JP2002249929A - Polyurethane yarn and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide polyurethane yarn capable of giving clothes excellent in removability, a fit, appearance quality, a feel of wearing, moisture absorption/ desorption, antistatic properties, resistance to change in color, etc. SOLUTION: This polyurethane yarn is made of a polyurethane which contains polyol(s) and diisocyanate(s) as main components, wherein polyvinyl alcohol and/or its copolymer are added to the polyurethane.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyurethane yarn and a method for producing the same.

More specifically, when used for clothing, etc., it has appropriate transparency and moderate elongation, has high heat setting properties, and has a certain degree of mechanical setability, detachability, fit, wearing feeling, and appearance. The present invention relates to a polyurethane yarn having excellent properties such as quality, moisture absorption / release properties, antistatic properties, and discoloration resistance, and a method for producing the same.

[0003]

2. Description of the Related Art Polyurethane yarns are widely used in legwear, innerwear, sportswear, etc. due to their excellent elastic properties. In order to further improve the stretch characteristics of such wear, the content of polyurethane yarns in fabrics is becoming increasingly higher. A typical example is the so-called zokki in the stocking market.

[0004] By using a zokki having a high mixing ratio of polyurethane yarn, the stretchability of stockings, the feeling of wearing, and the like can be made better than those of the conventional knitted product.

[0005] This also applies to other uses besides stockings. However, when the mixing ratio of the polyurethane yarn is increased, there are two problems. The first problem is that the detachability and the fit are deteriorated.

That is, when the mixing ratio of the polyurethane yarn is high, the size tends to be small, and the detachability is deteriorated.
The contact pressure tends to be slightly higher, and the fit is poor. The second problem is that polyurethane yarns are inferior in moisture absorption and release properties to mixed hard yarns, for example, polyamide fibers, so that the higher the percentage of polyurethane yarns, the lower the moisture absorption and release characteristics of the entire fabric. Several means have been tried for these problems, from raw yarn to high-order processing.

As a solution to the first problem, Japanese Patent Laid-Open No.
Japanese Patent No. 3815 discloses a method for obtaining a polyurethane fiber having high mechanical setting property and heat setting property.

Japanese Patent Application Laid-Open No. 2000-73233 discloses a method in which polyvinylidene fluoride is compounded with polyurethane as a compound for appropriately improving mechanical setting property and heat setting property.

As a solution to the second problem, Japanese Patent Laid-Open No. 5-271 discloses a method of blending a polyurethane salt with polyurethane as a compound for increasing the hygroscopicity.
No. 432.

A method of blending a polyurethane using polyethylene glycol as a raw material is disclosed in JP-A-2000-144.
No. 532. Japanese Patent Application Laid-Open No. 9-41204 discloses a method using a specific polyamide fiber having a high moisture absorption / release property for a hard yarn mixed with a polyurethane yarn as a means from a higher processing surface.

However, these methods are not sufficiently effective to simultaneously solve the above two objects, and in particular, impart appropriate mechanical setting properties, heat setting properties, and moisture absorption / release properties to the raw polyurethane yarn. I couldn't do that.

[0012] Also, when a hard yarn having high moisture absorption / release properties is used in the high-order processing stage, there are problems such as an increase in cost and difficulty in coping with all uses.

[0013]

When the polyurethane yarn of the present invention is used in clothes, the feeling of wearing, desorption, fit, moisture absorption / desorption, appearance quality, antistatic properties, and discoloration resistance of the obtained clothes and the like are obtained. Properties and the like can be improved.

An object of the present invention is to provide a polyurethane yarn having moderate transparency, moderate elongation, high heat setting, and a certain degree of mechanical setting, moisture absorption / desorption, antistatic properties, and discoloration resistance. And a method for manufacturing the same.

[0015]

The polyurethane yarn of the present invention has the following means for solving the above problems.

That is, a polyurethane yarn characterized in that the main constituent components of the polyurethane are a polyol and a diisocyanate, and the polyvinyl yarn contains polyvinyl alcohol and / or a copolymer thereof.

The method for producing a polyurethane yarn of the present invention has the following means for solving the above problems.

That is, polyvinyl alcohol and / or
Alternatively, a method for producing a polyurethane yarn, comprising adding the copolymer to a polyurethane solution and spinning.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail.

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

[0021] The polyurethane used in the present invention may be any, and is not particularly limited. Also, the synthesis method is not particularly limited.

That is, for example, a polyurethane urea composed of a polyol, a diisocyanate and a diamine, or a polyurethane composed of a polyol, a diisocyanate and a diol may be used.

Further, a polyurethane urea using a compound having a hydroxyl group and an amino group in a molecule as a chain extender may be used.

It is also preferable to use trifunctional or higher polyfunctional glycols or isocyanates as long as the effects of the present invention are not impaired.

Here, representative structural units constituting the polyurethane yarn of the present invention will be described.

The polyol used in the present invention is preferably a polyether glycol, a polyester glycol, a polycarbonate diol, or the like.

From the viewpoint of imparting flexibility and elongation to the yarn, it is preferable to use a polyether glycol. Examples of the polyether-based glycol include polyethylene oxide, polyethylene glycol,
Derivatives of polyethylene glycol, 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), THF and 2,3 Modified PTMG, which is a copolymer of -dimethyl THF, and polyols having side chains on both sides disclosed in Japanese Patent Publication No. 2615131 are preferably used. These polyether glycols may be used alone or in combination of two or more.

Further, from the viewpoint of obtaining abrasion resistance and light resistance as a polyurethane yarn, polyesters such as butylene adipate, polycaprolactone diol, and polyester polyol having a side chain disclosed in JP-A-61-26612 and the like. Glycol and Tokuhei 2-289
For example, polycarbonate diol disclosed in JP-A-516 and the like are preferably used.

Further, these polyols may be used alone or as a mixture or copolymer of two or more. The molecular weight of the polyol used in the present invention is preferably from 1,000 to 8,000, and more preferably from 1,000 to 8,000, from the viewpoint of obtaining elongation, strength, heat resistance and the like when formed into yarn.
800 or more and 6000 or less are more preferable. By using a polyol having a molecular weight in this range, an elastic yarn having excellent elongation, strength, elastic recovery force, and heat resistance can be obtained.

Next, as the diisocyanate used in the present invention, diphenylmethane diisocyanate (hereinafter, referred to as diphenylmethane diisocyanate)
MDI), tolylene diisocyanate, 1,4-
Aromatic diisocyanates such as diisocyanate benzene, xylylene diisocyanate, and 2,6-naphthalenedi isocyanate are particularly suitable for synthesizing a polyurethane having high heat resistance and strength. Further, as alicyclic diisocyanates, for example, methylene bis (cyclohexyl isocyanate) (hereinafter, referred to as H ₁₂ MDI),
Isophorone diisocyanate, methylcyclohexane 2,4-diisocyanate, methylcyclohexane 2,
Preferred are 6-diisocyanate, cyclohexane 1,4-diisocyanate, hexahydroxylylene diisocyanate, hexahydrotolylene diisocyanate, octahydro 1,5-naphthalenediisocyanate and the like. Aliphatic diisocyanates can be effectively used particularly for suppressing yellowing of polyurethane yarns. These diisocyanates may be used alone or in combination of two or more.

Next, as the chain extender in the present invention, it is preferable to use at least one of low molecular weight diamines and low molecular weight diols.

It should be noted that a compound having a hydroxyl group and an amino group in the molecule, such as ethanolamine, may be used. 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, a yarn excellent in elongation, elastic recovery, and heat resistance can be obtained. 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.

The low molecular weight diols include ethylene glycol, 1,3 propanediol, 1,4 butanediol, bishydroxyethoxybenzene, bishydroxyethylene terephthalate, 1-methyl-1,2-
Ethanediol and the like are typical. 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 having high heat resistance and high strength can be obtained.

The molecular weight of the elastic yarn of the present invention is preferably in the range of from 40,000 to 150,000 as a number average molecular weight from the viewpoint of obtaining fibers having high durability and strength.

The molecular weight in the present invention is measured by GPC, and is converted by polystyrene.

Then, as the polyurethane yarn of the present invention,
From the viewpoint of obtaining a product having excellent heat setting properties, including no process problems, including a process passability, particularly preferred are those composed of a diol and a diisocyanate, and the melting point of the polyurethane yarn on the high temperature side is 200 ° C. or higher. It is in the range of 260 ° C. or less. The melting point on the high temperature side in the present invention refers to a value of a second run when a yarn is measured by DSC, and corresponds to a so-called hard segment melting point of polyurethane.

The polyol has a molecular weight of 180.
Synthesized by using PTMG in the range of 0 or more and 6000 or less, MDI as a diisocyanate, and at least one selected from the group consisting of ethylene glycol, 1,3 propanediol and 1,4 butanediol as a diol, and The melting point on the high temperature side is 200 ° C or higher2
Polyurethane yarns having a temperature of 60 ° C. or lower are preferred because they have particularly high elongation and, as described above, have no practical problems including process passability and have excellent heat setting properties.

The high-temperature side melting point of the polyurethane yarn is 2
From the viewpoint of setting the temperature between 00 ° C. and 260 ° C. or less, it is preferable to conduct a test in advance and select the ratio of diisocyanate to polyol or diol. The structure of the polyurethane of the present invention preferably comprises such a material.

The polyurethane yarn of the present invention contains polyvinyl alcohol and / or a copolymer thereof.

In the present invention, if polyvinyl alcohol and / or a copolymer thereof are not contained, there is a problem that high heat setting properties and moisture absorbing / releasing properties cannot be obtained.

The polyvinyl alcohol and / or a copolymer thereof according to the present invention is a vinyl alcohol of the following general formula produced by converting a part or all of the acetyl group of polyvinyl acetate into a hydroxyl group by hydrolysis. Vinyl acetate copolymers are preferred.

[0042]

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The copolymer of polyvinyl alcohol is, for example, one obtained by esterifying the hydroxyl group of polyvinyl alcohol, ethylene, methacrylic acid ester, vinyl sulfonate, styrene sulfonic acid, sodium ethylene sulfonate, sodium propylene sulfonate, and the like. And the like are preferred. More specifically, vinyl alcohol-vinyl acetate-vinyl sulfonate copolymer, vinyl alcohol-vinyl acetate-vinyl phosphate copolymer, vinyl alcohol-vinyl acetate-ethylene copolymer, vinyl alcohol-vinyl acetate-methacrylic Acid esters and the like are preferred. Among these, a vinyl alcohol-vinyl acetate-vinyl sulfonate copolymer and a vinyl alcohol-vinyl acetate-sodium propylene sulfonate copolymer are more preferable.

The number average molecular weight of polyvinyl alcohol and / or its copolymer is 1,000 or more and 10 or more.
The range of 00000 or less is preferable. The number average molecular weight here can be determined by measuring with GPC, and is a value in terms of polystyrene.

In the present invention, the content of polyvinyl alcohol and / or its copolymer is preferably in the range of 0.5% by weight or more and 50% by weight or less from the viewpoint of obtaining good spinnability. From the viewpoint of obtaining the properties and moisture absorption / desorption properties, the content is more preferably 1% by weight or more and 30% by weight or less.

It is preferable that the contents are determined in advance by testing in advance according to the application and determining the contents as appropriate.

Further, using m and l in the above general formula,
The degree of saponification defined by [m / (m + 1)] × 100 is
A range of 1 or more and 99 or less is preferable, and from the viewpoint of adding to a polyurethane solution, good heat setting properties, and absorbing and releasing moisture,
10 or more and 90 or less are more preferable.

Further, the polyvinyl alcohol and / or its copolymer used in the present invention can be dispersed and dissolved in polyurethane at a high speed, and the properties of the produced polyurethane yarn can be set as desired properties, and the transparency can be appropriately adjusted. From the viewpoint of obtaining a polyurethane yarn of the above, and preventing the content of polyvinyl alcohol and / or its copolymer from being reduced or discoloring by receiving heat or the like in the spinning step, a 5% by weight DMAc solution was used. In this case, those having a viscosity at 20 ° C. of 200 cP or more and 10,000 P or less are preferable. Note that the measurement is preferably performed with a Brookfield viscometer.

Further, it is preferable that the polyurethane used in the present invention contains one or more terminal blocking agents. Monoamines such as dimethylamine, diisopropylamine, ethylmethylamine, diethylamine, methylpropylamine, isopropylmethylamine, diisopropylamine, butylmethylamine, isobutylmethylamine, isopentylmethylamine, dibutylamine, diamylamine, etc. , Propanol, butanol, isopropanol,
Monools such as allyl alcohol and cyclopentanol, and monoisocyanates such as phenyl isocyanate are preferred.

In the present invention, the polyurethane may contain various stabilizers and pigments. For example,
BHT and hindered phenolic agents such as "Sumilyzer GA-80" manufactured by Sumitomo Chemical Co., Ltd., various kinds of "Tinuvin" manufactured by Ciba Geigy, etc.
Benzotriazoles, benzophenones such as
Sumitomo Chemical Co., Ltd.'s "Sumilyzer P-16" phosphorus-based drugs, various hindered amine drugs, iron oxide, various pigments such as titanium oxide, zinc oxide, cerium oxide, magnesium oxide, inorganic substances such as carbon black, Fluorine or silicone resin powder, metal soap such as magnesium stearate, bactericide and deodorant containing silver, zinc and their compounds, lubricant such as silicone, mineral oil, barium sulfate, cerium oxide ,
It is preferable that various antistatic agents such as betaine and phosphoric acid are included, and it is also preferable that these are reacted with a polymer. In order to further increase the durability especially against light and various types of nitric oxide, 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.

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

In the present invention, it is preferable to first prepare a polyurethane solution. The method for producing the polyurethane solution and the method for producing the polyurethane as a solute of the solution may be either a melt polymerization method or a solution polymerization method, or may be another method. However, more preferred is the solution polymerization method. In the case of the solution polymerization method, the generation of foreign substances such as gel in the polyurethane is small, the spinning is easy, and the polyurethane yarn with low fineness is easily obtained.

As a matter of course, in the case of solution polymerization, there is an advantage that an operation for forming a solution can be omitted.

Polyurethane particularly suitable for the present invention is a polyol having a molecular weight of 1800 to 600.
It is synthesized using PTMG of 0 or less, MDI as a diisocyanate, and at least one of ethylene glycol, 1,3 propanediol and 1,4 butanediol as a diol, and has a melting point on the high temperature side of 200.
A temperature range of not less than ° C and not more than 260 ° C is exemplified.

Such polyurethane is, for example, DMA
c, DMF, DMSO, NMP, or the like, or a solvent containing these as a main component, and obtained by synthesizing the above-mentioned raw materials. For example, put each raw material in such a solvent,
Dissolved, heated to an appropriate temperature and reacted to form a polyurethane, so-called one-shot method, or a polyol and a diisocyanate are first melt-reacted, and then
A method in which the reactant is dissolved in a solvent and reacted with the above-mentioned diol to form a polyurethane can be employed as a particularly suitable method.

When a diol is used as the chain extender, a typical method for adjusting the high-temperature side melting point of the polyurethane to a range from 200 ° C. to 260 ° C. is to control the types and ratios of the polyol, MDI and diol. Can be achieved. When the molecular weight of the polyol is low, MDI
By increasing the ratio of the diol relatively, it is possible to obtain a polyurethane having a high melting point at a high temperature. Similarly, when the molecular weight of the diol is low, by decreasing the ratio of the polyol relatively, a polyurethane having a high melting point at a high temperature can be obtained. Can be obtained.

In the case where the polyol has a molecular weight of 1800 or more, the melting point on the high temperature side can be increased to 200 ° C. or more by (MDI
(Mol number of polyol) / (mol number of polyol) = 1.5 or more.

When synthesizing such a polyurethane,
One or more catalysts such as amine catalysts and organometallic catalysts
It is also preferable to use a mixture of two or more species. 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-dimethylaminoethylether, 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, N'-trimethylaminoethylethanolamine, N-methyl-N '-(2
-Hydroxyethyl) piperazine, 2,4,6-tris
(Dimethylaminomethyl) phenol, N, N-dimethylaminohexanol, triethanolamine and the like.

Examples of the organometallic catalyst include tin octoate, dibutyl tin dilaurate, and dibutyl lead octoate.

The concentration of 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 polyvinyl alcohol and / or a copolymer thereof to such a polyurethane solution. Any method can be adopted as a method for adding polyvinyl alcohol and / or its copolymer to the polyurethane solution. As a typical method, various methods such as a method using a static mixer, a method using stirring, a method using a homomixer, and a method using a twin screw extruder can be adopted. Here, the added polyvinyl alcohol and / or a copolymer thereof is, from the viewpoint of uniform addition to the polyurethane solution,
It is preferable to add in the form of a solution.

The addition of polyvinyl alcohol and / or its copolymer to the polyurethane solution may cause a phenomenon that the solution viscosity of the mixed solution after the addition is higher than expected than the solution viscosity of the polyurethane before the addition. There is, from the viewpoint of preventing this phenomenon, dimethylamine,
Monoamines such as diisopropylamine, ethylmethylamine, diethylamine, methylpropylamine, isopropylmethylamine, diisopropylamine, butylmethylamine, isobutylmethylamine, isopentylmethylamine, dibutylamine and diamylamine, ethanol, propanol, butanol, isopropanol, allyl It is also preferable to use one or a mixture of two or more terminal blocking agents such as alcohols, monools such as cyclopentanol, and monoisocyanates such as phenyl isocyanate.

When polyvinyl alcohol and / or its copolymer is added to the polyurethane solution, it may be added simultaneously with the above-mentioned agents such as light-proofing agents and antioxidants, pigments and the like.

The fineness and cross-sectional shape of the polyurethane yarn of the present invention are not particularly limited. For example, 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.

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 winding machine, it is preferable to appropriately determine the setting according to the intended use of the yarn.

That is, from the viewpoint of obtaining a polyurethane yarn having desired setting properties and stress relaxation, it is preferable that the speed ratio between the godet roller and the winder be in the range of 1.15 to 1.65. When a polyurethane yarn having particularly high setting property and low stress relaxation is obtained, the speed ratio between the godet roller and the winder is 1.15 or more and 1.4.
The following range is more preferable, and the range of 1.15 or more and 1.35 or less is still more preferable.

On the other hand, in order to obtain a polyurethane yarn having low setting property and high stress relaxation, it is preferable that the speed ratio between the godet roller and the winder be in the range of 1.25 or more and 1.65 or less. The range of 0.35 to 1.65 is more preferable.

The spinning speed is preferably 450 m / min or more from the viewpoint of improving the strength of the obtained polyurethane yarn.

[0070]

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

The method for measuring the setting property, stress relaxation, strength, elongation, heat setting property, moisture absorption / desorption property, quantification method of polyvinyl alcohol or its copolymer and discoloration resistance in the present invention will be described. [Setting property, stress relaxation, strength, elongation, heat setting property] The setting property, stress relaxation, strength, and elongation were measured by performing a tensile test on the polyurethane yarn using an Instron 4502 type tensile tester.

The 5 cm (L1) sample was subjected to 300% elongation five times at a tensile speed of 50 cm / min. The stress at this time was defined as (G1). Next, the length of the sample was held for 30 seconds. The stress after holding for 30 seconds was defined as (G2). Next, the elongation of the sample was recovered and the length of the sample when the stress became 0 was defined as (L2). The sample was further stretched for the sixth time until cutting. The stress at break was (G3), and the sample length at break was (L3). Hereinafter, the above characteristics are calculated by the following equations.

Strength = (G3) Stress relaxation = 100 × ((G1) − (G2)) / (G1) Setability = 100 × ((L2) − (L1)) / (L1) Elongation = 100 × ( (L3)-(L1)) / (L1) [Heat setting property] The heat setting property was measured as follows.

The sample yarn was free-flowed at 100 ° C. with steam.
Treatment was carried out for 0 minutes, followed by free treatment with boiling water at 100 ° C. for 2 hours and drying for 1 day at room temperature. Next, the sample yarn (length =
(L5)) was stretched by 100% (length = 2 × (L
5)). This length was treated with steam at 115 ° C. for 1 minute. Further, the same length was subjected to a dry heat treatment at 130 ° C., and the same length was left at room temperature for one day. Next, the elongated state of the sample yarn was removed, and the length (L6) was measured.
The heat setting property is calculated by the following equation.

Heat setting property = 100 × ((L6) − (L
5)) / (L5) [Hygroscopicity] Moisture absorption / desorption coefficient ΔM as an index indicating hygroscopicity
R was adopted.

The moisture absorption / desorption coefficient ΔMR is determined by measuring a knitted fabric obtained by knitting a sample raw yarn into a tubular shape in a desiccator after leaving it dry in a hot air oven at 105 ± 2 ° C. for 2 hours. (Cooling for 30 minutes) and the weight after standing for 24 hours in a thermo-hygrostat (Tubai PR-2G) in an atmosphere of 20 ° C. × 65% RH or 30 ° C. × 90% RH. It was found by the formula.

Moisture absorption (%) = [(weight after moisture absorption−weight at absolute dryness) / weight at absolute dryness] × 100 20 ° C. × 65% RH and 30 ° C. × 90% measured above.
From the moisture absorption rate under the condition of RH (referred to as MR1 and MR2, respectively), the moisture absorption / desorption coefficient ΔMR (%) = MR2-MR1
Was calculated.

The moisture absorption / desorption coefficient ΔMR is a driving force for obtaining comfort by releasing the moisture in the clothes when the clothes are worn to the outside air, and is a driving force for light-medium work or light-medium exercise. This is the difference in moisture absorption between the temperature inside the clothes represented by ° C × 90% RH and the outside temperature and humidity represented by 20 ° C. × 65% RH. The larger the ΔMR, the higher the hygroscopicity and the better the comfort when worn. [Content of Polyvinyl Alcohol or Its Copolymer] The method of calculating the content of polyvinyl alcohol or its copolymer in the sample yarn is described below.

First, 50 g of DMAc was added to 1 g of the sample yarn (A).
After completely dissolving the sample thread, add 10
0 ml was slowly added to precipitate polyvinyl alcohol or a copolymer thereof, and the remaining polyurethane solution was evaporated to dryness to isolate the polyurethane (B) in the sample yarn. Next, a calibration curve was prepared from an IR spectrum of a mixture of polyurethane (B) and polyvinyl alcohol or a copolymer thereof having a predetermined weight ratio.
The procedure was such that the content of polyvinyl alcohol or its copolymer was 0% by weight, 1% by weight, 3% by weight, 6% by weight, 1% by weight.
Samples of 0% by weight, 20% by weight and 40% by weight were prepared, and the characteristic absorption ν (CO) 1 in each IR spectrum was obtained.
700cm ^-1 ~1800cm ^-1 and ν (OH) 3400c
The peak area ratio (X) at m ^-1 was determined. For the IR spectrum measurement, FT-IR manufactured by Perkin Elmer Co., Ltd. was used, and as a measurement sample, a cast film by DMAc was used. A calibration curve of the content (wt%) of polyvinyl alcohol or its copolymer with respect to the peak area ratio (X) was prepared, and the slope (α) was obtained. Finally, the yarn sample (A) was washed with n-hexane, and then IR
The spectrum was measured. In the obtained spectrum, ν
(CO) 1700 cm ^{-1 to} 1800 cm ^-1 and ν (OH)
The peak area ratio (Xs) at 3400 cm ^-1 was determined.

The content was calculated by the following equation.

Content (% by weight) = (α) × (Xs) [Discoloration resistance] A sample yarn was placed on a 5 × 5 cm sample plate with a minimum load so that the color of the sample plate was not affected. The sample was wound up. Sample and standard white surface (JIS Z
The front surface of 4.3.4) of 8722 was covered with a flat and transparent glass plate of about 1 mm. The measurement of the b value was calculated based on the following formula using a Hunter type color difference meter according to the method C (Hunter method) of JIS L 1013. The number of measurements was set to 5 times, and the average value was adopted.

B = 7.0 (Y−0.847Z) / Y ^1/2 (where X, Y and Z were calculated according to JIS Z8701) The discoloration resistance was such that the sample was exposed to ultraviolet light (UV). The degree of yellowing upon exposure to nitrogen oxides (NOx) and the degree of yellowing upon exposure to chlorine bleach (Cl ₂ ) were evaluated. During each exposure treatment, the degree of yellowing (hereinafter abbreviated as Δb) was calculated as follows.

Δb = b value after exposure treatment−b value before exposure treatment Each exposure treatment was performed as follows. (Ultraviolet (UV) exposure treatment) Using a carbon arc type weather meter manufactured by Suga Test Instruments Co., Ltd.
The samples were exposed for 25 hours at a temperature and humidity of% RH. (Nitrogen oxide (NOx) exposure treatment) Using a closed container (Scott tester) with a rotating sample stand, NO.
Exposure treatment was performed for hours. (Exposure treatment with chlorine bleach (Cl ₂ )) A cycle of exposing the sample to a 500 ppm aqueous solution of “Kao Hiter” manufactured by Kao Corporation in a thermostat at 40 ° C. for 30 minutes and then washing with water for 10 minutes was repeated eight times.

[Example 1] PTMG having a molecular weight of 2900,
A DMAC solution (35% by weight) of polyurethane composed of MDI and ethylene glycol is polymerized to obtain a polymer solution A.
(Mol number of MDI) / (mol number of polyol)
= 3.97). Next, polyvinyl alcohol (Gohsenol (R), manufactured by Nippon Synthetic Chemical Co., Ltd., number average molecular weight 50,000)
DMAc solution having 0, saponification degree 88 and viscosity 2200P) was prepared. The horizontal mill WILLY A. BACH
85% using DYNO-MIL KDL manufactured by OFEN
Zirconia beads were filled, a uniform fine dispersion was prepared at a flow rate of 50 g / min, and this was designated as B1 (35% by weight). Further, a polyurethane formed by the reaction of t-butyldiethanolamine and methylene-bis- (4-cyclohexyl isocyanate) described in U.S. Pat. No. 3,555,115 and U.S. Pat.
No. 53290, DM of a mixture in a 2: 1 weight ratio of a condensation polymer of p-cresol and divinylbenzene.
An Ac solution (35% by weight) was prepared, and an antioxidant solution C1 was prepared.
(35% by weight). The polymer solutions A1, B1, and C1 were uniformly mixed at 93% by weight, 5% by weight, and 2% by weight to obtain a solution D1. The speed ratio between the godet roller and the winder is 1.
By dry spinning at a speed of 540 m / min as No. 4, a 200 g wound body of polyurethane yarn having a content of 20 dtex, monofilament, and polyvinyl alcohol of 5% by weight was obtained.

The breaking elongation, breaking strength, setting property, stress relaxation, heat setting property and melting point of the obtained yarn are shown in Table 1.
The moisture absorption / desorption coefficient ΔMR was increased 5 times as compared with Comparative Example 1 in which B1 was not blended. The heat setting property was higher than that of Comparative Example 1 in which B1 was not added, and the mechanical setting was moderate.

Further, the breaking elongation and the breaking strength were equal to or higher than Comparative Example 1 in which B1 was not blended. The obtained yarn and Toray Industries, Inc.
A covering thread (SCY) was formed using a nylon thread “Miracosmo” (22 decitex) and knitted with pantyhose. As a result, a pantyhose with excellent appearance quality could be obtained. Moisture absorption / desorption coefficient Δ
The MR was 4.4, which was about 1.6 times that of the Zocchi pantyhose of Comparative Example 1 using the same yarn without B1.

The resistance to discoloration against ultraviolet rays (UV), nitrogen oxides (NOx) and chlorine bleach (Cl ₂ ) was superior to those of the comparative examples.

[0088]

[Table 1]

Example 2 Polyvinyl alcohol (SMR resin (R), Shin-Etsu Chemical Co., Ltd., number average molecular weight 10,000)
A DMAc dispersion having a viscosity of 200 P) was prepared. The adjustment was performed in the same manner as in Example 1. This is called B2 (35
% By weight). The polymer solutions A1, B2 and C1 were uniformly mixed at 78% by weight, 20% by weight and 2% by weight, and a solution D2 was prepared.
And The speed ratio between the godet roller and the winder is 1.40.
By spinning at a speed of 540 m / min, a 200 g wound body of polyurethane yarn having a content of 20 dtex, monofilament, and polyvinyl alcohol of 20% by weight was obtained. Table 1 shows the breaking elongation, breaking strength, setting property, stress relaxation, heat setting property, and melting point of the yarn. The moisture absorption / desorption coefficient ΔMR was increased by a factor of 10 as compared with Comparative Example 1 not containing B2. The heat setting property was higher than that of Comparative Example 1 not containing B2, and the mechanical setting was also moderate.

Further, the breaking elongation and the breaking strength were equal to or greater than Comparative Example 1 in which B2 was not blended. Using the obtained yarn and a nylon yarn “Miracosmo” (22 decitex) manufactured by Toray Industries, Inc., forming a covering yarn (SCY) and knitting the ZOKI pantyhose, an excellent ZOKI pantyhose with excellent appearance quality is obtained. I was able to. The moisture absorption / desorption coefficient ΔMR of this ZOKI pantyhose was 4.4, which was about 1.6 times that of the ZOKI pantyhose of Comparative Example 1 using the same yarn without B2.

The resistance to discoloration against ultraviolet rays (UV), nitrogen oxides (NOx) and chlorine bleach (Cl ₂ ) was superior to those of the comparative examples.

Example 3 PTMG having a molecular weight of 1800,
A DMAc solution (35% by weight) of polyurethane urea comprising MDI, ethylenediamine and diethylamine as a terminal blocking agent was polymerized to obtain a solution A2 (moles of MDI) / (moles of polyol) = 1.58). next,
A DMAc solution of a polyvinyl alcohol sulfonic acid modified product (Goseilan (R), number average molecular weight 20,000, saponification degree 45, viscosity 110 P) manufactured by Nippon Synthetic Chemical Company was prepared, and B
It was set to 3. The adjustment was performed in the same manner as in Example 1. A
2, B3 and C1 were uniformly mixed at 68% by weight, 30% by weight and 2.0% by weight to obtain a solution D3. The solution D3 is dry-spun at a speed of 600 m / min with a speed ratio of a godet roller and a winder of 1.20, to obtain a polyurethane having a content of a 20 filament multi-filament / polyvinyl alcohol copolymer of 30% by weight. 50 of thread
0 g of a wound body was obtained. Table 1 shows the breaking elongation, breaking strength, setting property, stress relaxation, heat setting property, and melting point of the yarn. The moisture absorption / desorption coefficient ΔMR was increased 9-fold as compared with Comparative Example 2 not containing B3. The heat setting property was higher than that of Comparative Example 2 not containing B3, and the mechanical setting was also moderate.

The breaking elongation and the breaking strength are equal to or higher than those of Comparative Example 2 in which B3 is not blended. Was formed and knitted pantyhose was obtained. As a result, an excellent pantyhose with excellent appearance quality was obtained. Moisture absorption / desorption coefficient ΔMR
Was 4.9, which was about 1.8 times that of the Zocchi pantyhose of Comparative Example 2 using the same raw yarn not containing B3.

The discoloration resistance to ultraviolet light (UV), nitrogen oxides (NOx) and chlorine bleach (Cl ₂ ) was superior to those of the comparative examples.

Example 4 PTMG having a molecular weight of 1800,
MDI, 80/20 molar ratio of ethylenediamine and 1,3
DM of polyurethaneurea comprising cyclohexyldiamine and diethylamine as a terminal blocking agent
The AC solution (35% by weight) was polymerized to obtain a solution A3 (M
(Mol number of DI) / (mol number of polyol) = 1.7
4). 63% by weight, 35% by weight of A3, B3 and C1,
The mixture was uniformly mixed at 2.0% by weight to obtain a solution D3. Solution D
3 assuming that the speed ratio between the god roller and the winder is 1.30 and 6
By dry spinning at a speed of 00 m / min, 20
A 500 g wound body of polyurethane yarn having a content of the decitex multifilament and polyvinyl alcohol copolymer of 35% by weight was obtained. Table 1 shows the breaking elongation, breaking strength, setting property, stress relaxation, heat setting property, and melting point of the yarn. The moisture absorption / desorption coefficient ΔMR increased 13 times as compared with Comparative Example 3 not containing B3. The heat setting property was higher than that of Comparative Example 3 not containing B3, and the mechanical setting was also moderate. Also, the breaking elongation and breaking strength are Comparative Example 3 in which B3 is not blended.
Was equal to or greater than

Using the obtained yarn and a nylon yarn “Miracosmo” (22 decitex) manufactured by Toray Industries, Inc., forming a covering yarn (SCY) and knitting a pantyhose pantyhose, an excellent zokki with excellent appearance quality was obtained. I got pantyhose. The moisture absorption / desorption coefficient ΔMR of this ZOKI pantyhose was 5.0, and Comparative Example 3 using the same raw yarn not containing B3 was used.
Was about 2.0 times that of Zokki Pantyhose.

The discoloration resistance to ultraviolet light (UV), nitrogen oxides (NOx) and chlorine bleach (Cl ₂ ) was superior to those of the comparative examples.

Comparative Example 1 A polymer solution A1 and an additive solution C1 were mixed to obtain a uniform solution E1. The solution E1 was dry-spun at a speed of 540 m / min with a speed ratio of a godet roller and a winder of 1.40, to obtain a monofilament yarn of 18 dtex. The breaking elongation of this yarn,
Table 1 also shows the breaking strength, the setting property, the stress relaxation, the heat setting property, and the melting point of the yarn.

Using the obtained yarn, a covering yarn (SCY) was formed using a nylon yarn “Miracosmo” (22 decitex) manufactured by Toray Industries, Inc., and knitted pantyhose.
The moisture absorption / desorption coefficient ΔMR of this ZOKI pantyhose was 2.7.

The discoloration resistance to ultraviolet light (UV), nitrogen oxides (NOx) and chlorine bleach (Cl ₂ ) was inferior to each of the examples. Comparative Example 2 A polymer solution A2 and an additive solution C1 were mixed to obtain a uniform solution E2. The solution E2 was dry-spun at a speed of 600 m / min with a speed ratio of a godet roller and a winder of 1.20, thereby obtaining a 500 g wound body of 20 dtex multifilament. Table 1 also shows the breaking elongation, breaking strength, setting property, stress relaxation, heat setting property, and melting point of the yarn.

Using the obtained yarn, a covering yarn (SCY) was formed using a nylon yarn “Miracosmo” (22 decitex) manufactured by Toray Industries, Inc., and knitted pantyhose.
The moisture absorption / desorption coefficient ΔMR of this ZOKI pantyhose was 2.8.

The discoloration resistance to ultraviolet light (UV), nitrogen oxides (NOx) and chlorine bleach (Cl ₂ ) was inferior to each of the examples.

Comparative Example 3 A polymer solution A3 and an additive solution C1 were mixed to obtain a uniform solution E3. The solution E3 was dry-spun at a speed of 600 m / min with a speed ratio of a godet roller and a winder of 1.30 to obtain a 500 g wound body of multifilaments having 20 dtex. Table 1 also shows the breaking elongation, breaking strength, setting property, stress relaxation, heat setting property, and melting point of the yarn.

Using the obtained yarn, a covering yarn (SCY) was formed by a nylon yarn “Miracosmo” (22 decitex) manufactured by Toray Industries, Inc., and knitted pantyhose.
The moisture absorption / desorption coefficient ΔMR of this ZOKI pantyhose was 2.5.

The discoloration resistance to ultraviolet light (UV), nitrogen oxides (NOx) and chlorine bleach (Cl ₂ ) was inferior to those of the examples.

[0106]

The clothes and the like using the polyurethane yarn of the present invention have appropriate transparency and moderate elongation, have high heat setting properties, and have a certain degree of mechanical setting properties and detachability.
Excellent in fit, appearance quality, wearing feeling, moisture absorption / release properties, antistatic properties, discoloration resistance, etc. Due to 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 knits, tricots, swimwear, ski pants, work clothes, smoke fire, etc. Clothes, clothes, golf trousers, wet suits, bras, girdle, fastening materials for various fiber products such as gloves and socks, fastening materials for preventing leakage of sanitary items such as paper diapers, fastening materials for waterproof materials, mimic bait, artificial flowers, electricity It can be used for various applications such as insulating materials, wiping cloths, copy cleaners and gaskets.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Masahito Inoue 1-2-1, Sonoyama, Otsu-shi, Shiga F-term in the Shiga Plant of Toray Dupont Co., Ltd. (Reference) 4L035 AA04 BB11 DD14 EE01 EE05 EE08 EE13 EE20 FF01 FF04 GG04 HH01 KK05 MH02 MH13

Claims (7)

[Claims] 1. A polyurethane yarn, wherein the main components of the polyurethane are a polyol and a diisocyanate,
And a polyurethane yarn containing polyvinyl alcohol and / or a copolymer thereof. 2. The polyvinyl alcohol and / or its copolymer has a number average molecular weight of 1,000 to 1,000,000.
The polyurethane yarn according to claim 1, wherein: 3. The polyurethane yarn according to claim 1, wherein the content of the polyvinyl alcohol and / or a copolymer thereof is 0.5% by weight or more and 50% by weight or less. 4. A method for producing a polyurethane yarn, comprising adding polyvinyl alcohol and / or a copolymer thereof to a polyurethane solution and spinning. 5. The polyvinyl alcohol and / or a copolymer thereof has a number average molecular weight of 1,000 to 1,000,000.
The method for producing a polyurethane yarn according to claim 4, wherein: 6. The method for producing a polyurethane yarn according to claim 4, wherein the spinning method is dry. 7. The method for producing a polyurethane yarn according to claim 4, wherein the spinning speed is 450 m / min or more.