JP4968648B2 - Polyurethane elastic yarn and method for producing the same - Google Patents

Description

  The present invention relates to a polyurethane elastic yarn having alkali resistance, resistance to various drugs, high recovery, high strength elongation, high heat resistance, and the like, and a method for producing the same.

  Elastic fibers are widely used for stretch clothing and industrial materials such as leg wear, inner wear, and sports wear due to their excellent stretch properties.

  As such elastic fibers, in particular, polyurethane elastic yarns are required to have high tensile elongation, high recoverability, high chemical resistance, and high heat resistance. In particular, chemical resistance has been strongly demanded in recent years when used in mixed fabrics in combination with polyester yarns. Chemical resistance that can withstand polyester weight loss processing and extraction processing, that is, alkali, unsaturated fatty acid, quaternary Resistance to ammonium salts and the like is required.

  As a conventional technique for imparting such chemical resistance, for example, a technique of spinning by containing polyvinylidene fluoride in a polyurethane spinning solution is known (for example, see Patent Document 1).

However, in the case of polyurethane elastic yarns containing polyvinylidene fluoride in this way, recovery and heat resistance are not sufficient, and chemical resistance still remains particularly in the use of mixed fabrics with polyester yarns that require weight loss processing and high-temperature dyeing. It is an unsatisfactory level, and its use may be limited.
JP 2000-73233 A

  The present invention solves the above-mentioned problems of the prior art and provides a polyurethane elastic yarn having alkali resistance, resistance to various drugs, high recovery, high strength elongation, and high heat resistance, and a method for producing the same. Objective.

In order to achieve the above object, the polyurethane elastic yarn of the present invention employs any of the following means.
(1) A polyurethane elastic yarn starting from a polymer diol and a diisocyanate, wherein the aromatic condensed phosphate represented by the formula 1 is contained in the range of 0.5 wt% to 22 wt%. Polyurethane elastic yarn.

(R1 is an aromatic group, R2 is hydrogen or an alkyl group having 1 to 3 carbon atoms, a plurality of R2s may be the same or different, and R3 is hydrogen or carbon number. 1 to 3 alkyl groups, and a plurality of R3 may be the same or different.)
(2) The polyurethane elastic yarn according to the above (1), wherein the aromatic condensed phosphate ester is 1,3-phenylenebisdixylenyl phosphate.
(3) The polyurethane according to the above (1) or (2), which shows self-extinguishing properties when knitting a tubular knitted fabric having a width of 5 cm and performing a horizontal combustion test by the US automobile safety standard FMVSS-302 method. Elastic yarn.
(4) A polyurethane solution containing polyurethane starting from a polymer diol and a diisocyanate is mixed with an aromatic condensed phosphate represented by the formula 1 in a range of 0.5 wt% to 22 wt% , and spinning. A method for producing a polyurethane elastic yarn, comprising:

  The polyurethane elastic yarn of the present invention has alkali resistance, resistance to various drugs, high recovery, high strength elongation, and high heat resistance. Therefore, clothes using this elastic yarn can be attached and detached. It is excellent in properties, wear feeling, dyeability, discoloration resistance, appearance quality and the like. In addition, the polyurethane elastic yarn of the present invention is excellent in flame retardancy in addition to the above characteristics, and therefore can be suitably used in fields where flame retardancy is required. It is suitable as a material for vehicles and further for aircraft and ships.

  The present invention is described in further 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 polyurethane starting from a polymer diol and a diisocyanate. Also, the synthesis method is not particularly limited.

  That is, for example, it may be a polyurethane urea composed of a polymer diol, diisocyanate and a low molecular weight diamine, or may be a polyurethane composed of a polymer diol, diisocyanate and a low molecular weight diol. Moreover, the polyurethane urea which uses the compound which has a hydroxyl group and an amino group in a molecule | numerator as a chain extender may be used. In addition, it is also preferable to use trifunctional or higher polyfunctional glycol or isocyanate or the like as long as the effects of the present invention are not hindered.

  Here, typical structural units constituting the polyurethane used in the present invention will be described.

  As the polymer diol of the structural unit constituting the polyurethane, polyether glycol, polyester glycol, polycarbonate diol and the like are preferable. In particular, polyether glycol is preferably used from the viewpoint of imparting flexibility and elongation to the yarn.

  The polyether glycol preferably contains a copolymerized diol compound containing a unit represented by the following general formula (II).

(Where a and c are integers of 1 to 3, b is an integer of 0 to 3, R1 and R2 are H or an alkyl group of 1 to 3 carbon atoms)
Specific examples of the polyether diol compound include polyethylene glycol, modified polyethylene glycol, polypropylene glycol, polytrimethylene ether glycol, polytetramethylene ether glycol (hereinafter abbreviated as PTMG), tetrahydrofuran (hereinafter abbreviated as THF). ) And 3-methyl-THF copolymer modified PTMG, THF and 2,3-dimethyl-THF copolymer modified PTMG, THF and neopentyl glycol copolymer modified PTMG, THF and Examples thereof include random copolymers in which ethylene oxide and / or propylene oxide are irregularly arranged. One kind of these polyether glycols may be used, or two or more kinds may be mixed or copolymerized. Among these, PTMG or modified PTMG is preferable.

  Further, from the viewpoint of enhancing the abrasion resistance and light resistance of polyurethane yarn, it is obtained by polycondensing a mixture of butylene adipate, polycaprolactone diol, 3-methyl-1,5-pentanediol and polypropylene polyol with adipic acid or the like. Dicarboxylic acid ester units derived from a polyester glycol such as a polyester diol having a side chain and a dicarboxylic acid component consisting of 3,8-dimethyldecanedioic acid and / or 3,7-dimethyldecanedioic acid and a diol component A polycarbonate diol containing bismuth is preferably used.

  These polymer diols may be used alone or in combination of two or more.

  The molecular weight of the polymer diol used in the present invention is preferably 1000 to 8000, more preferably 1800 to 6000 in terms of number average molecular weight in order to obtain desired levels of elongation, strength, heat resistance and the like when elastic yarn is formed. . By using a polymer diol having a molecular weight within this range, an elastic yarn excellent in elongation, strength, elastic recovery, and heat resistance can be obtained.

  Next, as the diisocyanate of the structural unit constituting the polyurethane, aromatic diisocyanates such as diphenylmethane diisocyanate (hereinafter abbreviated as MDI), tolylene diisocyanate, 1,4-diisocyanate benzene, xylylene diisocyanate, 2,6-naphthalene diisocyanate, etc. However, it is particularly suitable for synthesizing polyurethane having high heat resistance and high strength. Further, as alicyclic diisocyanates, for example, methylene bis (cyclohexyl isocyanate), isophorone diisocyanate, methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate, cyclohexane-1,4-diisocyanate, hexahydroxylylene diisocyanate, hexa Hydrotolylene diisocyanate, octahydro-1,5-naphthalene diisocyanate and the like are preferable. Aliphatic diisocyanates can be used effectively particularly when suppressing yellowing of polyurethane yarns. And these diisocyanates may be used independently and may use 2 or more types together.

  Next, it is preferable to use at least one of a low molecular weight diamine and a low molecular weight diol as the chain extender of the structural unit constituting the polyurethane. In addition, you may have a hydroxyl group and amino groups in a molecule like ethanolamine.

  Preferred low molecular weight diamines include, for example, 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 and the like. It is also preferred that one or more of these are used. Particularly preferred is ethylenediamine. By using ethylenediamine, it is possible to obtain a yarn excellent in elongation, elastic recovery, and heat resistance. A triamine compound capable of forming a crosslinked structure such as diethylenetriamine may be added to these chain extenders to such an extent that the effect is not lost.

  Typical low molecular weight diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, bishydroxyethoxybenzene, bishydroxyethylene terephthalate, 1-methyl-1,2-ethanediol, and the like. Is. It is also preferred that one or more of these are used. Particularly preferred are ethylene glycol, 1,3-propanediol, and 1,4-butanediol. When these are used, a diol-extended polyurethane has a high heat resistance and a high strength yarn can be obtained.

  Furthermore, it is also preferable for the polyurethane in the present invention to use one or more end blockers. As end-capping agents, dimethylamine, diisopropylamine, ethylmethylamine, diethylamine, methylpropylamine, isopropylmethylamine, diisopropylamine, butylmethylamine, isobutylmethylamine, isopentylmethylamine, dibutylamine, diamylamine and other monoamines, ethanol Monools such as propanol, butanol, isopropanol, allyl alcohol and cyclopentanol, and monoisocyanates such as phenyl isocyanate are preferred.

  In addition, the molecular weight of the polyurethane elastic yarn of the present invention is preferably in the range of 40000 to 150,000 as the number average molecular weight from the viewpoint of obtaining fibers having high durability and strength. The molecular weight is a value measured by GPC and converted by polystyrene.

  And, particularly preferred as the polyurethane constituting the elastic yarn of the present invention, including the process passability, there is no practical problem, and from the viewpoint of obtaining an excellent high heat resistance, consisting of diol and diisocyanate, In addition, the melting point on the high temperature side is in the range of 200 ° C to 300 ° C. Here, the melting point on the high temperature side corresponds to the melting point of so-called hard segment crystals of polyurethane or polyurethane urea as measured by DSC.

  That is, PTMG having a molecular weight in the range of 1000 to 6000 as a polymer diol, MDI as a diisocyanate, ethylene glycol, 1,3-propanediol, 1,4-butanediol, ethylenediamine, 1,2-propanediamine as a chain extender A polyurethane produced by using at least one selected from the group consisting of 1,3-propanediamine and having a melting point on the high temperature side in the range of 200 ° C. to 300 ° C. Yarns are particularly preferred because they have a particularly high elongation and, as described above, have no practical problems including process passability and are excellent in high heat resistance.

  In addition, as a method for setting the melting point on the high temperature side of the polyurethane yarn to 200 ° C. or more and 300 ° C. or less, a method of selecting an optimum value of the ratio of diisocyanate, polymer diol, and chain extender by a prior test is preferable.

  Next, as the aromatic condensed phosphate ester in the present invention, two or more phosphoric acids are bonded via an aromatic group. In the present invention, an aromatic condensed phosphate having a structure represented by the general formula (I) can be preferably used.

(R1 is an aromatic group, R2 is hydrogen or an alkyl group having 1 to 3 carbon atoms, a plurality of R2s may be the same or different, and R3 is hydrogen or carbon number. 1 to 3 alkyl groups, and a plurality of R3 may be the same or different.)
Specifically, 1,3-phenylene bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), bisphenol S bis (diphenyl phosphate), 1,3-phenylene bis (dixylenyl phosphate) and the like are preferable. Among them, in order to exhibit higher chemical resistance and heat resistance, those in which R2 in the general formula (I) is substituted with an alkyl group are preferable, for example, 1,3-phenylenebis (dixylenyl phosphate) and the like. preferable.

The amount of the aromatic condensed phosphoric acid ester contained in the polyurethane elastic yarn of the present invention is in the range of 0.5 wt% to 22 wt% from the viewpoint of obtaining good spinnability, balanced mechanical properties, and heat resistance. From the viewpoint of reducing the drop in the strength and elongation of the polyurethane yarn, it is more preferably 5% by weight or more and 20% by weight or less.

  In the present invention, various stabilizers, pigments, and the like may be contained in the polyurethane elastic yarn or polyurethane spinning solution. For example, hindered phenolic chemicals such as 2,6-di-t-butyl-p-cresol (BHT) and “Sumilyzer GA-80” manufactured by Sumitomo Chemical Co., Ltd. Benzotriazole and benzophenone drugs such as “Tinuvin” manufactured by Sumitomo Chemical Co., Ltd. Phosphorus drugs such as “Sumilyzer P-16” manufactured by Sumitomo Chemical Co., Ltd., various hindered amine drugs, various pigments such as iron oxide and titanium oxide, oxidation Inorganic materials such as zinc, cerium oxide, magnesium oxide, carbon black, fluorine-based or silicone-based resin powder, metal soaps such as magnesium stearate, and bactericides and deodorants containing silver, zinc, and these compounds, Also, lubricants such as silicone and mineral oil, barium sulfate, cerium oxide, betaine and phosphate Preferably also be included, such as antistatic agents, It is also preferred to react the these with polymers. And in order to further improve the durability to light, various nitric oxides, and the like, it is also preferable to use a nitrogen oxide scavenger such as HN-150 manufactured by Nippon Hydrazine Co., Ltd.

  Further, from the viewpoint of easily increasing the spinning speed in the dry spinning process, fine particles of metal oxide such as titanium dioxide and zinc oxide may be added. In addition, from the viewpoint of improving heat resistance and functionality, inorganic substances and inorganic porous materials (such as bamboo charcoal, charcoal, carbon black, porous mud, clay, diatomaceous earth, coconut husk activated carbon, coal-based activated carbon, zeolite, pearlite, etc.) , And may be added within a range that does not inhibit the effects of the present invention.

  These other additives may be added when preparing the spinning dope by mixing the polyurethane solution with the aromatic condensed phosphate ester described above, or in the polyurethane solution or dispersion before mixing. You may make it contain beforehand. The content of these additives is appropriately determined according to the purpose and the like.

  The polyurethane elastic yarn of the present invention has excellent characteristics such as alkali resistance, resistance to various drugs, high recovery, high strength elongation, and high heat resistance by the above configuration. Furthermore, in addition to these excellent properties, a polyurethane elastic yarn having flame retardancy can be obtained.

  No flame retardant polyurethane elastic yarn has been known in the past, and in applications that require flame retardant properties, a conventional polyurethane elastic yarn is usually used to form a woven or knitted fabric, followed by flame retardant processing as post-processing. Has been. Therefore, even if a woven or knitted fabric is formed using a flame retardant yarn such as a flame retardant polyester as a yarn to be mixed with a polyurethane elastic yarn, post-processing is currently required. However, in a preferred embodiment of the present invention, a knitted fabric having a width of about 5 cm is knitted using only a flame retardant polyurethane elastic yarn, that is, a polyurethane elastic yarn, without being subjected to flame retardant processing as post-processing. However, it is possible to exhibit self-extinguishing properties (combustion treatment is 0 mm) when a horizontal combustion test is performed according to the US automobile safety standard FMVSS-302 method. Therefore, for example, when a woven or knitted fabric is formed by mixing with a flame retardant yarn such as a flame retardant polyester yarn, the flame retardant processing as a post-processing can be omitted. The details of the flame retardancy test method will be described in the examples described later.

  In order to express flame retardancy in the polyurethane elastic yarn of the present invention, the content of the aromatic condensed phosphate ester in the polyurethane elastic yarn is preferably 3.0% by weight or more, and the good as described above. Considering the spinnability, well-balanced mechanical properties, and maintenance of high elongation, it is preferably 5.0 to 20.0% by weight.

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

  In the present invention, it is preferable to prepare a polyurethane solution first. The method for producing a polyurethane solution and polyurethane as a solute in the solution may be either a melt polymerization method or a solution polymerization method, or may be another method. However, the solution polymerization method is more preferable. In the case of the solution polymerization method, since the generation of foreign matters such as gels is small in the polyurethane, it is easy to spin and it is easy to produce a polyurethane yarn with a low fineness. In addition, the solution polymerization method has an advantage that an operation for forming a solution can be omitted.

  As a polyurethane particularly suitable for the present invention, PTMG having a molecular weight of 1000 or more and 6000 or less is used as a polymer diol, MDI is used as a diisocyanate, ethylene glycol, 1,3-propanediol, 1,4 is used as a chain extender. -Synthesized using at least one of butanediol, ethylenediamine, 1,2-propanediamine and 1,3-propanediamine and having a melting point on the high temperature side in the range of 200 ° C to 300 ° C. Can be mentioned.

  Such polyurethanes include, for example, dimethylacetamide (abbreviated as DMAc), dimethylformamide (abbreviated as DMF), dimethyl sulfoxide (abbreviated as DMSO), N-methyl-2-pyrrolidone (abbreviated as NMP). It can be obtained by synthesizing using the above raw materials in a solvent mainly composed of these. For example, each raw material is charged in such a solvent, dissolved, heated to an appropriate temperature and reacted to form polyurethane, a so-called one-shot method, or polymer diol and diisocyanate are first melt-reacted and then reacted. A particularly preferable method is a method in which a product is dissolved in a solvent and reacted with the above-mentioned diol to form polyurethane.

  When using a diol as the chain extender, the typical method for setting the high-temperature melting point of polyurethane within the range of 200 ° C to 300 ° C is to control the types and ratios of polymer diol, MDI, and diol. Is mentioned. For example, when the molecular weight of the polymer diol is low, a polyurethane having a high melting point on the high temperature side can be obtained by relatively increasing the proportion of MDI. Similarly, when the molecular weight of the diol is low, a polyurethane having a high melting point on the high temperature side can be obtained by relatively reducing the proportion of the polymer diol. In the case where the molecular weight of the polymer diol is 1800 or more, in order to increase the melting point on the high temperature side to 200 ° C. or more, the polymerization is advanced at a ratio of (number of moles of MDI) / (number of moles of polymer diol) = 1.5 or more. Is preferred.

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

  Examples of the amine catalyst include N, N-dimethylcyclohexylamine, N, N-dimethylbenzylamine, triethylamine, N-methylmorpholine, N-ethylmorpholine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyl-1,3-propanediamine, N, N, N ′, N′-tetramethylhexanediamine, bis-2-dimethylaminoethyl ether, N, N, N ′ , N ′, N′-pentamethyldiethylenetriamine, tetramethylguanidine, triethylenediamine, N, N′-dimethylpiperazine, N-methyl-N′-dimethylaminoethyl-piperazine, N- (2-dimethylaminoethyl) morpholine, 1-methylimidazole, 1,2-dimethylimidazole, N, N-dimethylamido Noethanol, N, N, N′-trimethylaminoethylethanolamine, N-methyl-N ′-(2-hydroxyethyl) piperazine, 2,4,6-tris (dimethylaminomethyl) phenol, N, N-dimethyl Examples include aminohexanol and triethanolamine.

  Examples of organometallic catalysts include tin octoate, dibutyltin dilaurate, and lead dibutyl octoate.

  The concentration of polyurethane in the polyurethane solution thus obtained is usually preferably in the range of 30% by weight to 80% by weight.

  In the present invention, it is preferable to add an aromatic condensed phosphate to such a polyurethane solution. Any method can be adopted as a method for adding the aromatic condensed phosphate ester to the polyurethane solution. As typical methods, various means such as a method using a static mixer, a method using stirring, a method using a homomixer, a method using a biaxial extruder, and the like can be adopted. Here, the aromatic condensed phosphate ester to be added is preferably added as a solution from the viewpoint of uniform addition to the polyurethane solution.

  Note that the addition of aromatic condensed phosphate ester to the polyurethane solution may cause a phenomenon in which the solution viscosity of the mixed solution after the addition becomes higher than expected compared to the solution viscosity of the polyurethane before the addition. From the viewpoint of preventing dimethylamine, diisopropylamine, ethylmethylamine, diethylamine, methylpropylamine, isopropylmethylamine, diisopropylamine, butylmethylamine, isobutylmethylamine, isopentylmethylamine, dibutylamine, diamylamine and other monoamines, One or more end-capping agents such as monools such as ethanol, propanol, butanol, isopropanol, allyl alcohol, cyclopentanol, and monoisocyanates such as phenyl isocyanate are used in combination. It is it is also preferable to be.

  When the aromatic condensed phosphate ester is added to the polyurethane solution, for example, the above-mentioned chemicals such as a light-proofing agent and an antioxidant and pigments may be added simultaneously.

  The polyurethane elastic yarn of the present invention can be obtained by, for example, dry spinning, wet spinning, or melt spinning, and winding up the polyurethane solution configured as described above. Of these, dry spinning is preferred from the viewpoint of stable spinning at all finenesses from fine to thick.

  The fineness, the number of single yarns, the cross-sectional shape, etc. of the polyurethane elastic yarn of the present invention are not particularly limited. For example, the yarn may be a monofilament composed of one single yarn or a multifilament composed of a plurality of single yarns. The cross-sectional shape of the yarn may be circular or flat.

  Also, the dry spinning method is not particularly limited, and spinning may be performed by an arbitrary method, that is, by appropriately selecting a spinning condition suitable for desired characteristics and spinning equipment.

  For example, the permanent strain rate and stress relaxation characteristics of the polyurethane elastic yarn of the present invention are particularly easily influenced by the speed ratio of the godet roller and the winder, and therefore it is preferable to be determined appropriately according to the intended use of the yarn. That is, from the viewpoint of obtaining a polyurethane elastic yarn having a desired permanent set rate and stress relaxation, it is preferable that the speed ratio between the godet roller and the winder is 1.15 to 1.65. When obtaining a polyurethane elastic yarn having a particularly low permanent set rate and low stress relaxation, the speed ratio between the godet roller and the winder is more preferably in the range of 1.15 or more and 1.40 or less, and 1.15 or more. The range of 1.35 or less is more preferable. On the other hand, when obtaining a polyurethane elastic yarn having a high permanent set rate and high stress relaxation, it is preferable that the speed ratio between the godet roller and the winder is in the range of 1.25 to 1.65. The range of 35 or more and 1.65 or less is more preferable.

  Further, since the strength of the polyurethane elastic yarn can be improved by increasing the spinning speed, it is preferable to take a spinning speed of 450 m / min or more in order to obtain a practically suitable strength level. Further, considering the point of industrial production, about 450 to 1000 m / min is preferable.

  The polyurethane elastic yarn of the present invention obtained as described above can be mixed with other fibers to constitute a stretchable fabric. The form of the stretchable cloth is not limited at all, and the mixing ratio, the raw material fibers to be combined, and the mixing method may be appropriately selected and formed into a cloth by a known means. The polyurethane elastic yarn may be used as a bare yarn as it is, or one or more kinds of conventionally known fibers such as polyamide fibers, polyester fibers and synthetic fibers such as acrylic fibers, and natural fibers such as cotton and wool. You may use what was combined freely or was coat | covered.

  In addition, as a fiber to be combined with the polyurethane elastic yarn of the present invention in constituting the fabric, polyamide fiber such as nylon, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, and copolymer polyester fiber mainly composed of these are used. Polyester synthetic fiber, acrylic synthetic fiber, polypropylene synthetic fiber, semi-synthetic fiber typified by acetate fiber, natural fiber typified by cotton, hemp or wool, or a mixture of two or more Are preferably used.

  The invention is explained in more detail by means of examples.

  A method for measuring the breaking strength, breaking elongation, permanent strain rate, stress relaxation, chemical resistance, alkali resistance, and heat resistance (thermal softening point, melting point) of the polyurethane elastic yarn in the present invention will be described.

[Permanent distortion, stress relaxation, breaking strength, breaking elongation]
The permanent set rate, stress relaxation, breaking strength, and breaking elongation were measured by tensile testing polyurethane elastic yarn using an Instron 4502 type tensile tester. The number of measurements was measured at n = 3, and the average value thereof was adopted.

  A sample having a test length of 5 cm (L1) was repeatedly stretched 300% at a tensile rate of 50 cm / min five times. At this time, the stress at 300% elongation was defined as (G1). Next, the length of the sample was maintained for 30 seconds with 300% elongation. The stress after holding for 30 seconds was defined as (G2). Next, the length of the sample when the elongation of the sample was recovered and the stress became zero was defined as (L2). Furthermore, it extended until the sample cut | disconnected 6th time. The stress at the time of fracture was (G3), and the sample length at the time of fracture was (L3). Hereinafter, the above characteristics are calculated by the following formula.

Breaking strength (cN) = (G3)
Stress relaxation (%) = 100 × ((G1) − (G2)) / (G1)
Permanent distortion rate (%) = 100 × ((L2) − (L1)) / (L1)
Elongation at break (%) = 100 × ((L3) − (L1)) / (L1)
[chemical resistance]
The yarn was fixed at 100% elongation, and the following three types of exposure treatment were performed. First, it is immersed in a hexane solution of oleic acid (5% by weight) for 1 hour, then immersed in a prepared hypochlorous acid solution (chlorine concentration: 500 ppm) for 2 hours, and then exposed to UV for 2 hours. The UV exposure treatment was performed using a carbon arc type fade meter manufactured by Suga Test Instruments Co., Ltd. as a device at 63 ° C. and 60% RH. After this exposure treatment was performed twice in total, the yarn was left free for 24 hours at room temperature, and the breaking strength (G4) was measured by the same method as described above. The ratio (retention rate) of the breaking strength (G4) after the treatment to the breaking strength (G3) of the untreated yarn was defined as chemical resistance. The number of measurements was measured at n = 3, and the average value thereof was adopted.

Chemical resistance (%) = 100 × (G4) / (G3)
[Alkali resistance]
As an indicator of the alkali resistance of the polyurethane yarn, a treatment assuming the weight reduction processing of the polyester fiber is performed, and the breaking strength retention rate of the yarn is evaluated.

  The yarn was fixed in a 100% stretched state, sealed in a pressure vessel, filled with an aqueous solution (containing 8.0% by weight of each) containing a cationic weight loss accelerator (DXN-10 manufactured by one company) and sodium hydroxide, and 100 After the treatment at 120 ° C. for 120 minutes, the yarn was left free for 24 hours at room temperature, and the breaking strength (G5) was measured by the same method as described above. The ratio (retention rate) of the breaking strength (G5) after the treatment to the breaking strength (G3) of the untreated yarn was defined as alkali resistance. The number of measurements was measured at n = 3, and the average value thereof was adopted.

Alkali resistance (%) = 100 × (G5) / (G3)
[Thermal softening point]
The thermal softening point was measured as one of the heat resistance indicators of polyurethane yarn. The polyurethane yarn was measured for temperature dispersion of the dynamic storage elastic modulus E ′ at a heating rate of 10 ° C./min using a dynamic elastic modulus measuring device RSAII manufactured by Rheometric. The thermal softening point was determined from the intersection of the tangent line in the plateau region where the E ′ curve was 80 ° C. or higher and 130 ° C. or lower and the tangent line of the E ′ curve where E ′ decreased due to thermal softening at 160 ° C. or higher. Note that E ′ is a logarithmic axis, and temperature is a linear axis. The number of measurements was measured at n = 3, and the average value thereof was adopted.

[Melting point]
As one of the heat resistance indexes of the polyurethane yarn, the high temperature side melting point, that is, the melting point of the hard segment crystal was measured. For the polyurethane yarn, an irreversible heat flow was measured at a rate of temperature increase of 3 ° C./minute using a 2920 modulated DSC manufactured by EE Instruments, and the peak top was taken as the melting point. The number of measurements was measured at n = 3, and the average value thereof was adopted.

[Example 1]
A DMAc solution (35% by weight) of a polyurethane polymer (a1) comprising PTMG, MDI and ethylene glycol having a molecular weight of 2900 was polymerized by a conventional method to obtain a polymer solution A1. Next, the DMAc solution B1 was prepared by using 1,3-phenylenebisdixylenyl phosphate (b1) as the aromatic condensed phosphate ester. Further, as an antioxidant, a polyurethane solution produced by the reaction of t-butyldiethanolamine and methylene-bis- (4-cyclohexylisocyanate) (“Methacryl” (registered trademark) 2462, manufactured by DuPont) (c1) And a condensation polymer of p-cresol and divinylbenzene ("Megachlor" (registered trademark) 2390, (c2) manufactured by DuPont) in a 2 to 1 (weight ratio) mixture, and a DMAc solution of an antioxidant (Concentration 35% by weight) was prepared, and this was used as the other additive solution C1 (35% by weight).

  Polymer solution A1, aromatic condensed phosphate ester solution B1, and other additive solution C1 were uniformly mixed at 87 wt%, 10 wt%, and 3 wt%, respectively, to obtain spinning solution D1. This spinning solution was dry-spun at a spinning speed of 540 m / min with a speed ratio of 1.4 between the godet roller and the winder, and wound to prepare a 20 dtex, monofilament polyurethane elastic yarn (200 g wound body).

  The composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1.

  Table 2 shows the breaking elongation, breaking strength, permanent strain rate, stress relaxation, chemical resistance, alkali resistance, thermal softening point, and melting point of this polyurethane elastic yarn. Both the elongation at break and the strength at break increased compared to Comparative Example 1 (described later) containing no aromatic condensed phosphate ester. The permanent set rate and stress relaxation were reduced as compared with Comparative Example 1, and the recoverability was improved. Chemical resistance and alkali resistance were significantly increased as compared with Comparative Example 1, and each showed more than twice. The heat softening point and melting point, which are indicators of heat resistance, were also improved as compared with Comparative Example 1.

  Further, stretch fabrics were produced by the following method, and the appearance quality was evaluated.

  First, the obtained polyurethane elastic yarn was covered. A regular polyester fiber 168 dtex-48 fil was used as a covering yarn, and it was processed using a covering machine under the conditions of twist number = 450 t / m and draft = 3.0 to prepare a weft covering yarn. Similarly, a regular polyester fiber 168 dtex-48 fil is used as the covering yarn, and the covering yarn for the warp yarn is processed by using a covering machine under the conditions of twist number 700 T / M and draft = 3.5. Produced.

  Next, warping and weaving were performed. 5100 warp yarns (1100 rough winding warp) were glued and warped, and woven with a 2/1 twill structure using a rapier loom.

  Next, dyeing was performed. The raw machine obtained by weaving is scoured according to conventional methods, intermediate set (185 ° C), alkali weight reduction (N treatment), embossing (190 ° C), dyeing (130 ° C), drying, finish treatment, finishing set (180 ° C., cloth speed 20 m / min, set zone 24 m) were sequentially performed.

  The obtained stretch fabric had no defects and was excellent in appearance quality.

[Example 2]
The polymer solution A1, the aromatic condensed phosphate ester solution B1, and the other additive solution C1 prepared in Example 1 were uniformly mixed at 92 wt%, 5 wt%, and 3 wt%, respectively, and the spinning solution D2 and did.

  This spinning solution was dry-spun at a spinning speed of 540 m / min with a speed ratio of 1.40 between the godet roller and the winder, and wound to prepare a 20 dtex, monofilament polyurethane elastic yarn (200 g wound body).

  The composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1.

  Table 2 shows the breaking elongation, breaking strength, permanent strain rate, stress relaxation, chemical resistance, alkali resistance, thermal softening point, and melting point of this polyurethane elastic yarn. The breaking strength increased as compared with Comparative Example 1 (described later), and the elongation remained the same. The permanent set rate and stress relaxation were reduced as compared with Comparative Example 1, and the recoverability was improved. Chemical resistance and alkali resistance were significantly increased as compared with Comparative Example 1, and each showed more than twice. The heat softening point, which is an index of heat resistance, was maintained at the same level as in Comparative Example 1, and the melting point was improved from that in Comparative Example 1.

  Moreover, when the stretch fabric was manufactured by the same method as Example 1 and the external appearance quality was evaluated, the obtained stretch fabric had no fault and was excellent in the external appearance quality.

[Example 3]
A DMAc solution (35% by weight) of polyurethane urea polymer (a2) composed of PTMG having a molecular weight of 1800, MDI, ethylenediamine, and diethylamine as a terminal blocking agent was polymerized by a conventional method to obtain a polymer solution A2. Next, the DMAc solution A2, the aromatic condensed phosphate ester solution B1 prepared in Example 1, and the other additive solution C1 prepared in Example 1 were 87% by weight, 10% by weight, and 3.0%, respectively. The mixture was uniformly mixed by weight% to obtain a spinning solution D3. This spinning solution D3 is dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and winder of 1.20, and wound to produce a 20 dtex, 2 fil multifilament polyurethane elastic yarn (500 g wound body). did.

  Table 1 shows the composition (% by weight) of the obtained polyurethane elastic yarn. Table 2 shows the breaking elongation, breaking strength, permanent set rate, stress relaxation, chemical resistance, alkali resistance, thermal softening point, and melting point. The breaking strength and breaking elongation increased compared to Comparative Example 2 (described later) containing no B1. The permanent set rate was reduced as compared with Comparative Example 2, and the recoverability was improved. Chemical resistance and alkali resistance were significantly increased as compared with Comparative Example 2, reaching 2 times or more and 3 times, respectively. The heat softening point, which is an index of heat resistance, increased from Comparative Example 2, and the melting point increased by 10 ° C. from Comparative Example 2 containing no B1.

  Moreover, when the stretch fabric was manufactured by the same method as Example 1 and the external appearance quality was evaluated, the obtained stretch fabric had no fault and was excellent in the external appearance quality.

[Example 4]
The polymer solution A2, the aromatic condensed phosphate solution B1, and the other additive solution C1 prepared in Example 3 were uniformly mixed at 92 wt%, 5 wt%, and 3 wt%, respectively, and the spinning solution D4 and did. This spinning solution D4 was dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and winder of 1.30, and wound to produce a 20 dtex, 2 fil multifilament polyurethane elastic yarn (500 g wound body). did.

  The composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1.

  Table 2 shows the elongation at break, breaking strength, permanent set rate, stress relaxation, thermal softening point, thermal softening point, and chemical resistance of this polyurethane elastic yarn. Chemical resistance and alkali resistance increased 2.5 times or more compared to Comparative Example 2 containing no B1. The elongation at break and strength at break increased significantly compared to Comparative Example 2 containing no B1. The permanent strain rate, stress relaxation, and thermal softening point, which are recoverability indicators, were also equal to or higher than those of Comparative Example 1 containing no B1.

  Moreover, when the stretch fabric was manufactured by the same method as Example 1 and the external appearance quality was evaluated, the obtained stretch fabric had no fault and was excellent in the external appearance quality.

[Example 5]
The DMAc solution B2 was prepared using 1,3-phenylenebisdiphenyl phosphate (b2) as the aromatic condensed phosphate ester.

  Polymer solution A1, aromatic condensed phosphate solution B2 and other additive solution C1 prepared in Example 1 were uniformly mixed at 87 wt%, 10 wt% and 3 wt%, respectively, to obtain spinning solution D5. .

  This spinning solution was dry-spun at a spinning speed of 540 m / min with a speed ratio of 1.40 between the godet roller and the winder, and wound to prepare a 20 dtex, monofilament polyurethane elastic yarn (200 g wound body).

  The composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1.

  Table 2 shows the elongation at break, breaking strength, permanent set rate, stress relaxation, chemical resistance, alkali resistance, thermal softening point, and melting point of this polyurethane elastic yarn. Both elongation at break and strength at break increased compared to Comparative Example 1 (described later). The permanent set rate and stress relaxation were reduced as compared with Comparative Example 1, and the recoverability was improved. Chemical resistance and alkali resistance were significantly increased as compared with Comparative Example 1, and each showed more than twice. The heat softening point, which is an index of heat resistance, was maintained at the same level as in Comparative Example 1, and the melting point was improved from that in Comparative Example 1.

  Moreover, when the stretch fabric was manufactured by the same method as Example 1 and the external appearance quality was evaluated, the obtained stretch fabric had no fault and was excellent in the external appearance quality.

[Example 6]
The polymer solution A2, the aromatic condensed phosphate solution B1 and the other additive solution C1 prepared in Example 3 were uniformly mixed at 94.5 wt%, 2.5 wt%, and 3 wt%, respectively. A spinning solution D6 was obtained. This spinning solution D6 was dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and winder of 1.30, and wound to produce a 20 dtex, 2 fil multifilament polyurethane elastic yarn (500 g wound body). did.

  The composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1.

  Table 2 shows the elongation at break, breaking strength, permanent set rate, stress relaxation, thermal softening point, thermal softening point, and chemical resistance of this polyurethane elastic yarn. Compared to Comparative Example 2 containing no B1, the chemical resistance increased 1.8 times and the alkali resistance increased 1.6 times or more. The breaking elongation and breaking strength increased compared to Comparative Example 2 containing no B1. The permanent strain rate, the stress relaxation, and the thermal softening point, which are recoverability indicators, were also equal to or higher than those of Comparative Example 2 containing no B1.

  Moreover, when the stretch fabric was manufactured by the same method as Example 1 and the external appearance quality was evaluated, the obtained stretch fabric had no fault and was excellent in the external appearance quality.

[Example 7]
The polymer solution A2, the aromatic condensed phosphate solution B1 and the other additive solution C1 prepared in Example 3 were uniformly mixed at 77 wt%, 20 wt%, and 3 wt%, respectively, and the spinning solution D7 and did. This spinning solution D7 was dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and winder of 1.30, and wound to produce a 20 dtex, 2 fil multifilament polyurethane elastic yarn (500 g wound body). did.

  The composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1.

  Table 2 shows the elongation at break, breaking strength, permanent set rate, stress relaxation, thermal softening point, thermal softening point, and chemical resistance of this polyurethane elastic yarn. Compared to Comparative Example 2 containing no B1, the chemical resistance and alkali resistance increased more than twice. The elongation at break, the strength at break, and the permanent strain ratio and the stress relaxation, which are indicators of recoverability, were the same as in Comparative Example 2 containing no B1. The heat softening point was equal to or greater than that of Comparative Example 2 containing no B1.

  Moreover, when the stretch fabric was manufactured by the same method as Example 1 and the external appearance quality was evaluated, the obtained stretch fabric had no fault and was excellent in the external appearance quality.

[Example 8]
The polymer solution A2, the aromatic condensed phosphate solution B1 and the other additive solution C1 prepared in Example 3 were uniformly mixed at 75 wt%, 22 wt%, and 3 wt%, respectively, and the spinning solution D8 and did. This spinning solution D7 was dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and winder of 1.30, and wound to produce a 20 dtex, 2 fil multifilament polyurethane elastic yarn (500 g wound body). did.

  The composition (% by weight) of the obtained polyurethane elastic yarn was as shown in Table 1.

  Table 2 shows the elongation at break, breaking strength, permanent set rate, stress relaxation, thermal softening point, thermal softening point, and chemical resistance of this polyurethane elastic yarn. Compared to Comparative Example 2 containing no B1, the chemical resistance and alkali resistance increased more than twice. The breaking elongation and breaking strength increased compared to Comparative Example 2 containing no B1. In addition, the permanent strain rate and stress relaxation, which are indices of recoverability, were reduced and improved as compared with Comparative Example 2. The heat softening point was equal to or greater than that of Comparative Example 2 containing no B1.

  Moreover, when the stretch fabric was manufactured by the same method as Example 1 and the external appearance quality was evaluated, the obtained stretch fabric had no fault and was excellent in the external appearance quality.

[Comparative Example 1]
The polymer solution A1 prepared in Example 1 and the other additive solution additive solution C1 prepared in Example 1 were uniformly mixed at a ratio of 97% by weight and 3% by weight, respectively, to obtain a spinning solution E1. The spinning solution E1 was dry-spun at a spinning speed of 540 m / min with a speed ratio of the godet roller and the winder of 1.40, and wound to prepare a 20 dtex, monofilament polyurethane elastic yarn.

  Table 2 shows the elongation at break, breaking strength, permanent set rate, stress relaxation, chemical resistance, alkali resistance, thermal softening point, and melting point of the obtained polyurethane elastic yarn. Chemical resistance and alkali resistance were significantly inferior to those of Examples 1 and 2 containing an aromatic condensed phosphate ester.

  In addition, a stretch woven fabric was produced by the same method as in Example 1, and the appearance quality was evaluated. As a result, the appearance of the corrugated polyurethane yarn caused by various processing histories was observed, and 15/20 m. It was place and was unsatisfactory.

[Comparative Example 2]
The polymer solution A2 prepared in Example 3 and the other additive solution additive solution C1 prepared in Example 1 were uniformly mixed at a ratio of 97% by weight and 3% by weight, respectively, to obtain a spinning solution E2. This spinning solution E2 was dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and winder of 1.20, and wound to produce a 20 dtex, 2 fil multifilament polyurethane elastic yarn (500 g wound body). did.

  Table 2 shows the elongation at break, breaking strength, permanent set rate, stress relaxation, chemical resistance, alkali resistance, thermal softening point, and melting point of the obtained polyurethane elastic yarn. Chemical resistance and alkali resistance were significantly inferior to those of Examples 3 to 4 containing an aromatic condensed phosphate ester.

  In addition, a stretch woven fabric was produced in the same manner as in Example 1, and the appearance quality was evaluated. As a result, the appearance of the corrugated polyurethane yarn due to various processing histories was confirmed to be 4 per 20 m. It was place and was unsatisfactory.

[Comparative Example 3]
A DMAc solution F1 (35% by weight) of polyvinylidene fluoride (number average molecular weight 48,000, f1) manufactured by Kureha Chemical Industry Co., Ltd. described in JP-A No. 2000-73233 was prepared. The preparation was performed in the same manner as in Example 1. The polymer solution A2 prepared in Example 3, the above-described polyvinylidene fluoride solution F1, and the other additive solution C1 prepared in Example 1 were uniformly mixed at 92% by weight, 5% by weight, and 3.0% by weight, respectively. Thus, the spinning solution E3 was obtained. This spinning solution E3 was dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and winder of 1.30 and wound to produce a 20 dtex, 2 fil multifilament polyurethane elastic yarn (500 g wound body). did.

  Table 2 shows the elongation at break, breaking strength, permanent set rate, stress relaxation, thermal softening point, thermal softening point, and chemical resistance of the obtained polyurethane elastic yarn. The chemical resistance was inferior to that of Examples 3 and 4 and the like, which were improved 1.5 times compared to Comparative Example 2 in which no polyvinylidene fluoride was added. Furthermore, the permanent set was too large.

  In addition, a stretch woven fabric was produced by the same method as in Example 1, and the appearance quality was evaluated. As a result, the appearance of the undulation caused by sag, which seems to be due to an increase in the permanent distortion rate of the polyurethane yarn, occurred. It was unsatisfactory.

[Comparative Example 4]
A DMAc dispersion F2 (35% by weight) of TPP (triphenyl phosphate) manufactured by Daihachi Chemical Industry Co., Ltd. was prepared. The preparation was performed in the same manner as in Example 1. The polymer solution A2 prepared in Example 3, the above TPP dispersion F2, and the other additive solution C1 prepared in Example 1 were uniformly mixed at 87 wt%, 10 wt%, and 3.0 wt%, respectively. Spinning solution E4. This spinning solution E4 was dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and winder of 1.30, and wound to produce a 20 dtex, 2 fil multifilament polyurethane elastic yarn (500 g wound body). did.

  Table 2 shows the elongation at break, breaking strength, permanent set rate, stress relaxation, chemical resistance, alkali resistance, thermal softening point, and melting point of the obtained polyurethane elastic yarn. The breaking elongation, breaking strength, permanent distortion rate, chemical resistance, and alkali resistance are the same or inferior to those of Comparative Example 2 in which TPP was not added, and are significantly inferior to Examples 3 to 4 and the like. Met.

  In addition, a stretch woven fabric was manufactured in the same manner as in Example 1, and the appearance quality was evaluated. As a result, the appearance of this white bleed was estimated to be caused by TPP over the course of two months. Was unsatisfactory everywhere.

  The compositions (% by weight) of the polyurethane elastic yarns obtained in Examples 1 to 8 and Comparative Examples 1 to 4 are collectively shown in Table 1. Moreover, the breaking elongation, breaking strength, permanent set rate, stress relaxation, chemical resistance, alkali resistance, thermal softening point, melting point of the polyurethane elastic yarns obtained in Examples 1 to 8 and Comparative Examples 1 to 4 These are summarized in Table 2.

Next, flame retardancy was evaluated for each of the polyurethane elastic yarns obtained in the above Examples and Comparative Examples by the following method. The results are shown in Table 3 below.
[Flame retardancy evaluation method]
Using only yarn (40 dtex) made by aligning two polyurethane elastic yarns (20 dtex), knitting by supplying it to a single-necked cylinder knitting machine with 320 needles and a hook diameter of 3.5 inches (29 gauge) at 120 ° C. Steam setting for 1 minute was performed to obtain a tubular knitted fabric (55 g / m ² ) having a width of about 5 cm. This was used as a sample without opening (corresponding to two knitted fabrics of 55 g / m ² ), and three horizontal combustion tests were conducted in accordance with the US automobile safety standard FMVSS-302 method. The burning distance after the marked line and the burning time after the marked line were measured.

  In this standard, the distance before the marked line is set to 38 mm, and the burned distance after the marked line is 0, or the digested gas within 50 seconds or less within 60 seconds is determined to be self-extinguishing. Also, those with a burning rate of 100 mm / min or less are judged as slow flammability, and those with a burning rate of 100 mm / min or more are judged as flammable.

  From the above results, for the polyurethane elastic yarns of Examples 1 to 5 and Examples 7 and 8 containing the aromatic condensed phosphate ester, the burning distance before the marked line is less than 38 mm, and therefore the burning distance after the marked line is It was 0, and it was determined to be self-extinguishing. About Example 6, although it showed the tendency which is hard to burn, there existed combustion exceeding a marked line and it was determined that it was slow-flammability from the combustion speed.

  On the other hand, Comparative Example 4 to which TPP was added showed a tendency to be slightly flammable, but it was an unsatisfactory level, and Comparative Examples 1 to 4 were all flammable.

  Since the polyurethane elastic yarn of the present invention has alkali resistance, resistance to various chemicals, high recovery, high strength elongation, and high heat resistance, clothes using this elastic yarn can be attached and detached. It is excellent in wear feeling, dyeability, discoloration resistance, appearance quality and the like.

  Because of these excellent properties, the polyurethane yarn of the present invention can be used not only alone but also in combination with various fibers to obtain an excellent stretch fabric, which is suitable for knitting, weaving and string processing. It is. Specific applications that can be used include socks, stockings, circular knitting, tricots, swimwear, ski pants, work clothes, smoke fire clothes, golf trousers, wet suits, bras, girdles, various textile products such as gloves, fastening materials, Further examples include fastening materials for preventing sanitary items such as paper diapers, waterproofing materials, imitation baits, artificial flowers, electrical insulation materials, wiping cloths, copy cleaners, and gaskets.

  Further, since it is self-extinguishing or slow flammability, it can be suitably used even in a field where flame retardancy is required. For example, it can be used as materials for automobiles, railway vehicles, aircrafts and ships. .

Claims (4)

A polyurethane elastic yarn starting from a polymer diol and a diisocyanate, which contains an aromatic condensed phosphate represented by the formula 1 in a range of 0.5 wt% to 22 wt% Elastic yarn.

(R1 is an aromatic group, R2 is hydrogen or an alkyl group having 1 to 3 carbon atoms, a plurality of R2s may be the same or different, and R3 is hydrogen or carbon number. 1 to 3 alkyl groups, and a plurality of R3 may be the same or different.) The polyurethane elastic yarn according to claim 1, wherein the aromatic condensed phosphate ester is 1,3-phenylenebisdixylenyl phosphate. The polyurethane elastic yarn according to claim 1 or 2, which exhibits self-extinguishing properties when a tubular knitted fabric having a width of 5 cm is knitted and subjected to a horizontal combustion test according to the US automobile safety standard FMVSS-302 method. Spinning in a polyurethane solution containing a polyurethane starting from a polymer diol and a diisocyanate containing an aromatic condensed phosphate represented by the formula 1 in a range of 0.5 wt% to 22 wt%. A method for producing a polyurethane elastic yarn.