JP4356065B2 - Polyurethane yarn - Google Patents

Description

【００８０】
【発明の効果】
本発明のポリウレタン弾性糸は、高ヒートセット性、高耐熱性等の優れた特性を有するものであるので、この弾性糸を使用した衣服などは、脱着性、フィット性、外観品位、着用感、耐変色性などに優れたものとなる。
【００８１】
これらの優れた特性を有することから、本発明のポリウレタン糸は単独での使用はもとより、各種繊維との組み合わせにより、例えば、ソックス、ストッキング、丸編、トリコット、水着、スキーズボン、作業服、煙火服、洋服、ゴルフズボン、ウエットスーツ、ブラジャー、ガードル、手袋や靴下等の各種繊維製品の締め付け材料、紙おしめなどサニタニー品の漏れ防止用締め付け材料、防水資材の締め付け材料、似せ餌、造花、電気絶縁材、ワイピングクロス、コピークリーナー、ガスケットなど、種々の用途に使用することが可能である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polyurethane elastic yarn having high heat setting properties and high heat resistance and a method for producing the same.
[0002]
[Prior art]
Elastic fibers are widely used for stretchable clothing and industrial materials such as legwear, innerwear, and sportswear because of their excellent stretch properties.
As such an elastic fiber, in particular, a polyurethane elastic yarn has been required to have a high heat setting property and a high heat resistance.
[0003]
Conventionally, a technique for treating a polyurethane elastic yarn containing cellulose acetate with an alkali has been proposed (see, for example, Patent Document 1), but it has not been satisfactory in terms of high heat setting properties and high heat resistance. Moreover, although the technique about the polyurethane elastic yarn containing polyvinylpyrrolidone is proposed (for example, refer patent document 2), it was not satisfied regarding high heat resistance.
[0004]
[Patent Document 1]
JP 2000-303259 A [Patent Document 2]
Japanese Patent Laid-Open No. 11-200137
[Problems to be solved by the invention]
An object of the present invention is to solve the above-mentioned problems of the prior art and to provide a polyurethane elastic yarn having high heat setting properties and high heat resistance and a method for producing the same.
[0006]
[Means for Solving the Problems]
The polyurethane yarn of the present invention employs the following means in order to solve the above object.
That is, an elastic yarn made of polyurethane whose main constituent components are a polyol and a diisocyanate, containing a cellulose ester , and the content of the cellulose ester being 0.5 wt% or more and 8 wt% or less. It is a feature.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in further detail below.
First, the polyurethane used in the present invention will be described.
[0008]
The polyurethane used in the present invention may be any polyurethane as long as the main components are a polyol and a diisocyanate, and is not particularly limited. Also, the synthesis method is not particularly limited.
[0009]
That is, for example, polyurethane urea composed of polyol, diisocyanate and diamine may be used, and polyurethane composed of polyol, diisocyanate and diol may be used. 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.
[0010]
Here, typical structural units constituting the polyurethane used in the present invention will be described.
As the polyol 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.
[0011]
Examples of polyether glycols include polyethylene oxide, polyethylene glycol, polyethylene glycol derivatives, polypropylene glycol, polytetramethylene ether glycol (hereinafter abbreviated as PTMG), modified PTMG (which is a copolymer of THF and 3-MeTHF ( Hereinafter, abbreviated as 3M-PTMG), modified PTMG which is a copolymer of THF and 2,3-dimethyl THF, a polyol having side chains on both sides disclosed in Japanese Patent No. 2615131, THF and ethylene oxide, Random copolymers in which propylene oxide is irregularly arranged are preferably used. These polyether glycols may be used alone or in combination of two or more.
[0012]
Further, from the viewpoint of obtaining abrasion resistance and light resistance as a polyurethane yarn, butylene adipate, polycaprolactone diol, polyester glycol such as polyester polyol having a side chain disclosed in JP-A No. 61-26612 and the like, The polycarbonate diol disclosed in JP-B-2-289516 is preferably used.
[0013]
These polyols may be used alone, or may be used by mixing or copolymerizing two or more kinds. The molecular weight of the polyol used in the present invention is preferably from 1,000 to 8,000, more preferably from 1800 to 6,000, from the viewpoint of obtaining elongation, strength, heat resistance, and the like when it is made into a yarn. By using a polyol having a molecular weight within this range, an elastic yarn excellent in elongation, strength, elastic recovery, and heat resistance can be obtained.
[0014]
Next, as the diisocyanate 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, It is suitable for synthesizing polyurethane having high heat resistance and strength. Further, as the alicyclic diisocyanate, for example, methylene bis (cyclohexyl isocyanate) (hereinafter referred to as H ₁₂ MDI), isophorone diisocyanate, methylcyclohexane 2,4-diisocyanate, methylcyclohexane 2,6-diisocyanate, cyclohexane 1,4-diisocyanate , Hexahydroxylylene diisocyanate, hexahydrotolylene 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.
[0015]
Next, as the chain extender in the present invention, it is preferable to use at least one of low molecular weight diamine and low molecular weight diol. In addition, you may have a hydroxyl group and amino groups in a molecule like ethanolamine.
[0016]
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.
[0017]
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 there. 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.
[0018]
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 measured by GPC and converted by polystyrene.
[0019]
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 heat set property, it consists of diol and diisocyanate, In addition, the melting point on the high temperature side is in the range of 200 ° C to 260 ° C. Here, the melting point on the high temperature side refers to the value of second run when measured by DSC, and corresponds to the so-called hard segment melting point of polyurethane.
[0020]
And, at least one selected from the group consisting of PTMG having a molecular weight in the range of 1800 to 6000 as polyol, MDI as diisocyanate, ethylene glycol, diol, 1,3 propanediol and 1,4 butanediol is used. The elastic yarn made of polyurethane having a high-temperature melting point in the range of 200 ° C. or higher and 260 ° C. or lower is particularly high in elongation, and as described above, including process passability, There is no practical problem and it is preferable because it is excellent in heat setting.
[0021]
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, polyol, and diol by a prior test is preferable. The constitution of the polyurethane used in the present invention is preferably such.
[0022]
The polyurethane elastic yarn of the present invention contains a cellulose ester. When a polyurethane ester is not contained in the polyurethane elastic yarn, there is a problem that high heat setting properties cannot be obtained.
[0023]
The cellulose ester used in the present invention is a derivative obtained by esterifying three hydroxyl groups of cellulose with acids, and there are two types of esters with nitric acid, acetic acid, propionic acid, butyric acid, other higher fatty acids, or the aforementioned acids. Mixed esters using the above mixed acids are preferred. Furthermore, from the viewpoint of obtaining good spinnability, the acid is preferably a derivative esterified with a mixed acid containing an organic acid having 2 to 22 carbon atoms. For example, cellulose acetate derived from cellulose and acetic acid, cellulose Cellulose acetate butyrate derived from cellulose, acetic acid and butyric acid, cellulose acetate propionate derived from cellulose, acetic acid and propionic acid, and adjustment of acid-hydroxyl equivalents called cellulose acetate plastics to leave some hydroxyl groups Further, a molding plastic containing an adipic acid plasticizer or a phthalic acid plasticizer in an arbitrary ratio and having an appropriately adjusted heat softening point and melt viscosity can be preferably used.
[0024]
And in order to provide favorable heat set property in the high-order processing process of a polyurethane elastic yarn, it is preferable that the cellulose ester to contain is the range whose heat softening point is 100 degreeC or more and 200 degrees C or less. This is because the heat treatment temperature range of the polyurethane elastic yarn and the fabric containing the polyurethane yarn, for example, the heat setting temperature by a tenter or the pantyhose heat setting mold is 110 ° C. or more and 190 ° C. or less.
[0025]
In the present invention, the content of the cellulose ester is preferably in the range of 0.5% by weight or more and 8 % by weight or less from the viewpoint of obtaining good spinnability, well-balanced mechanical properties, and heat resistance. The lowering of the melting point is small, that is, from the viewpoint of obtaining good heat resistance of the polyurethane yarn, it is more preferably 1 wt% or more and 8 wt% or less. In addition, it is preferable to test these contents beforehand according to a use, and to determine an optimal value suitably.
[0026]
Furthermore, the cellulose ester used in the present invention accelerates the dispersion and dissolution in the polyurethane, makes the properties of the produced polyurethane yarn the target property, and further obtains a polyurethane yarn having an appropriate transparency, and the spinning process. From the viewpoint of preventing the cellulose ester content from being lowered and the yarn from being discolored by receiving heat, etc., when the 5 wt% DMAc solution is used, the viscosity at 20 ° C. is in the range of 200 cP to 10,000 P. Is preferred.
[0027]
Furthermore, it is also preferred that the polyurethane used in the present invention includes one or more terminal blocking agents. As end-capping agents, monoamines such as dimethylamine, diisopropylamine, ethylmethylamine, diethylamine, methylpropylamine, isopropylmethylamine, diisopropylamine, butylmethylamine, isobutylmethylamine, isopentylmethylamine, dibutylamine, diamylamine, ethanol Monools such as propanol, butanol, isopropanol, allyl alcohol and cyclopentanol, and monoisocyanates such as phenyl isocyanate are preferred.
[0028]
In the present invention, the polyurethane may contain various stabilizers, pigments and the like. For example, hindered phenolic agents such as BHT and Sumitomo Chemical Co., Ltd. “Smulizer GA-80” manufactured by Sumitomo Chemical Co., Ltd., and various benzotriazole and benzophenone based agents such as “Tinuvin” manufactured by Ciba Geigy Co., Ltd. , Sumitomo Chemical Co., Ltd. "Sumilyzer P-16" and other phosphorous agents, various hindered amine agents, various pigments such as iron oxide and titanium oxide, inorganic substances such as zinc oxide, cerium oxide, magnesium oxide and carbon black , Fluorine or silicone resin powders, metal soaps such as magnesium stearate, bactericides, deodorizers including silver, zinc and their compounds, lubricants such as silicone and mineral oil, barium sulfate, oxidation It is also preferable that various antistatic agents such as cerium, betaine and phosphate are included. Properly, It is also preferred that they are reacted with the polymer. In order to further enhance the durability to light and various nitric oxides, for example, a nitric oxide supplement such as HN-150 manufactured by Nippon Hydrazine Co., Ltd., for example, “Sumilyzer GA manufactured by Sumitomo Chemical Co., Ltd.” It is also preferable to use a thermal oxidation stabilizer such as -80 ", for example, a light stabilizer such as" Sumisorb 300 # 622 "manufactured by Sumitomo Chemical Co., Ltd.
[0029]
Next, the method for producing the polyurethane elastic yarn of the present invention will be described in detail.
[0030]
In the present invention, it is preferable to prepare a polyurethane solution first. A method for producing a polyurethane solution and a method for producing 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, there is little generation of foreign substances such as gel in the polyurethane, it is easy to spin, and it is easy to obtain a low-definition polyurethane yarn. Further, in the case of solution polymerization, there is an advantage that the operation of making a solution can be omitted.
[0031]
The polyurethane particularly suitable for the present invention includes PTMG having a molecular weight of 1800 to 6000 as polyol, MDI as diisocyanate, ethylene glycol, diol, 1,3 propanediol and 1,4 butanediol as diol. And those having a melting point on the high temperature side of 200 ° C. or higher and 260 ° C. or lower.
[0032]
Such polyurethane can be obtained, for example, by synthesizing using the above-mentioned raw materials in DMAc, DMF, DMSO, NMP, or the like or a solvent containing these as a main component. 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 a polyol and diisocyanate are first melt-reacted, and then the reaction product A method of dissolving polyurethane in a solvent and reacting with the above-mentioned diol to form polyurethane can be employed as a particularly suitable method.
[0033]
When a diol is used as the chain extender, a typical method for adjusting the melting point on the high temperature side of the polyurethane to a range of 200 ° C. or higher and 260 ° C. or lower can be achieved by controlling the types and ratios of polyol, MDI and diol. . When the molecular weight of the polyol 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 polyol.
[0034]
When the molecular weight of the polyol is 1800 or more, it is preferable to proceed the polymerization at a ratio of (number of moles of MDI) / (number of moles of polyol) = 1.5 or more in order to make the melting point on the high temperature side 200 ° C. or more. .
[0035]
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.
[0036]
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-dimethylaminoethanol, , N, N′-trimethylaminoethylethanolamine, N-methyl-N ′-(2-hydroxyethyl) piperazine, 2,4,6-tris (dimethylaminomethyl) phenol, N, N-dimethylaminohexanol, tri Examples include ethanolamine.
[0037]
Examples of organometallic catalysts include tin octoate, dibutyltin dilaurate, and lead dibutyl octoate.
[0038]
The concentration of the polyurethane solution thus obtained is usually preferably in the range of 30% by weight to 80% by weight.
[0039]
In the present invention, it is preferable to add a cellulose ester to such a polyurethane solution. As a method for adding the cellulose ester to the polyurethane solution, any method can be adopted. 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 added cellulose ester is preferably added as a solution from the viewpoint of uniform addition to the polyurethane solution.
[0040]
In addition, the addition of cellulose 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 this phenomenon. Monoamines such as dimethylamine, diisopropylamine, ethylmethylamine, diethylamine, methylpropylamine, isopropylmethylamine, diisopropylamine, butylmethylamine, isobutylmethylamine, isopentylmethylamine, dibutylamine, diamylamine, ethanol, propanol, butanol, One or more end-capping agents such as monools such as isopropanol, allyl alcohol and cyclopentanol, and monoisocyanates such as phenyl isocyanate are used in combination. Both are preferably carried out.
[0041]
When the cellulose ester is added to the polyurethane solution, it may be added at the same time as, for example, the agent such as the light-resistant agent and the antioxidant and the pigment.
[0042]
The fineness, the number of single yarns, the cross-sectional shape, etc. of the polyurethane 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.
The dry spinning method is not particularly limited, and any method can be applied.
[0043]
Since the setting property and stress relaxation of the polyurethane yarn of the present invention are particularly susceptible to the speed ratio between the godet roller and the winder, it is preferably determined as appropriate according to the intended use of the yarn.
[0044]
That is, from the viewpoint of obtaining a polyurethane yarn having desired setting properties and stress relaxation, it is preferable that the speed ratio of the godet roller and the winder is wound in a range of 1.15 to 1.65. And when obtaining the polyurethane yarn which has especially high setting property and low stress relaxation, the speed ratio of a godet roller and a winder has the more preferable range of 1.15 or more and 1.4 or less, and 1.15 or more and 1. A range of 35 or less is more preferable.
[0045]
On the other hand, when obtaining a polyurethane yarn having low setability and high stress relaxation, the speed ratio of the godet roller and the winder is preferably wound in the range of 1.25 or more and 1.65 or less, and 1.35 or more. The range of 1.65 or less is more preferable.
[0046]
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.
[0047]
【Example】
The invention is explained in more detail by means of examples.
A method for measuring the setting property, stress relaxation, strength, elongation, heat setting property, and heat softening point of the polyurethane elastic yarn in the present invention will be described.
[0048]
[Setability, stress relaxation, strength, elongation]
The setability, stress relaxation, strength, and elongation were measured by tensile testing polyurethane yarn using an Instron 4502 type tensile tester.
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 rupture was defined as (G3), and the sample length at the time of rupture was defined as (L3). Hereinafter, the above characteristics are calculated by the following formula.
[0049]
Strength = (G3)
Stress relaxation = 100 × ((G1) − (G2)) / (G1)
Set property = 100 × ((L2) − (L1)) / (L1)
Elongation = 100 × ((L3) − (L1)) / (L1)
[0050]
[Heat setting property]
The heat setting property was measured by the following.
The sample yarn was free treated with 100 ° C. steam for 10 minutes, then free treated with 100 ° C. boiling water for 2 hours and dried at room temperature for one day. Next, the sample yarn (length = (L5)) was stretched 150% (length = 2.5 × (L5)). This length was treated with 115 ° C. steam for 1 minute. Furthermore, the same length was subjected to a dry heat treatment at 120 ° C., and the same length was further allowed to stand at room temperature for one day. Next, the elongation state of the sample yarn was removed, and the length (L6) was measured. The value of heat setting property is calculated by the following formula.
Heat setting property = 100 × ((L6) − (L5)) / (L5)
[0051]
[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.
[0052]
[Discoloration resistance]
The discoloration resistance was measured as follows.
Preparation of the test piece and evaluation of anti-discoloration were performed according to JIS-L-1013, and the yellowing degree (hereinafter referred to as Δb) was calculated by the following formula.
Δb = b value after exposure treatment−b value before exposure treatment
In addition, the exposure treatment is UV exposure treatment modeled on light irradiation by store, sample storage, drying after washing, etc., nitrogen oxide (NOx) exposure treatment modeled on general household fuel appliances and automobile exhaust gas, etc., and The following three types of exposure to chlorine bleach were modeled on general household fabric bleach.
[0054]
In the UV exposure treatment, a carbon arc type fade meter manufactured by Suga Test Instruments Co., Ltd. was used as a device, and treatment was performed at 63 ° C. and 60% RH for 25 hours.
The nitrogen oxide (NOx) exposure treatment was carried out for 20 hours at a temperature and humidity of NO ₂ gas 10 ppm, 40 ° C., 60% RH, using an airtight container (Scott tester) with a rotating sample stand as an instrument.
For exposure to chlorine bleach, a high-temperature bath was used as an apparatus, and the operation of exposure to a 500 ppm aqueous solution of “Kao Hiter” (R) at 40 ° C. for 30 minutes followed by washing with water for 10 minutes was repeated 8 times.
[0055]
[Example 1]
A polymer solution A1 was prepared by polymerizing a DMAC solution (35% by weight) of a polyurethane polymerization raw material composed of PTMG, MDI and ethylene glycol having a molecular weight of 2900 by a conventional method. Next, a DMAc solution of cellulose ester (product name acetyl (R) resin, heat softening point 160 ° C., 78% main component cellulose acetate and 22% diethyl phthalate melt mixture) manufactured by Daicel Finechem Co., Ltd. was prepared. For the adjustment, horizontal mill WILLY A. Using DYNO-MIL KDL manufactured by BACHOFEN, 85% zirconia beads were filled and uniformly dispersed under the condition of a flow rate of 50 g / min to obtain a cellulose ester solution B1 (35% by weight). Further, polyurethanes produced by the reaction of t-butyldiethanolamine and methylene-bis- (4-cyclohexyl isocyanate) described in US Pat. No. 3,555,115 and those described in US Pat. No. 3,553,290 are disclosed. A DMAc solution (35% by weight) of a 2 to 1 (weight ratio) mixture of p-cresol and divinylbenzene condensation polymer was prepared to obtain an additive solution C1 (35% by weight).
[0056]
Polymer solution A1, cellulose ester solution B1, and additive solution C1 were uniformly mixed at 92 wt%, 6 wt%, and 2 wt%, respectively, to obtain spinning solution D1. When the spinning solution D1 is dry-spun at a spinning speed of 540 m / min with a speed ratio of 1.4 between the godet roller and the winder, the content of 20 dtex, monofilament, and cellulose ester is 6% by weight. A polyurethane elastic yarn (200 g wound yarn) was produced.
[0057]
Table 1 shows the breaking elongation, breaking strength, setting property, stress relaxation, heat setting property and heat softening point of the obtained yarn. The heat setting property was increased about twice as compared with Comparative Example 1 (described later) in which B1 was not blended. The heat softening point, which is an index of heat resistance, was 180 ° C. equivalent to Comparative Example 1 containing no B1, and the machine set was also appropriate. Further, the breaking strength and elongation were equal to or higher than those of Comparative Example 1 containing no B1, and the discoloration resistance was also good.
[0058]
The obtained polyurethane elastic yarn was covered with a nylon yarn “Miracosmo” (registered trademark) (22 decitex) manufactured by Toray Industries, Inc. to form a covering yarn (SCY), and a knitted pantyhose was knitted. We were able to obtain a Zokki pantyhose with excellent quality.
[0059]
[ Reference Example 1 ]
A DMAc dispersion of cellulose ester (product name Tenite (R) propionate, main component cellulose acetate propionate, thermal softening point 125 ° C.) manufactured by Eastman Co. was prepared. The adjustment was carried out in the same manner as in Example 1, and this was designated as cellulose ester solution B2 (35% by weight).
[0060]
The polymer solution A1 prepared in Example 1, the cellulose ester solution B2, and the additive solution C1 prepared in Example 1 were uniformly mixed at 86 wt%, 12 wt%, and 2 wt%, respectively, and the spinning solution D2 It was. This is a polyurethane elastic yarn having a content of 20 dtex, monofilament, and cellulose ester of 12 wt% by dry spinning at a spinning speed of 540 m / min at a speed ratio of 1.40 between the godet roller and winder. (200 g wound thread body) was manufactured.
[0061]
Table 1 shows the breaking elongation, breaking strength, setting property, stress relaxation, heat setting property and melting point of the obtained yarn. The heat setting property was increased about 3 times compared with Comparative Example 1 containing no B2. The heat softening point, which is an index of heat resistance, was equivalent to that of Comparative Example 1 containing no B2, and the discoloration resistance was also good. Further, the elongation at break and the strength at break were the same as or higher than those of Comparative Example 1 containing no B2.
[0062]
The obtained polyurethane elastic yarn was covered with a nylon yarn “Miracosmo” (registered trademark) (22 dtex) manufactured by Toray Industries, Inc. to form a covering yarn (SCY), and knitted pantyhose was knitted. An excellent Zokki pantyhose with excellent appearance quality could be obtained.
[0063]
[Example 2 ]
A polymer solution A2 was prepared by polymerizing a DMAc solution (35% by weight) of a polyurethane urea polymerization raw material consisting of PTMG having a molecular weight of 1800, MDI, ethylenediamine, and diethylamine as a terminal blocking agent by a conventional method. Next, a DMAc solution of cellulose ester (product name: Tenite (R) butyrate, main component cellulose acetate butyrate, thermal softening point 145 ° C.) manufactured by Eastman Co., Ltd. was prepared in the same manner as in Example 1, and cellulose ester solution B3 It was.
[0064]
The polymer solution A2, the cellulose ester solution B3, and the additive solution C1 prepared in Example 1 were uniformly mixed at 90 wt%, 8 wt%, and 2.0 wt%, respectively, to obtain a spinning solution D3. By spinning the spinning solution D3 by dry spinning at a spinning speed of 600 m / min with a speed ratio of the godet roller and the winder of 1.20, the content of 20 dtex multifilament (2fil) and cellulose ester is 8 A polyurethane elastic yarn (500 g wound body) having a weight% was produced.
[0065]
Table 1 shows the elongation at break, breaking strength, setability, stress relaxation, heat setability and heat softening point of the obtained yarn. The heat setting property was increased about 2.7 times compared with Comparative Example 2 containing no B3. The heat softening point, which is an index of heat resistance, was equivalent to Comparative Example 1 containing no B2, and the machine set and discoloration resistance were also good. Further, the breaking elongation and breaking strength were equal to or higher than those of Comparative Example 2 containing no B3.
[0066]
The obtained polyurethane elastic yarn was covered with a nylon yarn “Miracosmo” (registered trademark) (22 decitex) manufactured by Toray Industries, Inc. to form a covering yarn (SCY), and a knitted pantyhose was knitted. An excellent Zokki pantyhose with excellent quality could be obtained.
[0067]
[ Reference Example 2 ]
A conventional DMAC solution (35% by weight) of a polyurethaneurea polymerization raw material consisting of PTMG, MDI having a molecular weight of 1800, ethylenediamine having a molar ratio of 80/20, 1,3-cyclohexyldiamine and diethylamine as an end-capping agent was polymerized. A polymer solution A3 was obtained.
[0068]
[ Reference Example 2 ]
The polymer solution A3, the cellulose ester solution B3 prepared in Example 2 and the additive solution C1 prepared in Example 1 were uniformly mixed at 74% by weight, 24% by weight and 2.0% by weight, respectively, and spinning. Solution D3 was obtained. This spinning solution D3 was dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and the winder of 1.30, and wound to obtain a 20 dtex multifilament (2 fil) and a cellulose ester content of 35. A polyurethane elastic yarn (500 g wound body) having a weight% was produced.
[0069]
Table 1 shows the elongation at break, breaking strength, setability, stress relaxation, heat setability and heat softening point of the obtained yarn. The heat setting property was increased about 3 times as compared with Comparative Example 3 containing no B3. The heat softening point, which is an index of heat resistance, was equivalent to that of Comparative Example 3 containing no B3, and the discoloration resistance was also good.
[0070]
The obtained polyurethane elastic yarn was covered with a nylon yarn “Miracosmo” (registered trademark) (22 decitex) manufactured by Toray Industries, Inc. to form a covering yarn (SCY), and a knitted pantyhose was knitted. An excellent Zokki pantyhose with excellent quality could be obtained.
[0071]
[Comparative Example 1]
The polymer solution A1 and the additive solution C1 prepared in Example 1 were uniformly mixed at 98% by weight and 2% by weight, respectively, to obtain a spinning solution E1. This spinning solution E1 was dry-spun and wound at a spinning speed of 540 m / min with a speed ratio of the godet roller and winder of 1.40 to produce 18 dtex monofilament polyurethane elastic yarn. Table 1 shows the elongation at break, breaking strength, setability, stress relaxation, heat setability, and thermal softening point of the yarn.
[0072]
The obtained yarn was covered with nylon yarn “Miracosmo” (registered trademark) (22 dtex) manufactured by Toray Industries, Inc. to form a covering yarn (SCY), and knitted pantyhose was knitted. This placement size was small, 0.88 times that of the elastic yarn of Example 1 manufactured using the same polymer solution A1. The appearance quality was good.
[0073]
[Comparative Example 2]
The polymer solution A2 prepared in Example 2 and the additive solution C1 prepared in Example 1 were uniformly mixed at 98% by weight and 2% 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 yield a 20-dtex multifilament (2 fil) polyurethane elastic yarn (500 g winding). Thread body). Table 1 shows the breaking elongation, breaking strength, setability, stress relaxation, heat setability, and thermal softening point of the yarn.
[0074]
The obtained yarn was covered with nylon yarn “Miracosmo” (registered trademark) (22 dtex) manufactured by Toray Industries, Inc. to form a covering yarn (SCY), and knitted pantyhose was knitted. This placement size was small, 0.82 times that of the elastic yarn of Example 2 produced using the same polymer solution A2. The appearance quality was unsatisfactory.
[0075]
[Comparative Example 3]
The polymer solution A3 prepared in Reference Example 2 and the additive solution C1 prepared in Example 1 were uniformly mixed at 98% by weight and 2% by weight, respectively, to obtain a spinning solution E3. This spinning solution E3 was dry-spun at a spinning speed of 600 m / min with a speed ratio of a godet roller and a winder of 1.30, and wound to yield a 20-dtex multifilament (2 fil) polyurethane elastic yarn (500 g winding). Thread body). Table 1 shows the breaking elongation, breaking strength, setability, stress relaxation, heat setability, and thermal softening point of the yarn.
[0076]
The obtained yarn was covered with nylon yarn “Miracosmo” (registered trademark) (22 dtex) manufactured by Toray Industries, Inc. to form a covering yarn (SCY), and knitted pantyhose was knitted. This placement size was small, 0.78 times that of the elastic yarn of Reference Example 2 produced using the same polymer solution A3. The appearance quality was somewhat unsatisfactory.
[0077]
[Comparative Example 4]
A DMAc solution of polyvinyl pyrrolidone (K-30) disclosed in JP-A-11-200137 was prepared, and this was used as a polyvinyl pyrrolidone solution F4 (35% by weight). The adjustment was performed in the same manner as in Example 1. A2 prepared in Example 2 , the above-described polyvinyl pyrrolidone solution F4, and C1 prepared in Example 1 were uniformly mixed at 83 wt%, 15 wt%, and 2.0 wt%, respectively, to obtain a spinning solution G4. This spinning solution G4 was dry-spun at a spinning speed of 600 m / min with a speed ratio of the godet roller and the winder of 1.30, and wound to yield a 20-dtex multifilament (2 fil) polyurethane elastic yarn (500 g winding). Thread body). Table 1 shows the breaking elongation, breaking strength, setability, stress relaxation, heat setability, and thermal softening point of the yarn. Compared to the elastic yarns of Reference Example 1 and Comparative Example 2 produced using the same polymer solution A2, the heat softening point was lowered by 10 ° C. or more, and the discoloration resistance was also lowered.
[0078]
The obtained yarn was covered with a nylon yarn “Miracosmo” (registered trademark) (22 dtex) manufactured by Toray Industries, Inc. to form a covering yarn (SCY), and knitted pantyhose was knitted. The appearance of this was somewhat unsatisfactory.
[0079]
[Table 1]

[0080]
【The invention's effect】
Since the polyurethane elastic yarn of the present invention has excellent properties such as high heat setting properties and high heat resistance, clothes using this elastic yarn are removable, fit, appearance quality, feeling of wearing, Excellent discoloration resistance.
[0081]
Because of having these excellent properties, the polyurethane yarn of the present invention can be used alone or in combination with various fibers, for example, socks, stockings, circular knitting, tricot, swimsuit, ski pants, work clothes, smoke fire. Clothing, clothes, golf trousers, wet suits, bras, girdles, fastening materials for various textile products such as gloves and socks, fastening materials for preventing sanitary products such as paper diapers, fastening materials for waterproofing materials, imitation bait, artificial flowers, electricity It can be used for various applications such as insulating materials, wiping cloths, copy cleaners, and gaskets.

Claims (4)

An elastic yarn comprising a polyurethane whose main constituent component is a polyol and a diisocyanate, comprising a cellulose ester, and the content of the cellulose ester is 0.5 wt% or more and 8 wt% or less. Polyurethane yarn to do. The polyurethane yarn according to claim 1, wherein the polyurethane is polyurethane urea. The polyurethane yarn according to claim 1 or 2, wherein the cellulose ester is cellulose acetate butyrate . The polyurethane yarn according to any one of claims 1 to 3, wherein the polyurethane is formed by using ethylenediamine as a chain extender .