US20140148537A1

US20140148537A1 - Elastic polyurethane thread and manufacturing method thereof

Info

Publication number: US20140148537A1
Application number: US13/879,697
Authority: US
Inventors: Katsuya Suzuki; Tatsuaki Kanbayashi; Toshihiro Tanaka
Original assignee: Toray Opelontex Co Ltd
Current assignee: Toray Opelontex Co Ltd
Priority date: 2010-10-19
Filing date: 2011-10-12
Publication date: 2014-05-29
Also published as: CN103298985B; US20140033451A1; BR112013009233A2; EP2631338A1; JPWO2012053401A1; JP5870928B2; EP2631338A4; TW201221713A; TWI553176B; HK1189248A1; WO2012053401A1; CN103298985A; MX2013004238A; KR20130122622A; KR101851419B1

Abstract

In order to provide an elastic polyurethane thread with excellent antibacterial and deodorant properties as well as excellent color fastness, an elastic polyurethane thread is made which consists of polyurethanes which have polymer diols and diisocyanates as the starting materials, contains metallic phosphates in the range of 0.5-10 wt %, and has an emitted quantity of monoamine compounds with molecular weights of 120 or less of 100 μg/m²or more.

Description

TECHNOLOGICAL FIELD

This invention concerns an elastic polyurethane thread with excellent antibacterial and deodorant properties as well as excellent color fastness; it concerns an elastic polyurethane thread which is idea for obtaining fabrics with antibacterial and deodorant properties, as well as a method for manufacturing it.

BACKGROUND TECHNOLOGY

Because of their stretching ability, elastic fibers are widely used in stretching clothing applications, such as leg-ware, inner-ware, support ware, etc., sanitary applications, such as paper diapers and sanitary napkins, and industrial material applications.
In recent years, in a search for more comfortable living environments, a wide range of so-called “antibacterial products” have appeared, such as antibacterial coatings, films and sheets, filaments, toiletry products, kitchen goods, writing implements, sand, tissues, fibers, cosmetics, etc. Similarly, “deodorant products” have also appeared, such as clothing, sleep-ware, etc., which are provided with deodorant functions to deal with odors of aging, etc.
As antibacterial agents which are used in these products, many inorganic antibacterial agents have been developed, such as silver-based antibacterial agents. Moreover, active carbon, zeolites containing silver, other zeolites, zinc oxide microparticles, etc., are examples of deodorant agents.
These inorganic antibacterial agents have the properties that they have superior weather and chemical resistances to those of organic antibacterial agents and also have low acute oral toxicities. In addition, their resistances to heat are much higher than those of organic antibacterial agents. Therefore, they have come to be used in many fields in which they are added to synthetic resins. However, when inorganic antibacterial agents are added to synthetic resins and molding is performed, the molded articles are discolored by the activities of the metals contained in the agents and the effects of the heat at the time of molding and of light shining on the molded objects; thus, the problem of the value of the products being greatly lowered easily arises.
Therefore, there have been many proposals for technologies which inhibit the discoloration due to heat of antibacterial resins to which inorganic antibacterial agents are added (Patent Reference 1). However, although these technologies have shown certain antibacterial and deodorant performances, it cannot be said that the problem of yellowing has been completely solved, since they are greatly discolored by the environment and the passage of time.
Moreover, antibacterial and deodorant elastic polyurethane fibers have been proposed (Patent Reference 2) which contain, as organic antibacterial agents, antibacterial and deodorant elastic polyurethane fibers which contain hinokitiol and metal oxides containing at least one element selected from Zn, Si, Cu, Ni, Fe, Al, and Mg and/or composite metal oxides. Certain antibacterial and deodorant performances of these elastic polyurethane fibers have been observed. However, since the antibacterial agent hinokitiol has been observed to sublimate due to being heated during dry spinning, it is necessary to put an extra amount of it in the spinning dope. Moreover, since the amount of residual hinokitiol varies with the amount of heat and other spinning conditions, it is difficult to produce elastic polyurethane thread which maintains a stable antibacterial property. In addition, there is a problem with cost, since hinokitiol, a natural antibacterial agent, is expensive.
Furthermore, the use of synthetic organic antibacterial agents, etc., has been proposed (Patent Reference 3). However, they have no deodorant effectiveness if they are used by themselves, and there has been a problem with providing both antibacterial and deodorant properties.

PRIOR ART REFERENCES

Patent References

Patent Reference 1: Japanese Patent 4485871
Patent Reference 2: Japanese Laid-Open Patent Application No. 2002-105757
Patent Reference 3: Japanese Laid-Open Patent Application No. 2004-292471

OUTLINE OF THE INVENTION

Problems which the Invention Seeks to Solve

The purpose of this invention is to provide an elastic polyurethane thread with excellent antibacterial and deodorant properties as well as excellent color fastness and a method for manufacturing it.

Means of Solving these Problems

This invention employs the following means in order to solve these problems.

- 1. An elastic polyurethane thread which is an elastic thread consisting of polyurethanes which have polymer diols and diisocyanates as the starting materials, contains metallic phosphates, and has an emitted quantity of monoamine compounds with molecular weights of 120 or less of 100 μg/m²or more.
- 2. An elastic polyurethane thread in accordance with (1) above in which the content of the aforementioned metallic phosphates is in the range of 0.5-10 wt %.
- 3. An elastic polyurethane thread in accordance with (1) or (2) above in which the average primary particle diameter of the aforementioned metallic phosphates is 3.0μ or less.
- 4. An elastic polyurethane thread in accordance with any of (1)-(3) above in which the aforementioned metallic phosphates are at least one selected from a group comprising titanium phosphate, zirconium phosphate, and aluminum dihydrogen tripolyphosphate.
- 5. An elastic polyurethane thread in accordance with any of (1)-(4) above in which the aforementioned emitted monoamine compounds are secondary monoamine compounds.
- 6. An elastic polyurethane thread in accordance with any of (1)-(5) above which also contains quaternary ammonium salt compounds.
- 7. An elastic polyurethane thread in accordance with (6) above in which the aforementioned quaternary ammonium salt compounds have the following structure:

(wherein

- R1 and R2 are hydrogens or alkyl groups with carbon numbers of 1-3 (which may be the same or different),
- R3 is an alkyl group with a carbon number of 10-22,
- R4 is an alkyl group with a carbon number of 1-22 (which may be the same or different from R1, R2, and R3), and
- X is an acidic counterion).

(8) An elastic polyurethane thread in accordance with (6) or (7) above in which the content of the aforementioned quaternary ammonium salt compounds is in the range of 0.1-5 wt %.
(9) A method of manufacturing an elastic polyurethane thread in which metallic phosphates are mixed with a spinning dope which contains polyurethanes which have polymer diols and diisocyanates as starting materials, mixing is performed in such a way that the content of monoamine compounds with molecular weights of 120 or less is in the range of 0.01-0.5 mass %, and this spinning dope is dry-spun.
(10) A method of manufacturing an elastic polyurethane thread in accordance with (9) in which the aforementioned metallic phosphates are mixed in with the spinning dope which contains polyurethanes which have polymer diols and diisocyanates as starting materials as a dispersion liquid.
(11) An elastic polyurethane thread in accordance with (9) or (10) above in which the aforementioned metallic phosphates are at least one selected from a group comprising titanium phosphate, zirconium phosphate, and aluminum dihydrogen tripolyphosphate.
(12) An elastic polyurethane thread in accordance with any of (9)-(11) above in which the aforementioned monoamine compounds with molecular weights of 120 or less are secondary amine compounds.

Effectiveness of the Invention

By means of this invention, it is possible to obtain elastic polyurethane threads with excellent stretch abilities and deodorant, antibacterial, and color fastness properties, since they are elastic polyurethane threads the principal constituent ingredients of which are polymer diols and diisocyanates, they contain metallic phosphates, and the emitted quantities of monoamine compounds with molecular weights of 120 or less are 100 μg/m²or more. Therefore, fabrics using these elastic polyurethane threads have excellent stretch abilities and deodorant, antibacterial, and color fastness properties.

SIMPLE EXPLANATION OF DRAWINGS

FIG. 1: A schematic view showing the dimensions of various parts the package.

WORKING EMBODIMENTS OF THE INVENTION

This invention will be explained in further detail below.
First, the polyurethanes used in this invention will be explained.
The polyurethanes used in this invention may be any ones which have polymer diols and diisocyanates as starting materials; they are not particularly limited. Moreover, the methods of synthesizing them are not particularly limited. That is, they may be polyurethane ureas which consist of polymer diols, diisocyamates, and low-molecular-weight diamines, or polyurethane urethanes which consist of polymer diols, diisocyanates, and low-molecular-weight diols. Moreover, they may also be polyurethane ureas which use compounds containing hydroxyl and amino groups in their molecules as chain extenders. It is also desirable to use polyfunctional glycols or isocyanates, etc., with 3 or more functions, within ranges which do not obstruct the effectiveness of the invention.
The polymer diols are preferably polyether or polester diols, polycarbonate diols, etc. Moreover, it is especially desirable to use polyether diols from the point of view of giving the threads flexibility and ductility.
Desirable examples of the polyether diols are polyethylene oxide, polyethylene glycol, polyethylene glycol derivatives, polypropylene glycol, polytetramethylene ether glycol (abbreviated below as “PTMG”), modified PTMGs which are copolymers of tetrahydrofuran (THF) and 3-methyltetrahydrofuran (abbreviated below as “3M-PTMG”), modified PTMGs which are copolymers of THF and 2,3-dimethyl THF, polyols with side chains on both sides, disclosed in Japanese Patent No. 2615131, etc., and random copolymers in which THF and ethylene oxide and/or propylene oxide are disposed irregularly. These polyether diols may be of one kind or two or more kinds mixed or copolymerized.
From the point of view of obtaining abrasion resistance and light fastness, it is desirable to use polyester diols such as butylene adipates, polycaprolactone diols, polyester polyols with side chains which are disclosed in Japanese Laid-Open Patent Application No. 61-26612, etc., or polycarbonate diols which are disclosed in Japanese Patent No. 2-289516, etc.
These polymer diols may be used individually or in mixtures or copolymers of two or more.
The weight average molecular weights of the polymer diols are preferably in the range of 1000-8000, especially preferably 1500-6000, from the point of view of obtaining ductility, strength, heat resistance, etc., when they are spun. By using polyols with molecular weight is this range, elastic threads with excellent ductilities, strengths, elastic recovery forces, and heat resistances can be obtained easily.
Next, as the diisocyanates, aromatic diisocyanates such as diphenylmethane diisocyanate (abbreviated below as “MDI”), tolylene diisocyanate, 1,4-diisocyanate benzene, xylylene diisocyanate, 2,6-naphthalene diisocyanate, etc., are especially preferable for synthesizing polyurethanes with high heat resistances and strengths. Furthermore, the following are desirable examples of alicyclic diisocyanates: methylene bis(cyclohexyl isocyanate) (abbreviated below as “H12MDI”), isophorone diisocyanate, methylcyclohexane 2,4-diisocyanate, methyl cyclohexane 2,6-diisocyanate, cyclohexane 1,4-diisocyanate, hexahydroxylene diisocyanate, hexahydrotolylene diisocyanate, octahydro-1,5-naphthalene diisocyanate, etc. Aliphatic diisocyanates can be used especially effectively when one is suppressing the yellowing of elastic polyurethane threads. Moreover, these diisocyanates may be used individually or in mixtures or combinations of two or more.
Next, it is desirable to use at least one among low-molecular-weight diamines and low-molecular-weight diols as chain extenders which are used in synthesizing the polyurethanes. Furthermore, they may be ones which contain hydroxyl and amino groups in their molecules, such as ethanolamine.
Examples of desirable low-molecular-weight diamines are ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, hexamethylenediamine, p-phenylenediamine, p-xylylenediamine, m-xylylenediamine, p,p-′-methylenedianiline, 1,3-cyclohexyldiamine, hexahydrometaphenylenediamine, 2-methylpentamethylenediamine, bis(4-aminophenyl)phosphine oxide, etc. It is desirable to use 1 or 2 or more of these. Ethylenediamine is especially desirable. By using ethylenediamine, threads with excellent ductility and elastic recovery as well as heat resistance can be easily obtained. Triamine compounds, for example, diethylenetriamine, which can form cross-linked structures, may be added to these chain extenders to an extent that does not inhibit efficacy.
Moreover, typical low-molecular-weight diols are ethylene glycol, 1,3-propane diol, 1,4-butane diol, bishydroxyethoxybenzene, bishydroxyethylene terephthalate, 1-methyl-1,2-ethanediol, etc. It is desirable to use 1 or 2 or more of these. Especially desirable ones are ethylene glycol, 1,3-propanediol, and 1,4-butanediol. If these are used, the heat resistances as diol-extended polyurethanes become higher, and threads with higher strengths can be obtained.
The molecular weights of the polyurethanes in this invention are preferably in the range of 30,000-150,000 as number average molecular weights, from the point of view of obtaining fibers with high durability and strengths. Furthermore, the molecular weights are measured by GPC and converted by polystyrene.
It is also desirable for one or two or more end sequestering agents to be mixed into the polyurethanes.
Desirable examples of end sequestering agents are monoamines, such as dimethylamine, diisopropylamine, ethylmethylamine, diethylamine, methylpropylamine, isopropylmethylamine, diisopropylamine, butylmethylamine, isobutylmethylamine, isopentylmethylamine, dibutylamine, diamylamine, etc., monools, such as ethanol, propanol, butanol, isopropanol, allyl alcohol, cyclopentanol, etc., and monoisocyanates, such as phenyl isocyanate. Among them, it is preferable to use monoamines with molecular weights of 120 or less as end sequestering agents from the point of view of making the emitted quantity of monoamine compounds with molecular weights of 120 or less in the elastic polyurethane threads 100 μg/m², as a condition when the polyurethanes are polymerized.
In this invention, it is possible to improve the deodorant property with respect to ammonia gas also, without inhibiting the deodorant properties with respect to acetic acid gas, nonenal gas, and isovaleric acid gas which the elastic polyurethane threads contain as inherent constituents, by including metallic phosphates in the elastic polyurethane threads which consist of polyurethanes with the fundamental constitutions mentioned above. Moreover, it is possible to preserve excellent antibacterial activity at the same time by including monoamine compounds with molecular weights of 120 or less in the elastic polyurethane threads, making the quantity emitted from the elastic polyurethane threads 100 μg/m²or more, preferably 100-500 μg/m².
It is desirable for the metallic phosphates in this invention to be quaternary metallic acidic phosphates, such as zirconium phosphate and titanium phosphate, which have laminate structures, and aluminum dihydrogen tripolyphosphate, etc., from the point of view of the deodorant properties. Preferably, it is zirconium phosphate. These may be used individually or in mixtures of 2 or more.
The content of the metallic phosphates is preferably in the range of 0.5-10 wt % of the total weight of the elastic polyurethane threads. It is not desirable for the content of the metallic phosphates to be less than 0.5 wt %, since it will be hard to obtain sufficient deodorant property with respect to ammonia gas when fabrics are made. It is preferable for the content to be 1.0 wt % or greater. On the other hand, if the content exceeds 10 wt %, it is not desirable from the point of view of worsening the stretching property and the point of view of cost. It is preferable for the content to be 7.0 wt % or less. Considering the balance of the deodorant property with respect to ammonia gas, the physical properties, and the cost, it is especially desirable to make the content in the range of 1.5-5.0 wt %.
It is desirable for the metallic phosphates to be ones with average primary particle diameters of 3.0 μm or less from the point of view of suppressing the clogging up of the spinnerets with the spinning dope. It is still more preferable for the diameters to be 1.5 μm or less. Furthermore, from the point of view of dispersibility, if the average primary particle diameter is smaller than 0.05 μm, the cohesive force will be high and it will be difficult to mix them uniformly in the spinning dope; therefore, it is desirable for the average primary particle diameter to be 0.05 μm or larger. It is still more desirable for it to be 0.15 μm or larger.
On the other hand, in order to make the emitted quantity of monoamine compounds with molecular weights of 120 or less in the elastic polyurethane threads 100 μg/m²or more, it is desirable to include 0.01-0.5 wt % of monoamine compounds in the spinning dope containing polyurethanes. If the quantity of these monoamine compounds in the spinning dope is less than 0.01 wt %, sufficient monoamines will not be containing in the spun elastic polyurethane thread, and as a result, sufficient antibacterial property will not be obtained. On the other hand, if the content of the monoamine compounds in the spinning dope is greater than 0.5 wt %, the quality of the elastic polyurethane thread obtained, its yellowing property, etc., will be worsened.
Moreover, it is also possible to make the emitted quantity of the monoamine compounds in the elastic polyurethane thread threads 100 μg/m²or more by using monoamines with molecular weights of 120 or less as end sequestering agents when the polyurethane is synthesized, rather than adding the monoamines after the polymerization. Specifically, it is desirable to use a mixture of chain lengtheners such as diamine compounds and the aforementioned monoamine compounds prepared beforehand when the isocyanate and amino groups are reacted. It is desirable for the proportion of the amino groups in the chain lengthening agents to these monoamine and amino groups to be in the range of 5:1-25:1, preferably 5:1-20:1. It is desirable for the quantity of the mixture of the chain lengtheners and the aforementioned monoamine compounds used in the reaction to be such that the molar ratio of the isocyanate group concentration and the amino end group concentration at the time of the reaction to be in the range of 1:1.04-1:1.15. In this way, a polymer solution which contains more amino groups than in ordinary polymerization is obtained, and the quantity of these monoamines that is emitted can be maintained at 100 μg/m²even after the spinning.
Examples of the monoamine compounds with molecular weights of 120 or less are secondary amine compounds such as diethylamine, dimethylamine, diisopropylamine, ethylmethylamine, N-methylpropylamine, isopropylmethylamine, N-butylmethylamine, N-methylisobutylamine, etc., and primary amine compounds such as ethylamine, N-propylamine, isopropylamine, N-butylamine, cyclohexylmonoamine, etc. Secondary amine compounds are preferable from the point of view of the stability of the polyurethane spinning dope.
In order to further raise the antibacterial activity in the aforementioned kinds of elastic polyurethane threads, it is desirable for them to contain quaternary ammonium salt compounds as well. The quaternary ammonium salt compounds have different antibacterial strengths depending on the chain lengths of the alkyl groups in the ammonium ions; if the length differential of the alkyl groups is long, it will be easy for the antibacterial strength to be relatively high. Moreover, if the chain length is too short, it will be volatilized by the heat at the time of the spinning, and the quality will be easily altered. On the other hand, if the length differential of the alkyl groups is too long, the handling will become difficult. Therefore, it is desirable to choose the kinds of chains and chain lengths of the alkyl groups, etc., so that the desired properties are obtained.
Especially desirable ammonium ions from the point of view of antibacterial strength are stearyltrimethyl, cetyltrimethyl, didecyldimethyl, oleyltrimethyl, etc., ammonium ions. These ordinarily have the structure which is shown below; this structure is provided by organic acid salts such as sulfonic acid, phosphoric acid, etc., salts and salts such as chlorides, bromides, iodides, etc. Among these, sulfonic acid salts are preferable from the point of view of stability, that is, discoloration, heat resistance, etc.
(wherein

- R1 and R2 are hydrogens or alkyl groups with carbon numbers of 1-3 (which may be the same or different),
- R3 is an alkyl group with a carbon number of 10-22,
- R4 is an alkyl group with a carbon number of 1-22 (which may be the same or different from R1, R2, and R3), and R4 is an alkyl group with a carbon number of 1-22 (which may be the same or different from R1, R2, and R3), and X is an acidic counterion).
- X is an acidic counterion.

Specific examples of salts with this structure are didecyldimethylammonium 3-methylfluoride sulfonate, di-n-decyldimethylammonium trifluoromethyl sulfonate, di-n-decyldimethylammonium pentafluoroethyl sulfonate, n-hexadecyltrimethylammonium trifluoromethane sulfonate, and benzyldimethyl coconut oil alkyl ammonium pentafluoroethane sulfonate.
It is desirable for the quaternary ammonium salt compounds to be contained within the range of 0.1-5 wt %, preferably 0.2-2 wt %, with respect to the total weight of the elastic polyurethane thread, from the point of view of exhibiting the antibacterial property and maintaining the balance of the discoloration and the stretching property.
Furthermore, various stabilizers, pigments, etc., may be contained in the elastic polyurethane thread. For example, hindered phenol agents, such as BHT and “Sumilizer” GA-80 (trade name of Sumitomo Chemical Co.), various kinds of benzotriazoles such as “Chinubin” (trade name of Chiba Geigy Co.), benzophenone agents, phosphorus agents, such as “Sumilizer” P-16 (trade name of Sumitomo Chemical Industries Co.), various kinds of hindered amine agents, various kinds of pigments, such as iron oxide, titanium oxide, etc., inorganic substances, such as zinc oxide, cerium oxide, magnesium oxide, calcium carbonate, carbon black, etc., fluorine or silicone resin powders, metal soaps, such as magnesium stearate, etc., lubricants such as silicone, mineral oil, etc., and various kinds of antistatic agents, such as cerium oxide, betaine, phosphate agents, etc. Moreover, in order to further raise the durability, especially with respect to light and various nitrogen oxides, it is also desirable to use nitrogen acid scavengers, such as HN-150 (Nippon Hydrazine Co.), thermal oxidation stabilizers, such as “Sumilizer” GA-80 (trade name of Sumitomo Chemical Co.), and photostabilizers, such as “Sumisoap” 300 #622 (trade name of Sumitomo Chemical Co.), etc.
Next, the method of manufacturing the elastic polyurethane thread of this invention will be explained in detail.
In this invention, metallic phosphates and monoamine compounds with molecular weights of 120 or less are put into (that is, made to be present in) a polyurethane spinning dope obtained by using polymer diols and diisocyanates as starting materials, and this is spun. From the point of view of stabilizing the polymerization, it is desirable to make the polyurethane solution first and add a metallic phosphate dispersion and the monoamine compounds with molecular weights of 120 or less to it. Furthermore, the “spinning dope” in this invention means the liquid which is ultimately spun; on the other hand, “polyurethane solution” means a solution containing a polyurethane; it may be a liquid in any state.
The method of producing the polyurethane solution and the method of producing the polyurethane which is the solute of this solution may be either the melt polymerization or the solution polymerization method, or another method may be used. However, the solution polymerization method is preferable. In the case of the solution polymerization method, there is little production of foreign substances, such as a gel, in the polyurethane, the spinning is facilitated, and elastic polyurethane threads with low finenesses are easily obtained. Moreover, there is of course the advantage that the operation of making a solution can be omitted in the case of solution polymerization.
The polyurethane can be polymerized by using the aforementioned kinds of polymer diols, diisocyanates, and chain extenders and, if necessary, the aforementioned kinds of end sequestering agents. Examples of especially preferable polyurethanes are ones which use PTMGs with molecular weights of in the range of 1500-6000 as the polymer diols, MDI as the diisocyanate, and at least one of ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, or hexamethylenediamine as the chain extender.
The polyurethane is obtained by synthesizing it using the aforementioned raw materials in, for example, DMAc, DMF, DMSO, NMP, etc., or solutions containing them as the principal ingredient. Especially desirable methods which can be employed are, for example, the so-called “one-shot” method, in which the polyurethane is made by putting the raw materials into such a solvent, dissolving them, and performing the reaction by heating the solution to a suitable temperature, or a method in which the polyurethane is made by first melting and reacting the polymer diol and diisocyanate and then dissolving the reaction product in a solvent and reacting the aforementioned chain extender.
When a diol is used as the chain extender, it is desirable to adjust the melting point of the polyurethane on the high side, from 200° C. to 260° C. As a typical method, this is accomplished by controlling the kinds and proportions of the polymer diol, MDI, and diol. If the molecular weight of the polymer diol is low, a polyurethane with a high melting point can be obtained by making the proportion of the MDI relatively large; similarly, if the molecular weight of the diol is low, a polyurethane with a high melting point can be obtained by making the proportion of the polymer diol relatively small.
If the molecular weight of the polymer diol is 1800 or higher, it is desirable to perform the polymerization with a ratio of (number of moles of MDI)/(number of moles of the polymer diol)=1.5 or more, to make the melting point on the high side, 200° C. or higher.
Furthermore, in synthesizing this polyurethane, it is desirable to use one or a mixture of two or more solvents such as amine, organometallic, etc., solvents.
Examples of the amine solvents are 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′-tetramethylhexanediamine, bis-2-dimethylaminoethylether, N,N,N′,N′,N′-pentamethyldiethylenetriamine, tetramethylguanidine, triethylenediamine, N,N′-dimethylpiperazine, N-methyl-N′-dimethylaminoethylpiperidine, N-(2-dimethylaminoethyl)morpholine, 1-methylimidazol, 1,2-dimethylimidazole, N,N-dimethylaminoethanol, N,N,N′-trimethylaminoethylethanolamine, N′-methyl-N′-(2-hydroxyethyl)peperazine, 2,4,6-tris(dimethylaminomethyl)phenol, N,N-dimethylaminohexanol, triethanolamine, etc.
Moreover, as organometallic solvents, one can use tin octanoate, dibutyltin dilaurate, dibutyl lead octanoate, etc.
It is desirable, in this invention, to make the spinning dope by adding metal phosphates and monoamine compounds with molecular weights of 120 or less to this polyurethane solution. Any desired method may be employed to add the metal phosphates and monoamine compounds to the polyurethane solution. Typical such methods are ones using a static mixer, stirring, using a homomixer, using a twin-screw extruder, etc.
The metallic phosphate and monoamine compound may each be added individually to the polyurethane solution, or they may be mixed beforehand and the mixture added to the solution. It is preferable, from the point of view of realizing the deodorant property with respect to ammonia gas, to add them to the polyurethane solution after mixing them to make a dispersion.
It is desirable for the metallic phosphates to be contained in the elastic polyurethane thread in the range of 0.5-10 wt % in order to improve the deodorant property with respect to ammonia gas. To do this, the metallic phosphates must be dispersed without clumps in the polyurethane spinning dope, before spinning, in the range of 0.5-10 wt % of the dope; it is preferable to obtain the dope by adding the aforementioned metallic phosphates to a polyurethane solution which has N,N-dimethylformamide, N,N-dimethyl acetamide, etc., as the solvent and perform a mixing operation by stirring them so that they are dispersed without clumps. Specifically, it is desirable to make a metallic phosphate dispersion by dispersing the metallic phosphates beforehand in a solvent such as N,N-dimethylformamide, N,N-dimethylacetamide, etc., and then mix this dispersion with the polyurethane solution. Here, it is desirable to use a solvent of the metallic phosphate dispersion which is added which is the same as the solvent of the polyurethane solution, from the point of view of performing a uniform addition to the polyurethane solution. Moreover, when the metallic phosphate is added to the polyurethane solution, one may add, for example, the aforementioned light fastness agents, antioxidants, etc., and pigments, etc., simultaneously.
Furthermore, in this invention, the monoamine compounds may be put into the spinning dope used for the spinning in the end by using a large quantity of a monoamine with a molecular weight of 120 or less as the end sequestering agent when the polyurethane is synthesized, without adding a monoamine to the solution containing the polyurethane after the polyurethane is polymerized.
In this invention, metallic phosphates and monoamines with molecular weights of 120 or less are put into the spinning dope with the polyurethanes, as stated above, but in order to raise the antibacterial property against various kinds of bacteria it is desirable for the monoamine compounds with molecular weights of 120 or less to be contained in the spinning dope in the range of 0.01-0.5 wt %.
Moreover, it is ordinarily desirable for the concentration of the polyurethane in the polyurethane spinning dope to be in the rage of 30-80 wt %.
Furthermore, in this invention, it is desirable for quaternary ammonium salt compounds to be added in order to raise the antibacterial property against various kinds of bacteria. To do this, the quaternary ammonium salt compounds mentioned above are added to the polyurethane spinning dope before the spinning is performed. As the method of adding the quaternary ammonium salt compounds to the spinning dope, they may be added to the polyurethane solution by themselves, or they may be mixed with the aforementioned metallic phosphate solution beforehand.
The elastic polyurethane thread of this invention can be obtained by spinning the spinning dope constituted as described above by, for example, dry spinning, wet spinning, or melt spinning and winding them. Among these methods, dry spinning is preferable from the point of view that spinning can be performed stably at any fineness from fine to thick threads.
The fineness, cross sectional shape, etc., of the elastic polyurethane thread of this invention are not particularly limited. For example, the cross sectional shapes of the threads may be round or flat.
Moreover, the mode of dry spinning is not particularly limited; spinning conditions suitable for the desired properties and the spinning equipment may be selected.
For example, since the permanent strain rates and the stress relaxation percentages of the elastic polyurethane thread are easily affected by the ratio of the speeds of the godet rollers and the winding reel in particular, it is desirable to decide on suitable ratios for the purposes for which the threads will be used. That is, it is desirable for the ratio of the speeds of the godet rollers and the winding reel to be in the range of 1.10-1.65, from the point of view of obtaining elastic polyurethane thread with the desired permanent strain rates and stress relaxation percentages.
Moreover, it is desirable for the spinning speed to be 250 m/min or higher from the point of view of increasing the strengths of the elastic polyurethane thread obtained.

WORKING EXAMPLES

This invention will be explained in more detail by using working examples.
Strengths, stress relaxation percentages, permanent strain rates, and ductility of the elastic polyurethane thread:
The strengths, stress relaxation percentages, permanent strain rates, and ductility of the elastic polyurethane thread were measured by performing tensile tests with an Instron 4502 tensile tester.
They are defined below.
A 5 cm (L1) sample was stretched 300% 5 times at a tensile speed of 50 cm/min. The stress at the 5th time was taken to be (G1). Next, a 300% elongation was held for 30 seconds. The stress after it was held for 30 seconds was taken to be (G2). Next, the length of the sample when the elongation was repeated and the stress became 0 was taken to be (L2). Furthermore, the sample thread was elongated a 6th time until it broke. The stress at the time of the break was taken to be (G3) and the length of the sample thread when it broke was taken to be (L3).
The properties mentioned above are given by the following formulas:
Strength[cN]=(G3)
Stress relaxation percentage[%]=100×((G1)−(G2))/(G1)
Permanent strain rate[%]=100×(L2)−(L1))/(L1)
Ductility[%}=((L3)−(L1)/(L1))
Furthermore, the tensile tests were performed 3 times and the average values were obtained.
Production of knit for evaluating the deodorant and antibacterial properties: A 22 dtex elastic polyurethane thread was stretched 3-fold and covered with a polyamide finished thread (trade name “Kyuupu,” Toray Co., 33 desitex 26 filaments) at 800 twists/m, as a sheath thread to produce S twist and Z twist single covered yarns (SCY).
Furthermore, a knit was made by knitting the aforementioned S twist SCY in spinnerets 1 and 3 of a pantyhose knitting machine (Lonati Co., 400 needles) and the aforementioned Z twist SCY in spinnerets 2 and 4, with a knitting tension of 1.0 g. The content of the elastic polyurethane thread in the knit was 16%.
Next, the knit was dyed as follows to obtain knitted tights.
(1) Preset: 90° C.×10 minutes, using a vacuum drier.
(2) Dyeing: A treatment was performed for 60 minutes at 90° C., using the “Lanaset”™ Black B dye (Chiba Specialty Chemicals Co.) at 2.0 owf %, to dye the fabric black. The pH adjustment during the dyeing was performed with acetic acid and ammonium sulfate.
(3) Finally, a flexibility treatment was performed and a setting process (using a pantyhose setting machine; setting: 115° C.×10 seconds, drying: 120° C.×30 seconds) was then performed to finish the tights.
Washing Method:
The washing was performed according to the washing method manual prescribed by the Japanese Association for the Functional Evaluation of Textiles (JIS L0217: 1995 Appendix 1, Washing Method 103). That is, a home washing machine prescribed in JIS L0217: 1995 Appendix 1, Washing Method 103 was used. The washing liquid was made by dissolving 40 milliliters of JAFET standard detergent (Japanese Association for the Functional Evaluation of Textiles) in 30 liters of 40° C. water. The material to be washed, which was a 1 kg sample, was put into this washing liquid and washed for 5 minutes. The water was removed and it was rinsed for 2 minutes. The water was removed and it was rinsed for 2 minutes again, and dehydrated. These steps were counted as one washing.
Deodorant Property:
The deodorant property tests were performed according to the deodorant processing textile certification standards (Japan Textile Evaluation Technology Council, Product Certification Division; date of establishment of standards: Sep. 1, 2002). The evaluations of the deodorant properties of the odor ingredients were performed by means of an equipment test, as follows. Furthermore, Table 1 shows the standards criteria for a judgment of “has a deodorant effectiveness” concerning the percentages of reduction of the various odor ingredients by means of this machine analysis tester established by the Japan Textile Evaluation Technology Council.
Detector Method:
1. The sample (10 cm×10 cm) is put into a Tedlar bag.
2. A specific quantity of the test gas, shown in Table 1, is injected; the concentration of the gas remaining after 2 hours (ppm) is measured by the detector tube corresponding to the ingredient (Gasutekku Co.). The gas filling quantity is 3 L and the dilution gas is dry air or nitrogen gas.
TABLE 1

Starting Standard for Standards

Gas concentration (ppm) passing test established by:

Ammonia 100 70% or higher JAFET

Acetic acid 50 80% or higher JAFET

Nonenal 14 75% or higher JAFET

3. The same evaluation is performed without using the sample, as a blank test.
4. The evaluation is made according to the following formula; the percentage of reduction of the residual gas concentration is calculated and shown as the deodorant percentage.
$Reduction percentage (%) = \frac{(\begin{matrix} residual gas concentration of blank test - \\ residual gas concentration of sample \end{matrix})}{(Residual gas concentration of blank test)} \times 100$
Furthermore, the measurement values were obtained as the average values of n=3.
Antibacterial Property:
The antibacterial tests were performed according to the antibacterial property test procedures established by the Japan Textile Evaluation Technology Council (JIS L1902: 2008, bacterial suspension absorption method). The antibacterial potency was evaluated by calculating the bacteriostatic activity values using the following formula, in which X is the live bacteria count after culturing the unaltered sample for 18 hours and Y is the live bacteria count after culturing the test fabric for 18 hours. Furthermore, the measurement values were obtained from the average values of n=3.
Bacteriostatic activity=log X−log Y
Moreover, according to the Japan Textile Evaluation Technology Council, the samples were considered to be “effective” when the bacteriostatic activity value for Staphylococcus aureus was 2.2 or higher.
Quantity of Monoamine Compounds Emitted:
Pretreatment:
After the elastic polyurethane thread was wound, it was stored for 14 days at 35° C.×65% RH. After this, the thread was put into a plastic chuck bag (Seisannipponsha Ltd., J-4; 340 mm×240 mm×0.04 mm), clean air was injected into the bag, and it was quickly sealed, after which it was stored for 100 hours in a 23° C. room.
Analysis:
The entire quantity of the gas from the bag with the treated elastic polyurethane thread in it was collected in a collection tube. The collected organic component was heated and separated from the collection tube, introduced into a GC/MS apparatus, and analyzed. The measurement results are shown in Table 2.

TABLE 2

GAS CHROMATOGRAPH	6890 SERIES (Hewlett Packard)
COLUMN	CP-WAX52CB
	(Column no. 9020991)
	25 m × 0.32 mm, F.T 1.2 μm
INJECTION	TDU
	DESORB TEMP. 300° C. (8 min)
	LINE TEMP. 220° C.
COLUMN OVEN TEMP.	40° C. (6 min) → 100° C. (0 min) →
	250° C. (5 min) 7° C./min 20° C./min
MASS SPECTROMETER	JMS-AMSUN200 (JEOL)
IONIZATION/POLARITY	El+
IONIZATION VOLTAGE	70 eV
ION SOURCE TEMP.	220° C.
INTERFACE TEMP.	240° C.
APPIED VOLTAGE	10 kV
SCAN RANGE	26, 27, 29-230
CYCLE TIME	70 msec

The determination was performed by the absolute calibration method, by means of the total ion absolute area, using a toluene calibration curve. Furthermore, the quantity emitted from the sample per unit area was measured by the following formula; the measurement values were obtained by measuring the same sample level at 2 points and taking the average value of n=2.
Quantity emitted(μg/m²)=component quantity(μg)/exposed area of thread part(cm²)×10
Exposed area of thread part(cm²)=((A/2)²×3.14−(B/2)²×3.14)×2+((C+D)/2)×A×3.14
Here, A, B, C, and D were defined as shown in FIG. 1. Furthermore, in FIG. 1, (a) is a top view of the package and (b) is a side view of the package.
NOx Yellowing Resistance:
A sample card was made by winding 10 g of an elastic polyurethane thread on a stainless steel plate. This sample was exposed for 50 hours in a gas containing the prescribed concentration (7 ppm) of NO2 gas in air, using a Scott tester. Before and after this exposure treatment, the “b” color was measured with a Color Master (Model D25 DP-9000, Signal Processor), and the degree of yellowing was evaluated by the difference Δb before and after the treatment. Furthermore, the measurement values were obtained from the average values of n=3.
Average Primary Particle Diameter:
The inorganic particles were photographed with a Hitachi Ltd. field emission scanning electron microscope (FE-SEM) S-800; the images were analyzed with Image-Pro Version 4.0 image processing software. Furthermore, the diameters corresponding to the projected area circles were measured, and the average of n=20 per sample was obtained.
Metallic Phosphate Content:
The elastic polyurethane thread was analyzed by the original thread absorptiometric method and the concentrations of the metallic phosphates were measured. The measurements were performed with respect to the metals (Al, Zr, and Ti) in the metallic phosphates. Furthermore, the measurement values were obtained from the average values of n=3, and the contents of the metallic phosphates were obtained from the following formula:
$Metallic phosphate content (%) = measurement value (ppm) \times ((\frac{molecular weight of metallic phosphate}{molecular weight of metal constituting the metallic phosphate})) \times 10, 000$
Quaternary Ammonium Salt Content:
One gram of the sample (polyurethane thread) was weighed and put into 100 ml methanol, extracting the quaternary ammonium salt. The termination of the extract solution was performed from a standard solution which was made previously by liquid chromatography. The analysis conditions are shown below. Furthermore, the measurement values were obtained from the average values of n=2.
Column: LiChrospher 100 RP-18 (5 μm), inner diameter 4.6 mm, length 150 mm, column temperature: 35° C.

Detection: UV 210 nm

Mobile phase: methanol/water mixture (60/40 vol %); flow rate: 1 ml/min; quantity injected: 2 μl

Working Example 1

PTMG with a molecular weight of 1800 and MDI were reacted for 2 hours at 90° C. in the molar ratio 1:1.58 to produce a prepolymer with isocyanate ends, after which it was dissolved in DMAc at 35 wt % to prepare a prepolymer solution. Moreover, an amine solution was prepared by mixing ethylenediamine and 1,2-propanediamine as chain extenders and diethylamine as a chain terminator (end sequestering agent) in the proportions of 10:2:1 amino end group concentrations and dissolving this mixture in DMAc at 35 wt %. The prepolymer solution and the amine solution were mixed while stirring so that the molar ratio of the isocyanate end groups and amine end groups became 1:1.02, to prepare a DMAC solution (concentration 35 wt %) of a polyurethane urea polymer. Next, as an antioxidant, a polyurethane solution (Dupont Co. “Methacrol”™ 2462) produced by a reaction of t-butyldiethanolamine and methylene-bis(4-cyclohexyl isocyanate) and a condensation polymer of p-cresol and divinylbenzene (Dupont Co. “Methacrol”™ 2390) were mixed in a weight ratio of 2 to 1 to prepare an antioxidant DMAc solution (concentration 35 wt %). Ninety-six parts by weight of the aforementioned polyurethane urea polymer DMAc solution and 4 parts by weight of the antioxidant DMAc solution were mixed to make the polymer solution A1.
Next, the zirconium phosphate disodorant “Kesumon”™ NS-10 (Toagosei Co., average primary particle diameter 0.9 μm) was dispersed in DMAc with a homomixer to make the zirconium phosphate dispersion B1 (35 wt %).
Next, diethylamine (molecular weight 73.14) was prepared in DMAc at 35 wt % to make the monoamine solution C1.
The polymer solutions A1, B1, and C1 were uniformly mixed at 96.9 wt %, 3 wt %, and 0.1 wt % to make the spinning dope D1. This was dry-spun at a speed of 720 m/min, with a speed ratio of the godet rollers and the winder of 1.3. 200 g of a wound polyurethane 22 desitex, 2 filament thread with a zirconium phosphate content of 3 wt % was obtained.
A knit for evaluation was made with the elastic polyurethane thread obtained; its deodorant and antibacterial properties were measured. The results, together with the quantity of monoamine compound emitted and the NOx yellowing resistance of the elastic polyurethane thread itself, are shown in Tables 3, 4, and 5.

Working Example 2

The polymer solutions A1, B1, and C1 were uniformly mixed at 97.98 wt %, 2 wt %, and 0.02 wt % to make the spinning dope D2. This was dry-spun in the same manner as in Working Example 1 to make 200 g of a wound polyurethane 22 desitex, 2 filament thread with a zirconium phosphate content of 2 wt %.
The evaluation results are shown in Tables 3, 4, and 5.

Working Example 3

Instead of the zirconium phosphate dispersion B1, synthesized titanium phosphate (average primary particle diameter 1.1 μm) was dispersed in DMAc with a homomixer to make the titanium phosphate dispersion B2 (35 wt %).
The polymer solutions A1, B2, and C1 were uniformly mixed at 96.98 wt %, 3 wt %, and 0.02 wt % to make the spinning dope D3. This was dry-spun in the same manner as in Working Example 1 to make 200 g of a wound polyurethane 22 desitex, 2 filament thread with a titanium phosphate content of 3 wt %.
The evaluation results are shown in Tables 3, 4, and 5.

Working Example 4

Instead of the monoamine solution C1, ethylmethylamine (molecular weight 89.14) was prepared in DMAc at 35 wt % to make the monoamine solution C2 (35 wt %).
The polymer solutions A1, B1, and C2 were uniformly mixed at 94.88 wt %, 5 wt %, and 0.12 wt % to make the spinning dope D4. This was dry-spun in the same manner as in Working Example 1 to make 200 g of a wound polyurethane 22 desitex, 2 filament thread with a zirconium phosphate content of 5 wt %.
The evaluation results are shown in Tables 3, 4, and 5.

Working Example 5

Instead of the monoamine solution C1, diisopropylamine (molecular weight 101.19) was prepared in DMAc at 35 wt % to make the monoamine solution C3 (35 wt %).
The polymer solutions A1, B1, and C3 were uniformly mixed at 99.35 wt %, 0.5 wt %, and 0.15 wt % to make the spinning dope D5. This was dry-spun in the same manner as in Working Example 1 to make 200 g of a wound polyurethane 22 desitex, 2 filament thread with a zirconium phosphate content of 0.5 wt %.
The evaluation results are shown in Tables 3, 4, and 5.

Working Example 6

Instead of the monoamine solution C1, isopropylmethylamine (molecular weight 73.14) was prepared in DMAc at 35 wt % to make the monoamine solution C4 (35 wt %).
The polymer solutions A1, B1, and C4 were uniformly mixed at 89.5 wt %, 10.0 wt %, and 0.5 wt % to make the spinning dope D6. This was dry-spun in the same manner as in Working Example 1 to make 200 g of a wound polyurethane 22 desitex, 2 filament thread with a zirconium phosphate content of 10 wt %. However, thread breaking, which appeared to be plugging up of the spinneret, was produced during the spinning, so that the spinning ability was not good.
The evaluation results are shown in Tables 3, 4, and 5.

Working Example 7

Instead of the monoamine solution C1, N-butylamine (molecular weight 73.14) was prepared in DMAc at 35 wt % to make the monoamine solution C5 (35 wt %).
The polymer solutions A1, B1, and C5 were uniformly mixed at 95.9 wt %, 4.0 wt %, and 0.1 wt % to make the spinning dope D7. This was dry-spun in the same manner as in Working Example 1 to make 200 g of a wound polyurethane 22 desitex, 2 filament thread with a zirconium phosphate content of 4 wt %.
The evaluation results are shown in Tables 3, 4, and 5.

Working Example 8

The polymer solutions A1, B2, and C1 were uniformly mixed at 92.9 wt %, 7.0 wt %, and 0.1 wt % to make the spinning dope D8. This was dry-spun in the same manner as in Working Example 1 to make 200 g of a wound polyurethane 22 desitex, 2 filament thread with a titanium phosphate content of 7 wt %.
The evaluation results are shown in Tables 3 and 4.

Working Example 9

Instead of the zirconium phosphate dispersion B1, separately synthesized zirconium phosphate (average primary particle diameter 3.5 μm) was dispersed in DMAc with a homomixer to make the zirconium phosphate dispersion B3 (35 wt %).
The polymer solutions A1, B3, and C1 were uniformly mixed at 97.4 wt %, 2.5 wt %, and 0.1 wt % to make the spinning dope D9. This was dry-spun in the same manner as in Working Example 1 to make 50 g of a wound polyurethane 22 desitex, 2 filament thread with a titanium phosphate content of 2.5 wt %. However, thread breaking, which appeared to be plugging up of the spinneret, was produced during the spinning, so that the spinning ability was not good.
The evaluation results are shown in Tables 3, 4, and 5.

Working Example 10

The polymer solutions A1, B1, and C1 were uniformly mixed at 93.99 wt %, 6 wt %, and 0.01 wt % to make the spinning dope D10. This was dry-spun in the same manner as in Working Example 1 to make 200 g of a wound polyurethane 22 desitex, 2 filament thread with a zirconium phosphate content of 6 wt %.
The evaluation results are shown in Tables 3, 4, and 5.

Working Example 11

A DMAC (35 wt %) solution of a polyurethane urethane polymer consisting of PTMG with a molecular weight of 2100, MDI, ethylene glycol, and 1-butanol as an end sequestering agent was prepared. Next, as an antioxidant, a polyurethane solution (Dupont Co. “Methacrol”™ 2462) produced by a reaction of 5-butyldiethanolamine and methylene-bis(4-cyclohexyl isocyanate) and a condensation polymer of p-cresol and divinylbenzene (Dupont Co. “Methacrol”™ 2390) were mixed in a weight ratio of 2 to 1 to prepare an antioxidant DMAc solution (concentration 35 wt %). Ninety-six parts by weight of the aforementioned DMAc polyurethane polymer solution and 4 parts by weight of the antioxidant DMAc solution were mixed to make the polymer solution A2.
The quaternary ammonium chloride compound “Barquat”™ MS-100 (benzyldimethyltetradecyl ammonium chloride, Lonza Japan Co.) was dissolved in DMAc at 35 wt % to make the antibacterial 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 make the spinning dope D11. This was dry-spun in the same manner as in Working Example 1 to make 200 g of a wound polyurethane 22 desitex, 2 filament thread with a zirconium phosphate content of 2.5 wt %.
The evaluation results are shown in Tables 3, 4, and 5.

Working Example 12

Instead of the zirconium phosphate dispersion B1, an aluminum dihydrogen tripolyphosphate deodorant “K-Fresh”™ #100P (Teika Co., average primary particle diameter 1.0 μm) was dispersed in DMAc with a homomixer to make the aluminum dihydrogen tripolyphosphate dispersion B4 (35 wt %).
The polymer solutions A1, B4, and C1 were uniformly mixed at 94.8 wt %, 5 wt %, and 0.2 wt % to make the spinning dope D12. This was dry-spun in the same manner as in Working Example 1 to make 200 g of a wound polyurethane 22 desitex, 2 filament thread with an aluminum dihydrogen tripolyphosphate content of 5 wt %.
The evaluation results are shown in Tables 3, 4, and 5.

Working Example 13

The polymer solutions A2, B1, and C1 were uniformly mixed at 96.9 wt %, 3 wt %, and 0.1 wt % to make the spinning dope D13. This was dry-spun in the same manner as in Working Example 1 to make 200 g of a wound polyurethane 22 desitex, 2 filament thread with a zirconium phosphate content of 3 wt %.
The evaluation results are shown in Tables 3, 4, and 5.

Working Example 14

PTMG with a molecular weight of 1800 and MDI were mixed in the molar ratio 1:1.58 and reacted for 2 hours at 90° C. to produce a prepolymer with isocyanate ends, after which it was dissolved in DMAc at 35 wt % to prepare a prepolymer solution. Moreover, ethylene diamine, as a chain extender, and diethylamine, as a chain terminator, were mixed in the proportions of 14:1 amino end group concentrations and dissolved in DMAc at 35 wt % to prepare an amine solution.
The prepolymer solution and the amine solution were mixed, while stirring, so that the molar ratio of the isocyanate and amine end groups became 1:1.06 to prepare a DMAC solution (concentration 35 wt %) of a polyurethane urea polymer. Next, as an antioxidant, a polyurethane solution (Dupont Co. “Methacrol”™ 2462) produced by a reaction of t-butyldiethanolamine and methylene-bis(4-cyclohexyl isocyanate) and a condensation polymer of p-cresol and divinylbenzene (Dupont Co. “Methacrol”™ 2390) were mixed in a weight ratio of 2 to 1 to prepare an antioxidant DMAc solution (concentration 35 wt %). Ninety-six parts by weight of the aforementioned polyurethane polymer DMAc solution and 4 parts by weight of the antioxidant DMAc solution were mixed to make the polymer solution A3.
The polymer solutions A3 and B1 were uniformly mixed at 97 wt % and 3 wt % to make the spinning dope D14. This was dry-spun in the same manner as in Working Example 1 to make 200 g of a wound polyurethane 22 desitex, 2 filament thread with a zirconium phosphate content of 3 wt %.
The evaluation results are shown in Tables 3, 4, and 5.

Working Example 15

The quaternary ammonium salt compound “Nissan Cation”™ EQ-01D (Nichiyu Kagaku Co.) was made into a 35 wt % solution in DMCAc to make the antibacterial agent solution C7.
The polymer solutions A1, B1, C1, and C7 were uniformly mixed at 96.8 wt %, 2.5 wt %, 0.12 wt %, and 0.5 wt % to make the spinning dope D15. This was dry-spun in the same manner as in Working Example 1 to make 200 g of a wound polyurethane 22 desitex, 2 filament thread with a zirconium phosphate content of 2.5 wt %.
The evaluation results are shown in Tables 3, 4, and 5.

Working Example 16

The quaternary ammonium salt compound “Neojaami DFS” (Sanyo Kasei Co.) was made into a 35 wt % solution in DMCAc to make the antibacterial agent 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 make the spinning dope D16. This was dry-spun in the same manner as in Working Example 1 to make 200 g of a wound polyurethane 22 desitex, 2 filament thread with a zirconium phosphate content of 2.6 wt %.
The evaluation results are shown in Tables 3, 4, and 5.

Working Example 17

The polymer solutions A3, B1, and C8 were uniformly mixed at 97.4 wt %, 2.5 wt %, and 0.1 wt % to make the spinning dope D17. This was dry-spun in the same manner as in Working Example 1 to make 200 g of a wound polyurethane 22 desitex, 2 filament thread with a zirconium phosphate content of 2.5 wt %.
The evaluation results are shown in Tables 3, 4, and 5.

Comparison Example 1

Polymer solution A1 was dry-spun in the same manner as in Working Example 1 to make 200 g of a wound polyurethane 22 desitex, 2 filament thread.
The evaluation results are shown in Tables 3, 4, and 5.

Comparison Example 2

The polymer solutions A1 and B1 were uniformly mixed at 97.5 wt % and 2.5 wt % to make the spinning dope D18. This was dry-spun in the same manner as in Working Example 1 to make 200 g of a wound polyurethane 22 desitex, 2 filament thread with a zirconium phosphate content of 2.5 wt %.
The evaluation results are shown in Tables 3, 4, and 5.

Comparison Example 3

The polymer solutions A1 and C2 were uniformly mixed at 99.8 wt % and 0.2 wt % to make the spinning dope D19. This was dry-spun in the same manner as in Working Example 1 to make 200 g of a wound polyurethane 22 desitex, 2 filament thread.
The evaluation results are shown in Tables 3, 4, and 5.

Comparison Example 4

Instead of the zirconium phosphate dispersion B1, the silver-containing zeolite “Zeomikku”™ SW-10N (Shinanen Zeomikku Co.) (average primary particle diameter 1.0 μm) was dispersed in DMAc with a homomixer to make the zeolite dispersion Be (35 wt %).
The polymer solutions A1 and B3 were uniformly mixed at 96 wt % and 4 wt % to make the spinning dope D20. This was dry-spun in the same manner as in Working Example 1 to make 200 g of a wound polyurethane 22 desitex, 2 filament thread with a silver-containing zeolite content of 4 wt %.
The evaluation results are shown in Tables 3, 4, and 5.

Comparison Example 5

Instead of the monoamine solution C1, diamylamine (molecular weight 157.3) was prepared in DMAc at 35 wt % to make the monoamine solution C9 (35 wt %).
The polymer solutions A1, B1, and C9 were uniformly mixed at 97.9 wt %, 2.0 wt %, and 0.1 wt % to make the spinning dope D21. This was dry-spun in the same manner as in Working Example 1 to make 200 g of a wound polyurethane 22 desitex, 2 filament thread with a zirconium phosphate content of 2 wt %.
The evaluation results are shown in Tables 3, 4, and 5.

Comparison Example 6

Instead of the zirconium phosphate dispersion B1, the high-silica zeolite HSZ-980HOA (Tosoh Co.) (average primary particle diameter 2.0 μm) was dispersed in DMAc with a homomixer to make the zeolite dispersion B5 (35 wt %).
The polymer solutions A1, B5, and C1 were uniformly mixed at 96.8 wt %, 3 wt %, and 0.2 wt % to make the spinning dope D22. This was dry-spun in the same manner as in Working Example 1 to make 200 g of a wound polyurethane 22 desitex, 2 filament thread with a zeolite content of 3 wt %.
The evaluation results are shown in Tables 3, 4, and 5.

Comparison Example 7

Instead of the zirconium phosphate dispersion B1, the ultrafine particle zinc oxide “FINEX”-25 (Sakai Chemical Industry Co.) (average primary particle diameter 0.04 μm) was dispersed in DMAc with a homomixer to make the zeolite dispersion B6 (35 wt %).
The polymer solutions A1, B6, and C1 were uniformly mixed at 96.9 wt %, 3 wt %, and 0.1 wt % to make the spinning dope D23. This was dry-spun in the same manner as in Working Example 1 to make 200 g of a wound polyurethane 22 desitex, 2 filament thread with a zinc oxide content of 3 wt %.
The evaluation results are shown in Tables 3, 4, and 5.

Comparison Example 8

Instead of the monoamine solution C1, the natural antibacterial agent hinokitiol was prepared in DMAc at 35 wt % to make the monoamine solution C10 (35 wt %).
The polymer solutions A1, B6, and C10 were uniformly mixed at 96.9 wt %, 3 wt %, and 0.1 wt % to make the spinning dope D24. This was dry-spun in the same manner as in Working Example 1 to make 200 g of a wound polyurethane 22 desitex, 2 filament thread with a zinc oxide content of 3 wt %.
The evaluation results are shown in Tables 3, 4, and 5.

Working Example 9

The polymer solutions A1 and C8 were uniformly mixed at 99 wt % and 1 wt % to make the spinning dope D25. This was dry-spun in the same manner as in Working Example 1 to make 200 g of a wound polyurethane 22 desitex, 2 filament thread with a zinc oxide content of 3 wt %.
The evaluation results are shown in Tables 3, 4, and 5.

Comparison Example 10

Instead of the monoamine solution C1, the silver-containing antibacterial agent “Nobaron”™ AGT330 (Toagosei Co.) (average primary particle diameter 0.5 μm} was dispersed in DMAc with a homomixer to make the inorganic antibacterial dispersion C11 (35 wt %). 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 make the spinning dope D26. This was dry-spun in the same manner as in Working Example 1 to make 200 g of a wound polyurethane 22 desitex, 2 filament thread with a zirconium phosphate content of 1.5 wt %.
The evaluation results are shown in Tables 3, 4, and 5.

Comparison Example 11

The polymer solutions A12 and B1 were uniformly mixed at 97.5 wt % and 2.5 wt % to make the spinning dope D27. This was dry-spun in the same manner as in Working Example 1 to make 200 g of a wound polyurethane 22 desitex, 2 filament thread with a zirconium phosphate content of 2.5 wt %.
The evaluation results are shown in Tables 3, 4, and 5.

	TABLE 3

	Quantity of
	monoamines

Deodorant

Antibacterial agent

with molecular

			Content in		Content in	weights of 120
	Polymer		polyurethane		polyurethane	or less emitted

	solution	Ingredient	thread (wt %)	Ingredient	thread (wt %)	(μg/m²)

Working	A1	Zirconium	3	Diethylamine	0.1	300
Example 1		phosphate
Working	A1	Zirconium	2	Diethylamine	0.02	168
Example 2		phosphate
Working	A1	Titanium	3	Diethylamine	0.02	149
Example 3		phosphate
Working	A1	Zirconium	5	Ethylmethyl-	0.12	280
Example 4		phosphate		amine
Working	A1	Zirconium	0.5	Diisopropyl-	0.15	330
Example 5		phosphate		amine
Working	A1	Zirconium	10	Isopropyl	0.5	411
Example 6		phosphate		methylamine
Working	A1	Zirconium	4	N-butylamine	0.1	146
Example 7		phosphate
Working	A1	Titanium	7	Diethylamine	0.1	207
Example 8		phosphate
Working	A1	Zirconium	2.5	Diethylamine	0.1	254
Example 9		phosphate
Working	A1	Zirconium	6	Diethylamine	0.01	111
Example 10		phosphate
Working	A2	Zirconium	2.5	Diethylamine	0.2	290
Example 11		phosphate		Barquat	0.5
				MS-100
Working	A1	Zirconium	5	Diethylamine	0.2	283
Example 12		phosphate
Working	A2	Zirconium	3	Diethylamine	0.1	240
Example 13		phosphate
Working	A3	Zirconium	3	None	0	133
Example 14		phosphate
Working	A1	Zirconium	2.5	Diethylamine	0.2	270
Example 15		phosphate		Nissan Cation	0.5
				(R) EQ-01D
Working	A3	Zirconium	2.5	Neojaami DFS	1	124
Example 16		phosphate
Working	A3	Zirconium	2.5	Neojaami DFS	0.1	117
Example 17		phosphate
Comparison	A1	None	0	None	0	32
Example 1
Comparison	A1	Zirconium	2.5	None	0	6
Example 2		phosphate
Comparison	A1	None	0	Ethylmethyl-	0.2	323
Example 3				diamine
Comparison	A1	Silver-	4	None	0	5
Example 4		containing
		zeolite
Comparison	A1	Zirconium	2	Diamylamine	0.2	72
Example 5		phosphate
Comparison	A1	Zeolite	3	Diethylamine	0.2	90
Example 6
Comparison	A1	Zinc oxide	3	Diethylamine	0.1	241
Example 7
Comparison	A1	Zinc oxide	3	Hinokitiol	0.1	29
Example 8
Comparison	A1	None	0	Neojaami DFS	1	30
Example 9
Comparison	A1	Zirconium	1.5	Nobaron	1	10
Example 10		phosphate		AGT330
		Zinc oxide	1.0
Comparison	A2	Zirconium	3	None	0	0
Example 11		phosphate

TABLE 4

	Antibacterial property
	(Bacteriostatic
	activity value)
Deodorant property (reduction %)	Staphylococcus	NOx gas

Ammonia

Acetic acid

Nonenal

aureus

yellowing

No	After 10	No	After 10	No	After 10	No	After 10	discoloration
washing	washes	washing	washes	washing	washes	washing	washes	Δb

Working	83	85	88	90	89	91	5.1	4.3	6.8
Example 1
Working	79	79	87	87	95	95	4.6	4.2	6.7
Example 2
Working	84	79	86	88	90	92	4.2	3.9	6.9
Example 3
Working	85	89	89	88	89	88	4.8	4.0	7.0
Example 4
Working	71	72	88	90	89	90	5.2	4.2	7.9
Example 5
Working	90	92	88	87	83	84	5.3	4.4	5.9
Example 6
Working	72	78	90	91	91	91	3.3	3.2	8.0
Example 7
Working	95	90	92	92	84	85	4.1	3.8	7.1
Example 8
Working	77	78	91	89	84	85	4.5	4.0	7.1
Example 9
Working	96	92	85	87	84	83	3.9	3.3	6.5
Example 10
Working	76	75	84	83	90	92	5.4	5.5	8.1
Example 11
Working	76	74	90	89	91	93	4.6	4.3	6.9
Example 12
Working	78	77	82	81	89	91	3.2	2.8	5.5
Example 13
Working	80	74	90	88	92	90	4.1	3.4	5.3
Example 14
Working	77	76	87	84	91	91	4.7	3.9	8.0
Example 15
Working	74	74	90	89	92	93	5.2	4.9	9.6
Example 16
Working	78	75	88	85	91	90	4.5	3.5	8.2
Example 17
Comparison	23	28	82	84	77	75	0.9	0.5	5.0
Example 1
Comparison	80	77	91	90	78	80	0.2	0.3	5.1
Example 2
Comparison	22	20	80	84	82	88	5.0	3.1	7.7
Example 3
Comparison	71	66	91	90	86	86	4.9	4.8	24.4
Example 4
Comparison	74	70	85	86	94	96	1.9	1.7	8.1
Example 5
Comparison	55	56	86	86	98	95	2.0	2.1	14.5
Example 6
Comparison	56	50	83	85	82	87	5.1	4.1	10.3
Example 7
Comparison	54	48	85	88	84	83	5.2	4.3	12.2
Example 8
Comparison	25	25	88	86	90	91	4.8	4.4	9.5
Example 9
Comparison	69	47	88	85	90	88	5.2	5.3	9.4
Example 10
Comparison	65	58	80	81	87	86	0.1	0.1	4.9
Example 11

TABLE 5

	Duc-		Permanent	Stress
	tili-		strain	relaxation
Polymer	ty	Strength	rate	percentage
solution	(%)	(cN)	(%)	(%)

Working Example 1	A1	520	29	24	30
Working Example 2	A1	522	29	24	30
Working Example 3	A1	510	31	25	30
Working Example 4	A1	521	28	24	31
Working Example 5	A1	515	26	26	33
Working Example 6	A1	478	26	25	31
Working Example 7	A1	509	27	23	30
Working Example 8	A1	485	30	23	30
Working Example 9	A1	514	29	24	30
Working Example 10	A1	489	28	24	29
Working Example 11	A2	448	23	30	29
Working Example 12	A1	514	24	25	29
Working Example 13	A2	453	23	30	29
Working Example 14	A3	513	31	19	28
Working Example 15	A1	527	23	24	30
Working Example 16	A3	514	31	20	28
Working Example 17	A3	515	31	20	28
Comparison Example	A1	544	25	23	31
1
Comparison Example	A1	541	25	24	30
2
Comparison Example	A1	521	24	24	30
3
Comparison Example	A1	520	24	24	30
4
Comparison Example	A1	521	24	23	29
5
Comparison Example	A1	524	24	24	30
6
Comparison Example	A1	517	24	23	30
7
Comparison Example	A1	533	24	24	30
8
Comparison Example	A1	507	24	22	30
9
Comparison Example	A1	512	24	23	29
10
Comparison Example	A2	455	23	30	30
11

Possible Uses in Industry:

By means of this invention, it is possible to obtain elastic polyurethane thread with excellent stretch abilities and deodorant, antibacterial, and colorfastness properties; therefore, it is possible to obtain fabrics with excellent stretch abilities and deodorant, antibacterial, and colorfastness properties.

EXPLANATION OF SYMBOLS

A Outer diameter of package
B Outer diameter of paper tube
C Thread winding width of outermost layer
D Thread winding width of innermost layer

Claims

1. An elastic polyurethane thread which is an elastic thread consisting of a polyurethane which has polymer diols and diisocyanates as the starting materials, contains metallic phosphates, and has an emitted quantity of monoamine compounds with molecular weights of 120 or less of 100 μg/m²or more.

2. An elastic polyurethane thread in accordance with claim (1) above in which the content of the aforementioned metallic phosphates is in the range of 0.5-10 wt %.

3. An elastic polyurethane thread in accordance with claim (1) above in which the average primary particle diameter of the aforementioned metallic phosphates is 3.0μ or less.

4. An elastic polyurethane thread in accordance with claim (1) above in which the aforementioned metallic phosphates are at least one selected from a group comprising titanium phosphate, zirconium phosphate, and aluminum dihydrogen tripolyphosphate.

5. An elastic polyurethane thread in accordance with claim (1) above in which the aforementioned emitted monoamine compounds are secondary monoamine compounds.

6. An elastic polyurethane thread in accordance with claim (1) above which also contains quaternary ammonium salt compounds.

7. An elastic polyurethane thread in accordance with claim (6) above in which the aforementioned quaternary ammonium salt compounds have the following structure:

(wherein

R1 and R2 are hydrogens or alkyl groups with carbon numbers of 1-3 (which may be the same or different),

R3 is an alkyl group with a carbon number of 10-22,

R4 is an alkyl group with a carbon number of 1-22 (which may be the same or different from R1, R2, and R3), and R4 is an alkyl group with a carbon number of 1-22 (which may be the same or different from R1, R2, and R3), and

X is an acidic counterion).

8. An elastic polyurethane thread in accordance with claim (6) above in which the content of the aforementioned quaternary ammonium salt compounds is in the range of 0.1-5 wt %.

9. A method of manufacturing an elastic polyurethane thread in which metallic phosphates are mixed with a spinning dope which contains polyurethanes which have polymer diols and diisocyanates as starting materials, mixing is performed in such a way that the content of monoamine compounds with molecular weights of 120 or less is in the range of 0.01-0.5 mass %, and this spinning dope is dry-spun.

10. A method of manufacturing an elastic polyurethane thread in accordance with claim (9) in which the aforementioned metallic phosphates are mixed in with the spinning dope which contains polyurethanes which have polymer diols and diisocyanates as starting materials as a dispersion liquid.

11. An elastic polyurethane thread in accordance with claim (9) in which the aforementioned metallic phosphates are at least one selected from a group comprising titanium phosphate, zirconium phosphate, and aluminum dihydrogen tripolyphosphate.

12. An elastic polyurethane thread in accordance with claim (9) in which the aforementioned monoamine compounds with molecular weights of 120 or less are secondary amine compounds.