. The stress at the time of the fracture was set to (G3), and the length of the sample yarn at the time of the fracture was set to (L3).

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

Strength [cN]=(G3)

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

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

Elongation [%]=100×((L3)-(L1))/(L1)

Further, the tensile test was carried out three times and was determined from the average value.

[Production of weaving material for evaluation of deodorant and antibacterial properties]

The 22dtex polyurethane elastic yarn was stretched to 3 times, and it was used as a sheath yarn of polyamide processing yarn (trademark QuuP, Toray (share), 33 points, decitex, 26 shares Silk) was coated with a number of turns of 800 T/m to produce single-coated yarns (SCY) of S捻 and Z捻.

Furthermore, the above-mentioned S捻SCY was supplied to the yarn feeders 1, 3 of the pantyhose knitting machine (manufactured by LONATI Co., Ltd., 400 stitches) at a weaving tension of 1.0 g, and the above Z捻SCY was supplied at 2 and 4, and was prepared. Braiding material. In the woven material, the content of the polyurethane elastic yarn was 16%.

Next, the dyeing process of the woven material was carried out in the following manner to obtain a tights trousers.

(1) Pre-formed processing: using a vacuum dryer, 90 ° C × 10 minutes

(2) Dyeing: The dye was dyed black at 60 ° C for 60 minutes using a dye "Lanaset" (registered trademark) Black B manufactured by Ciba Specialty Chemicals Co., Ltd. at 2.00 wf%. The pH adjustment at the time of dyeing with acetic acid and ammonium sulfate.

(3) Finally, the softening treatment was carried out, and the finishing step (using a pantyhose setting machine, setting: 115 ° C × 10 seconds, drying: 120 ° C × 30 seconds) was completed.

[Washing method]

According to the Washing Method Manual (JIS LO217: 1995, Schedule 1, Cleaning Method 103) developed by the New Functional Assessment of Fiber Products. In other words, the home appliance washing machine specified in JIS LO217:1995, Table 1 and Cleaning Method 103 is used to dissolve 40 ml of JAFET standard lotion (fiber product new function evaluation council system) in 30 liters of 40 ° C water. The washing liquid was placed in the washing liquid of 1 kg of the sample. The washing was carried out for 5 minutes, dehydration, washing for 2 minutes, dehydration, washing for 2 minutes, and dehydration for 1 time, and washing was carried out.

[deodorant]

Deodorization test is based on the certification standard for deodorized processed fiber products (developer: Japan Society of Corporate Fiber Evaluation Technology Agreement Product Certification Department, date of preparation: September 1, 2004), as follows, the odor component is measured by machine test. Deodorant assessment. In addition, the standard of the "deodorizing effect" is shown in Table 1 by the Japanese Society of Corporate Fiber Evaluation Technology Co., Ltd. regarding the reduction rate of each odor component measured by the machine analysis test.

(Detective management method)

1. Place the sample (10 cm x 10 cm) into a gas sampling bag (Tedlar Bag).

2. The predetermined test gas shown in Table 1 was injected, and the residual gas concentration (ppm) after 2 hours was measured by a component-corresponding detection tube (manufactured by Gastec). Further, the gas filling amount was 3 L, and the dilution gas was dry air or nitrogen.

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

4. According to the following formula, the reduction rate of the residual gas concentration is calculated and expressed as the deodorization rate.

Further, the measured values were obtained by an average value of n=3.

[antibacterial]

The antibacterial test was carried out in accordance with the antibacterial test procedure (JIS L1902: 2008, bacterial liquid absorption method) specified by the Japanese Society of Corporate Fiber Evaluation Technology. X was determined as the number of bacteria (s) after 18 hours of culture in the unprocessed sample, and Y was determined as the number of bacteria (s) after 18 hours of culture of the test material, and the activity of the bacteria was calculated from the following formula. To assess the antibacterial power. Further, the measured values were obtained by an average value of n=3.

Static bacteria activity value = LogX-LogY

In addition, when the bacteriostatic activity value of S. aureus is 2.2 or more, it is evaluated as "effective" in antibacterial.

[Amount of monoamine compound released]

Pre-processing:

After the polyurethane elastic yarn was wound, it was stored under the conditions of 35 ° C × 65% RH for 14 days. Then, the polyurethane elastic yarn was placed in a zipper bag (manufactured by JEOL Ltd., J-4, 340 mm × 240 mm × 0.04 mm), and the air was injected and quickly sealed, and stored at room temperature of 23 ° C. hour.

analysis:

The gas is collected in its entirety into the collection tube from the zipper bag in which the treated polyurethane elastomer yarn is placed. The collected organic components were heated off by a collection tube and introduced into a GC/MS analysis. The measurement conditions are disclosed in Table 2.

The calibration curve using toluene was quantified by absolute measurement of the absolute area of total ions. Further, the amount of release per unit area of the sample was measured by the following formula, and the measured values were obtained by measuring two samples of the same level, and the average value of n = 2 was obtained.

Amount of release (μg/m ² ) = component amount (μg) / exposed area of the yarn portion (cm ² ) × 10

The exposed area of the yarn portion (cm ² ) = ((A/2) ² × 3.14 - (B / 2) ² × 3.14) × 2 + ((C + D) / 2) × A × 3.14

Here, A, B, C, and D are defined as shown in Fig. 1. Further, in the first drawing, (a) is a plan view of the package, and (b) is a front view of the package.

[NOx resistance to fading]

10 g of the polyurethane elastic yarn was wound up to a stainless steel plate to prepare a sample card. This sample was exposed to a gas containing a predetermined concentration (7 ppm) of NO ₂ gas for 50 hours using a Scott Tester. After the exposure treatment, ColorMaster (D25 DP-9000 type signal processor) was used to measure the "b" color, and the degree of fading was evaluated by the difference "Δb" before and after the treatment. Further, the measured value is obtained from the average value of n=3.

[Average primary particle size]

The inorganic particles were imaged by an electrolysis-radiation scanning electron microscope (FE-SEM) S-800 manufactured by Hitachi, Ltd., and analyzed by image processing software Image-Pro Version 4.0. Further, the equivalent circle diameter of the projected area was measured, and the number of n=20 per sample was averaged.

[Content of metal phosphate]

The concentration of the metal phosphate was determined by analyzing the polyurethane elastic yarn by atomic absorption spectrophotometry. The measurement is carried out for metals (Al, Zr, Ti) in the metal phosphate. Further, the measured value was obtained from the average of n = 3, and the content of the metal phosphate was determined by the following formula.

[Content of 4-grade ammonium salt]

A 1 g sample (polyurethane yarn) was weighed and placed in 100 ml of methanol to extract a grade 4 ammonium salt. The extract was quantified by liquid chromatography from a previously prepared standard solution. The analytical conditions are disclosed below. Further, the measurement was obtained from the average of n=2.

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

Detection: UV210nm

Mobile phase: methanol/water mixed solution (60/40% by volume), flow rate: 1 ml/min, injection amount: 2 μl

[Example 1]

PTMG having a molecular weight of 1800 and MDI were reacted at a molar ratio of 1:1.58 at 90 ° C for 2 hours to prepare an isocyanate-terminated prepolymer, which was dissolved in DMAc to be 35% by weight, and a prepolymer solution was prepared. . Further, ethylenediamine, 1,2 propanediamine as a chain extender, and diethylamine as a chain terminator (endblocking agent) are mixed at a ratio of an amine group terminal group concentration of 10:2:1, and It was dissolved in DMAc to be 35% by weight, and an amine solution was formulated.

The prepolymer solution and the amine solution were mixed while stirring, and the molar ratio of the isocyanate terminal group to the amine terminal group was 1:1.02, and the DMC solution of the polyurethane polyurethane polymer (concentration: 35 wt%) was prepared. Next, a polyurethane solution ("Methacrol" manufactured by Dupont Co., Ltd.) produced by the reaction of a third butyl diethanolamine and methylene-bis-(4-cyclohexyl isocyanate) as an antioxidant is used. Registered trademark) 2462), and a polycondensate of p-cresol and divinylbenzene ("Methacrol" (registered trademark) 2390, manufactured by Dupont Co., Ltd.) is mixed in an amount of 2 to 1 (by weight) to form an antioxidant DMAc solution (concentration: 35 weight) %). 96 parts by weight of the DMAc solution of the polyurethane urea polymer and 4 parts by weight of the antioxidant DMAc solution were mixed to form a polymer solution A1.

Next, a zirconium phosphate-based deodorant "Kesmon" (registered trademark) NS-10 (average primary particle diameter: 0.9 μm) manufactured by Toagosei Co., Ltd. was dispersed in DMAc by a homomixer to prepare a zirconium phosphate dispersion B1 (35). weight%).

Next, diethylamine (molecular weight: 73.14) was blended in DMAc to a 35 wt% monoamine solution C1.

The polymer solutions A1, B1, and C1 were uniformly mixed into a spinning dope D1 at 96.9 wt%, 3% by weight, and 0.1 wt%. The speed ratio of the guide roller to the coiler was set to 1.3, and dry spinning was performed at a speed of 720 m/min to obtain a polyurethane of 22 dtex, 2 monofilaments, and a zirconium phosphate content of 3% by weight. 200g of yarn yarn.

About the obtained polyurethane elastic yarn, the evaluation weaving material was prepared, and the deodorizing property and the antibacterial property were measured. The amount of monoamine compound released from the polyurethane elastic yarn itself and the fading resistance of NOx were one and the results are shown in Tables 3, 4, and 5.

[Embodiment 2]

The polymer solutions A1, B1, and C1 were uniformly mixed at 97.98 wt%, 2 wt%, and 0.02 wt% to form a spinning dope D2. Dry spinning was carried out in the same manner as in Example 1 to obtain 200 g of a corrugated yarn of 22 parts of a taxi, two strands of monofilament, and a zirconium phosphate content of 2% by weight.

Regarding the results of each evaluation, the results are disclosed in Tables 3, 4, and 5.

[Example 3]

Instead of the zirconium phosphate dispersion B1, a titanium phosphate dispersion B2 (35 wt%) obtained by dispersing the synthesized titanium phosphate (average primary particle diameter: 1.1 μm) in DMAc by a homomixer was used.

The polymer solutions A1, B2, and C1 were uniformly mixed into a spinning dope D3 at 96.98 wt%, 3% by weight, and 0.02 wt%. Dry-spinning was carried out in the same manner as in Example 1 to obtain 200 g of a corrugated yarn of 22 dtex, two strands of monofilament, and a polyurethane having a titanium phosphate content of 3% by weight.

Regarding the results of each evaluation, the results are disclosed in Tables 3, 4, and 5.

[Example 4]

Instead of the monoamine solution C1, a monoamine solution C2 (35 wt%) in which ethylmethylamine (molecular weight: 89.14) was blended in DMAc to 35% by weight was used.

The polymer solutions A1, B1, and C2 were uniformly mixed into a spinning dope D4 at 94.88 wt%, 5% by weight, and 0.12 wt%. Dry-spinning was carried out in the same manner as in Example 1 to obtain 200 g of a corrugated yarn of 22 dtex, two strands of monofilament, and a polyurethane dye having a zirconium phosphate content of 5% by weight.

Regarding the results of each evaluation, the results are disclosed in Tables 3, 4, and 5.

[Example 5]

Instead of the monoamine solution C1, a monoamine solution C3 (35 wt%) prepared by dissolving diisopropylamine (molecular weight 101.19) in DMAc to 35% by weight was used.

The polymer solutions A1, B1, and C3 were uniformly mixed at 99.35% by weight, 0.5% by weight, and 0.15% by weight to form a spinning dope D5. Dry-spinning was carried out in the same manner as in Example 1 to obtain 200 g of a corrugated yarn of 22 dtex, 2 monofilament, and a zirconium phosphate content of 0.5% by weight of a polyurethane yarn.

Regarding the results of each evaluation, the results are disclosed in Tables 3, 4, and 5.

[Embodiment 6]

Instead of the monoamine solution C1, a monoamine solution C4 (35 wt%) prepared by mixing isopropylmethylamine (molecular weight: 73.14) in DMAc to 35% by weight was used.

The polymer solutions A1, B1, and C4 were uniformly mixed into a spinning stock solution D6 at 89.5% by weight, 10.0% by weight, and 0.5% by weight. Dry spinning was carried out in the same manner as in Example 1 to obtain 200 g of a corrugated yarn of 22 dtex, 2 monofilament, and a zirconium phosphate content of 10% by weight. However, in the spinning, a yarn breakage which is considered to be blocked by the metal spun yarn occurs, and the spinning property is not good.

Regarding the results of each evaluation, the results are disclosed in Tables 3, 4, and 5.

[Embodiment 7]

Instead of the monoamine solution C1, a monoamine solution C5. (35 wt%) in which N-butylamine (molecular weight: 73.14) was blended in DMAc to 35% by weight was used.

The polymer solutions A1, B1, and C5 were uniformly mixed at 95.9 wt%, 4.0 wt%, and 0.1 wt% to form a spinning stock solution D7. Dry spinning was carried out in the same manner as in Example 1 to obtain 200 g of a corrugated yarn of 22 dtex, 2 monofilament, and a zirconium phosphate content of 4 wt%.

Regarding the results of each evaluation, the results are disclosed in Tables 3, 4, and 5.

[Embodiment 8]

The polymer solutions A1, B2, and C1 were uniformly mixed into a spinning dope D8 at 92.9 wt%, 7.0 wt%, and 0.1 wt%. Dry-spinning was carried out in the same manner as in Example 1 to obtain a 200 g-wound body of a polyurethane yarn of 22 minutes, 2 strands of monofilament, and a titanium phosphate content of 7 wt%.

Regarding the results of each evaluation, the results are disclosed in Tables 3 and 4.

[Embodiment 9]

Instead of the zirconium phosphate dispersion B1, a zirconium phosphate dispersion B3 (35 wt%) obtained by dispersing separately synthesized zirconium phosphate (average primary particle diameter: 3.5 μm) in DMAc was used in a homomixer.

The polymer solutions A1, B3, and C1 were uniformly mixed into a spinning dope D9 at 97.4% by weight, 2.5% by weight, and 0.1% by weight. Dry-spinning was carried out in the same manner as in Example 1 to obtain a 50 g-wound body of a polyurethane yarn of 22 dtex, two strands of monofilament, and a titanium phosphate content of 2.5% by weight. However, many yarn breaks which are considered to be blocked by the metal spun yarn occur in the spinning, and the spinning property is poor.

Regarding the results of each evaluation, the results are disclosed in Tables 3, 4, and 5.

[Embodiment 10]

The polymer solutions A1, B1, and C1 were uniformly mixed into a spinning dope D10 at 93.99% by weight, 6% by weight, and 0.01% by weight. Dry spinning was carried out in the same manner as in Example 1 to obtain 200 g of a corrugated yarn of 22 parts of a taxi, two strands of monofilament, and a urethane content of 6% by weight of a zirconium phosphate.

Regarding the results of each evaluation, the results are disclosed in Tables 3, 4, and 5.

[Example 11]

A DMAC solution (35 wt%) containing a PTMG, MDI, ethylene glycol having a molecular weight of 2,100 and a 1-butanol polyurethane urethane polymer as a terminal mounting agent was formulated. Next, a polyurethane solution ("Methacrol" manufactured by Dupont Co., Ltd.) produced by the reaction of a third butyl diethanolamine and methylene-bis-(4-cyclohexyl isocyanate) as an antioxidant is used. Registered trademark) 2462), and a polycondensate of p-cresol and divinylbenzene ("Methacrol" (registered trademark) 2390, manufactured by Dupont Co., Ltd.) 2 to 1 (by weight) mixed into 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 form a polymer solution A2.

A 4-grade ammonium salt compound "BARQUAT" (registered trademark) MS-100 (benzyl dimethyltetradecyl ammonium chloride) manufactured by Lonza Japan Co., Ltd. was formulated in DMAc to be a 35 wt% antibacterial agent solution C6. .

The polymer solutions A2, B1, C1, and C6 were uniformly mixed into a spinning dope D11 at 96.8 wt%, 2.5 wt%, 0.2 wt%, and 0.5 wt%. Dry spinning was carried out in the same manner as in Example 1 to obtain 200 g of a corrugated yarn of 22 dtex, two monofilaments, and a polyurethane dye having a zirconium phosphate content of 2.5% by weight.

Regarding the results of each evaluation, the results are disclosed in Tables 3, 4, and 5.

[Embodiment 12]

A tripolyphosphoric acid obtained by dispersing a polyaluminum dihydrogen phosphate deodorant "K-FRESH" (registered trademark) #100P (average primary particle diameter: 1.0 μm) made of Tayca (manufactured by Tayca) in DMAc by a homomixer The aluminum dihydrogen dispersion B4 (35 wt%) was substituted for the zirconium phosphate dispersion B1.

The polymer solutions A1, B4, and C1 were uniformly mixed into a spinning dope D12 at 94.8% by weight, 5% by weight, and 0.2% by weight. Dry-spinning was carried out in the same manner as in Example 1 to obtain a 200 g-wound body of a polyurethane yarn having a fraction of 22 dtex, two strands of monofilament, and a tripolyphosphoric acid dihydrogenate content of 5% by weight.

Regarding the results of each evaluation, the results are disclosed in Tables 3, 4, and 5.

[Example 13]

The polymer solutions A2, B1, and C1 were uniformly mixed into a spinning stock solution D13 at 96.9 wt%, 3% by weight, and 0.1 wt%. Dry-spinning was carried out in the same manner as in Example 1 to obtain a 200 g-wound body of a polyurethane yarn of 22 dtex, two strands of monofilament, and a zirconium phosphate content of 3% by weight.

Regarding the results of each evaluation, the results are disclosed in Tables 3, 4, and 5.

[Embodiment 14]

PTMG having a molecular weight of 1800 and MDI were mixed at a molar ratio of 1:1.58, and reacted at 90 ° C for 2 hours to form a prepolymer of an isocyanate terminal, and then dissolved in DMAc to obtain a prepolymer solution of 35% by weight. Further, ethylenediamine as a chain extender and diethylamine as a chain terminator were mixed at a ratio of an amine group terminal group concentration of 14:1, and dissolved in an amine solution in which DMAc became 35% by weight.

The prepolymer solution and the amine solution were mixed while stirring, and the molar ratio of the isocyanate terminal group to the amine terminal group was 1:1.06, and the DMAC solution of the polyurethane ethyl urea polymer (35 wt%) was formulated. Next, a polyurethane solution ("Methacrol" manufactured by Dupont Co., Ltd.) produced by the reaction of tert-butyldiethanolamine and methylene-bis-(4-cyclohexyl isocyanate) as an antioxidant (registered) Trademark) 2462), and a polycondensate of p-cresol and divinylbenzene ("Methacrol" (registered trademark) 2390, manufactured by Dupont Co., Ltd.) was mixed in an amount of 2 to 1 (weight ratio) to form 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 form a polymer solution A3.

The polymer solutions A3 and B1 were uniformly mixed at 97% by weight and 3% by weight to form a spinning dope D14. Dry-spinning was carried out in the same manner as in Example 1 to obtain a 200 g-wound body of a polyurethane yarn of 22 dtex, two strands of monofilament, and a zirconium phosphate content of 3% by weight.

Regarding the results of each evaluation, the results are disclosed in Tables 3, 4, and 5.

[Example 15]

The NISSAN CATION (registered trademark) EQ-01D, a fourth-grade ammonium salt compound manufactured by Nippon Oil Chemical Co., Ltd., was formulated in DMAc to be a 35 wt% antibacterial agent solution C7.

The polymer solutions A1, B1, C1, and C7 were uniformly mixed into a spinning dope D15 at 96.8 wt%, 2.5 wt%, 0.2 wt%, and 0.5 wt%. Dry spinning was carried out in the same manner as in Example 1 to obtain 200 g of a corrugated yarn of 22 dtex, two monofilaments, and a polyurethane dye having a zirconium phosphate content of 2.5% by weight.

Regarding the results of each evaluation, the results are disclosed in Tables 3, 4, and 5.

[Example 16]

A three-stage ammonium salt compound "NeoJami DFS" manufactured by Sanyo Chemical Co., Ltd. was blended in DMAc to a 35 wt% solution C8 (35 wt%).

The polymer solutions A3, B1, and C8 were uniformly mixed into a spinning dope D16 at 96.5 wt%, 2.5% by weight, and 1 wt%. Dry spinning was carried out in the same manner as in Example 1 to obtain 200 g of a corrugated yarn of 22 dtex, two monofilaments, and a polyurethane dye having a zirconium phosphate content of 2.5% by weight.

Regarding the results of each evaluation, the results are disclosed in Tables 3, 4, and 5.

[Example 17]

The polymer solutions A3, B1, and C8 were uniformly mixed into a spinning dope D17 at 97.4% by weight, 2.5% by weight, and 0.1% by weight. Dry spinning was carried out in the same manner as in Example 1 to obtain 200 g of a corrugated yarn of 22 dtex, two monofilaments, and a polyurethane dye having a zirconium phosphate content of 2.5% by weight.

Regarding the results of each evaluation, the results are disclosed 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 200 g-wound body of a 22-cent taxi and two-strand polyurethane yarn.

Regarding the results of each evaluation, the results are disclosed in Tables 3, 4, and 5.

[Comparative Example 2]

The polymer solutions A1 and B1 were uniformly mixed at 97.5 wt% and 2.5% by weight to form a spinning dope D18. Dry spinning was carried out in the same manner as in Example 1 to obtain 200 g of a corrugated yarn of 22 dtex, two monofilaments, and a polyurethane dye having a zirconium phosphate content of 2.5% by weight.

Regarding the results of each evaluation, the results are disclosed in Tables 3, 4, and 5.

[Comparative Example 3]

The polymer solutions A1 and C2 were uniformly mixed into a spinning dope D19 at 99.8% by weight and 0.2% by weight. Dry-spinning was carried out in the same manner as in Example 1 to obtain a 200 g-wound body of a 22-cent taxi and two-strand polyurethane yarn.

Regarding the results of each evaluation, the results are disclosed in Tables 3, 4, and 5.

[Comparative Example 4]

The zeolite dispersion liquid B3 (35 wt%) obtained by dispersing a silver-containing zeolite "ZEOMIC" (registered trademark) SW-10N (average primary particle diameter: 1.0 μm) in DMAc was replaced by a homomixer. Zirconium phosphate dispersion B1.

The polymer solutions A1 and B3 were uniformly mixed into a spinning stock solution D20 at 96% by weight and 4% by weight. Dry spinning was carried out in the same manner as in Example 1 to obtain a 200 g wrap yarn of 22 dtex, two strands of monofilament, and silver containing a polyurethane yarn having a zeolite content of 4% by weight.

Regarding the results of each evaluation, the results are disclosed in Tables 3, 4, and 5.

[Comparative Example 5]

Instead of the monoamine solution C1, a monoamine solution C9 (3.5% by weight) in which dipentylamine (molecular weight: 157.3) was blended in DMAc to 35% by weight was used.

The polymer solutions A1, B1, and C9 were uniformly mixed into a spinning stock solution D21 at 97.9% by weight, 2.0% by weight, and 0.1% by weight. Dry spinning was carried out in the same manner as in Example 1 to obtain 200 g of a corrugated yarn of 22 parts of a taxi, two strands of monofilament, and a zirconium phosphate content of 2% by weight.

Regarding the results of each evaluation, the results are disclosed in Tables 3, 4, and 5.

[Comparative Example 6]

Instead of the zirconium phosphate dispersion B1, a zeolite dispersion B5 (35 wt%) obtained by dispersing High Silica Zeolites HSZ-980HOA (average primary particle diameter 2.0 μm) made of Tosoh Co., Ltd. in DMAc was prepared by a homomixer.

The polymer solutions A1, B5, and C1 were uniformly mixed into a spinning dope D22 at 96.8 wt%, 3% by weight, and 0.2 wt%. Dry spinning was carried out in the same manner as in Example 1 to obtain 200 g of a corrugated yarn of 22 parts of a taxi, two strands of monofilament, and a polyurethane having a zeolite content of 3% by weight.

Regarding the results of each evaluation, the results are disclosed in Tables 3, 4, and 5.

[Comparative Example 7]

Instead of dispersing zirconium phosphate, a zinc oxide dispersion B6 (35 wt%) obtained by dispersing ultrafine particle zinc oxide "FINEX"-25 (average primary particle diameter 0.04 μm) prepared by hydrazine chemical (strand) in DMAc by a homomixer is used. Liquid B1.

The polymer solutions A1, B6, and C1 were uniformly mixed into a spinning stock solution D23 at 96.9 wt%, 3. wt%, and 0.1 wt%. Dry spinning was carried out in the same manner as in Example 1 to obtain 200 g of a corrugated yarn of 22 dtex, two strands of monofilament, and a polyurethane dye having a zinc oxide content of 3% by weight.

Regarding the results of each evaluation, the results are disclosed in Tables 3, 4, and 5.

[Comparative Example 8]

Instead of the monoamine solution C1, a solution C10 (35 wt%) in which the natural antibacterial agent of eucalyptus alcohol was blended in DMAc to 35% by weight was used.

The polymer solutions A1, B6, and C10 were uniformly mixed into a spinning stock solution D24 at 96.9 wt%, 3% by weight, and 0.1 wt%. Dry spinning was carried out in the same manner as in Example 1 to obtain 200 g of a corrugated yarn of 22 dtex, two strands of monofilament, and a polyurethane dye having a zinc oxide content of 3% by weight.

Regarding the results of each evaluation, the results are disclosed in Tables 3, 4, and 5.

[Comparative Example 9]

The polymer solutions A1 and C8 were uniformly mixed at 99% by weight and 1% by weight to form a spinning dope D25. Dry spinning was carried out in the same manner as in Example 1 to obtain 200 g of a corrugated yarn of 22 dtex, two strands of monofilament, and a polyurethane dye having a zinc oxide content of 3% by weight.

Regarding the results of each evaluation, the results are disclosed in Tables 3, 4, and 5.

[Comparative Example 10]

Inorganic antibacterial agent dispersion liquid C11 (35 wt%) obtained by dispersing an antibacterial agent "Novaron" (registered trademark) AGT330 (average primary particle diameter 0.5 μm) in DMAc by a homomixer. Instead of the monoamine solution C1. The polymer solutions A1, B1, B6, and C11 were uniformly mixed into a spinning dope D26 at 96.5 wt%, 1.5 wt%, 1.0 wt%, and 1.0 wt%. Dry spinning was carried out in the same manner as in Example 1 to obtain 200 g of a corrugated yarn of 22 dtex, two strands of monofilament, and a polyurethane dye having a zirconium phosphate content of 1.5% by weight.

Regarding the results of each evaluation, the results are disclosed in Tables 3, 4, and 5.

[Comparative Example 11]

The polymer solutions A2 and B1 were uniformly mixed at 97.5 wt% and 2.5% by weight to form a spinning dope D27. Dry spinning was carried out in the same manner as in Example 1 to obtain 200 g of a corrugated yarn of 22 dtex, two monofilaments, and a polyurethane dye having a zirconium phosphate content of 2.5% by weight.

Regarding the results of each evaluation, the results are disclosed in Tables 3, 4, and 5.

[Industrial availability]

According to the present invention, a polyurethane elastic yarn excellent in stretchability, deodorant property, antibacterial property, and color solidity can be obtained. Therefore, by using the polyurethane elastic yarn, stretchability and deodorization can be obtained. A fabric with excellent properties, antibacterial properties and color fastness.

A. . . Outer diameter of the package

B. . . Paper tube outer diameter

C. . . Winding width of the outermost yarn

D. . . Winding width of the innermost layer of yarn

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

Claims (12)

A polyurethane elastic yarn comprising an elastic yarn of a polyurethane containing a polymer diol and a diisocyanate as a starting material, which contains a metal phosphate and a monoamine having a molecular weight of 120 or less The amount of the compound released is 100 μg/m ² or more. The polyurethane elastic yarn of claim 1, wherein the metal phosphate is contained in an amount of from 0.5% by weight to 10% by weight. 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. The polyurethane elastic yarn according to 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 phosphate. The polyurethane elastic yarn of claim 1 or 2, wherein the monoamine compound is a secondary amine compound. The polyurethane elastic yarn of claim 1 or 2, further comprising a quaternary ammonium salt compound. The polyurethane elastic yarn of claim 6, wherein the quaternary ammonium salt compound has the following structure: Further, R1 and R2 are hydrogen or an alkyl group having 1 to 3 carbon atoms (which may be the same or different), R3 is an alkyl group having 10 to 22 carbon atoms, and R4 is an alkyl group having 1 to 22 carbon atoms (which may be combined with R1). R2, R3 are the same or different), X- is an acidic relative ion. The polyurethane elastic yarn of claim 6, wherein the content of the fourth-order ammonium salt compound is in the range of 0.1% by weight or more and 5% by weight or less. A method for producing a polyurethane elastic yarn by mixing a metal phosphate in a spinning stock solution containing a polymer diol and a diisocyanate as a starting material, and mixing the molecular weight The monoamine compound of 120 or less is contained in a range of 0.01% by weight or more and 0.5% by weight or less based on the spinning stock solution, and the spinning stock solution is dry-spun. A method for producing a polyurethane elastic yarn according to claim 9 in the spinning stock solution containing the polyurethane having a polymer diol and a diisocyanate as a starting material, The metal phosphate is mixed as a dispersion. The method for producing a polyurethane elastic yarn according to claim 9 or 10, wherein the metal phosphate is at least selected from the group consisting of titanium phosphate, zirconium phosphate, and aluminum dihydrogen phosphate. 1 species. A 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.