JPH11200146A - Polyurethane yarn and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a product excellent in appearance grade, fitness, wearability, a feeling of wearing, etc. SOLUTION: This polyurethane yarn contains a polyol, a diisocyanate and a diol which are main constituent components of the polyurethane and further a polyvinylpyrrolidone and/or its copolymer. The content of the polyvinylpyrrolidone and/or its copolymer is >=0.1 and <=10 wt.%. The K-value of the polyvinylpyrrolidone and/or its copolymer is >=20 and <=70.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a polyurethane yarn and a method for producing the same.

[0002] More specifically, by using the polyurethane yarn of the present invention for high-level processing and using it for clothes, etc.
The present invention relates to a polyurethane yarn capable of obtaining a material excellent in appearance quality, fit, wearability, wear feeling, and the like, 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 elasticity.

[0004] In order to make the most of these characteristics, polyurethane yarns account for a higher proportion of fabrics. A typical example is the so-called zokki in the stocking market.

[0005] The appearance of the stockings, the fit, the wearability, the feeling of wearing, etc. of the stockings are all reduced by using the zokki.
It is better than the conventional knitted product.

That is, by increasing the mixing ratio of the polyurethane yarn, a good yarn could be obtained.
And this is not limited to stockings.

[0007] However, there is a problem with the pressure and size that has not been completely solved by the conventional techniques. In other words, when the mixing ratio of the polyurethane yarn increases, the compression pressure tends to increase slightly and the size tends to decrease.

As a solution to such a problem, several means have been adopted from raw yarn to high-order processing.

[0009] As a representative means, in the case of a raw yarn, for example, a method of improving the setting property and the heat setting property has been adopted. In the high-order processing, for example, a method of lowering a draft in a processing step has been adopted.

However, the effect of the former alone is low for these purposes. In the latter case, there is a problem that the cost is increased.

Japanese Patent Application Laid-Open No. 48-80150 discloses a technique in which polyvinylpyrrolidone is added to polyurethane urea chain-extended with a low-molecular-weight diamine compound to perform wet spinning.

[0012]

However, the technique disclosed in Japanese Patent Application Laid-Open No. 48-80150 discloses a so-called polyurethane which is chain-extended with a low molecular weight diamine compound for the purpose of improving white retention. It was obtained by wet spinning of urea, and did not improve appearance quality, fit, wearability, and wearing feeling when polyurethane yarn was used for clothes and the like.

According to the present invention, it is possible to obtain a product excellent in appearance quality, fit, wearability, wear feeling, etc., which cannot be obtained by the conventional technology.

[0014] Further, the combination of the polyurethane yarn according to the present invention with various fibers can be applied to various uses.

[0015]

Means for Solving the Problems The polyurethane yarn of the present invention has the following matters specifying the invention in order to solve the above-mentioned problems.

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

Further, the method for producing a polyurethane yarn of the present invention has the following items for specifying the invention in order to solve the above-mentioned problems.

That is, a polyurethane is produced by synthesizing a polyurethane in a solution using a polyol, diisocyanate and a diol as main raw materials, adding polyvinylpyrrolidone and / or a copolymer thereof to the solution, and performing dry spinning. Is the way.

[0019]

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

First, the polyurethane according to the present invention will be described.

The main components of the polyurethane according to the present invention are polyols, diisocyanates and diols. Also, the synthesis method is not particularly limited. In particular, polymerization is preferably performed in a solution from the viewpoint of efficiently performing the reaction. Note that trifunctional or higher polyfunctional glycols and isocyanates may be used 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.

As the polyol used in the present invention, polyether glycol, polyester glycol, polycarbonate diol and the like can be used as typical examples.

[0024] In particular, when flexibility and elongation of the yarn are required, it is preferable to use a polyether glycol. Examples of the polyether glycol include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol (hereinafter abbreviated as PTMG), modified PTMG (hereinafter abbreviated as 3M-PTMG) which is a copolymer of THF and 3-MeTHF, Typical examples thereof include modified PTMG which is a copolymer of THF and 2,3-dimethyl THF, and polyols such as polyalkylene ether glycol having a side chain on both sides disclosed in Japanese Patent No. 2615131. it can. These polyether-based glycols may be used alone or as a mixture or copolymer of two or more.

Further, when abrasion resistance and light resistance are particularly required as the polyurethane yarn, butylene adipate, polycaprolactone diol, polyester having a side chain disclosed in JP-A-61-26612 and the like can be used. Polyester glycols such as polyols and polycarbonate diols disclosed in Japanese Patent Publication No. 2-289516 may be used.

These polyols may be used alone or as a mixture or copolymer of two or more.

The number average molecular weight of the polyol used in the present invention is 1 from the viewpoint of elongation, strength, heat resistance and the like when formed into a yarn.
It is preferably in the range of 000 or more and 8000 or less.

More preferably, the range is 2500 or more and 6000 or less. 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, the diisocyanate used in the present invention is diphenylmethane diisocyanate (hereinafter abbreviated as MDI), tolylene diisocyanate, 1,4-diisocyanate benzene, xylylene diisocyanate, 2,6
-An aromatic diisocyanate such as naphthalene diisocyanate is particularly suitable for synthesizing a polyurethane having high heat resistance and strength.

Further, as the alicyclic diisocyanate, for example, methylene bis (cyclohexyl isocyanate)
(Hereinafter abbreviated 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 can be used. 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, a low molecular weight diol is used as the chain extender used in the present invention.

As the low molecular weight diol, ethylene glycol, 1,3 propanediol, 1,4 butanediol, bishydroxyethoxybenzene, bishydroxyethylene terephthalate and the like can be used.

One or more of these can be selected and 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.

From the viewpoint of obtaining fibers having high durability and strength, the number average molecular weight of the elastic yarn of the present invention is from 40,000 to 15
It is preferably in the range of 10,000 or less.

The molecular weight in the present invention is measured by GPC, and is converted by polystyrene. The polyurethane yarn of the present invention preferably has such a configuration.

And further, ethylene glycol,
At least one diol selected from the group consisting of 1,3 propanediol and 1,4 butanediol; a polyol having a molecular weight in the range of 2500 to 6000; Polyurethane yarns having a melting point of 180 ° C. or more and 250 ° C. or less have a particularly high elongation, and, as described above, have no practical problems, including process passability, and have excellent heat setting properties. preferable.

The melting point on the high temperature side in the present invention is defined as DSC
The value of the second run when the yarn is measured in the above, and corresponds to the so-called hard segment melting point of polyurethane.

The melting point of the high-temperature side of the polyurethane yarn is 1
In order to make the temperature between 80 ° C. and 250 ° C. or less, it is preferable to conduct a test in advance and appropriately select the ratio of diisocyanate to polyol and diol.

The structure of the polyurethane of the present invention preferably comprises such a material.

Next, the polyurethane yarn of the present invention contains at least one of polyvinylpyrrolidone (hereinafter abbreviated as PVP) and a copolymer thereof.

If at least one of polyvinylpyrrolidone and its copolymer is not contained, heat setting property,
There is a problem in that the setting property is low and the size is small and the feeling of pressure is too high when various types of clothes are used.

The preferred content of at least one of PVP and its copolymer is from 0.1% by weight to 10% by weight.

If the polyurethane yarn contains at least one of PVP and its copolymer, the cause is unknown, but the heat setting property and the mechanical setting property are improved, and the strength is improved. But does not adversely affect properties such as elongation and stress relaxation, and even if PVP and at least one of its copolymers are present in the yarn, the yarn is fibrillated. In addition, an unexpected and surprising phenomenon appears to be no different from conventional polyurethane yarns in use.

Also, in the process aspect, when PVP and its copolymer are added to a polyurethane solution and dry-spinning is performed, an effect that spinnability is extremely improved can be obtained.

Particularly preferred as the content of at least one of PVP and its copolymer is 1
It is in the range of at least 7% by weight.

When the content of PVP and its copolymer is 1
When it is in the range of not less than 7% by weight and not more than 7% by weight, setability, stress relaxation, strength, elongation, and heat setability are particularly good, and spinnability is also good.

Since these characteristic values need to be changed depending on the use of the polyurethane yarn, it is preferable to conduct a test in advance according to the use and determine the content ratio of PVP and its copolymer appropriately.

In the present invention, the copolymerization compound used for synthesizing the copolymer of PVP is not particularly limited. For example, N-isopropenyl 2-pyrrolidone, N-vinyl 4-methyl 2- Pyrrolidone, N-vinyl piperidone, N-vinyl caprolactam, N-vinyl enantholactam, N-vinyl valerolactam, N-butenyl-2,4-di (1-butenyl) -2-pyrrolidone vinyl acetate, dimethylaminoethyl methacrylate,
Styrene, acrylic acid, or the like can be used. These copolymers may be either block copolymers or random copolymers.

Next, the production of the polyurethane yarn is made particularly easy, and the characteristics of the produced polyurethane yarn are set as the target characteristics. Further, in practical use, at least one of PVP and its copolymer is dropped off. From the viewpoint of not substantially generating the K value, the K value of at least one of PVP and the copolymer thereof used in the present invention is 20 or more and 70 or more.
It is preferable to be within the following range.

In the present invention, the K value refers to a value calculated from the viscosity equation of Fikenscher.

The required content of PVP and its copolymer in the polyurethane yarn depends on the target properties of the polyurethane yarn,
In particular, the value of the K value is considered to be affected. Therefore, it is preferable to appropriately select the K value and the contents of PVP and its copolymer according to the target properties of the yarn.

Particularly preferred as PVP and its copolymer are those obtained by synthesizing PVP and isopropyl alcohol as a solvent. PVP and its copolymers synthesized using isopropyl alcohol as a solvent have a low content of pyrrolidone as a by-product, and it is difficult for the PVP and its copolymers themselves to be colored. This is preferable because it does not cause a problem.

The fineness and cross-sectional shape of the yarn of the present invention are not particularly limited. For example, the cross section of the yarn may be circular or flat. Further, there is no problem even if the polyurethane yarn of the present invention contains various stabilizers and pigments. For example, hindered phenol-based drugs such as BHT and Sumitomo Chemical Co., Ltd.'s "Sumilyzer" GA-80, and various benzotriazole-based drugs such as various "tinuvins" as light-fast and antioxidant agents. Phosphorus drugs such as "Sumilyzer" P-16 manufactured by Sumitomo Chemical Co., Ltd .; hindered amine drugs such as various "tinuvins"; and inorganic materials such as titanium oxide, zinc oxide and carbon black. Pigments, metal soaps such as magnesium stearate, bactericides and deodorants containing silver, zinc and their compounds, lubricants such as silicone and mineral oil, barium sulfate, cerium oxide, betaine and phosphoric acid Even if it contains various antistatic agents such as system, or reacts with polymer, It does not matter.

In order to further enhance the durability especially against light and various types of nitric oxide, a nitric oxide supplement such as HN-150 manufactured by Nippon Hydrazine Co., Ltd.
For example, "Sumilyzer" GA- manufactured by Sumitomo Chemical Co., Ltd.
80, it is effective to use a light stabilizer such as "Sumisorb" 300 # 622 manufactured by Sumitomo Chemical Co., Ltd.

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

In the present invention, first, a polyurethane solution is prepared.

In the present invention, any method may be used for producing a polyurethane solution which is a solute of a polyurethane solution or a polyurethane solution. That is, either the melt polymerization method or the solution polymerization method may be used. 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. Also, needless to say, solution polymerization is preferable from the viewpoint of production efficiency because labor for preparing a solution is omitted.

As the particularly preferred polyurethane in the present invention, those described above can be used.

Among these, particularly preferred polyurethane is a polyol having a molecular weight of 2,500 to 6,000, and the diol as a chain extender is selected from the group consisting of ethylene glycol, 1,3 propanediol and 1,4 butanediol. The diisocyanate is at least one selected from the group consisting of MDI as a main raw material, and is synthesized in a solution.
This is a polyurethane solution having a temperature of 250 ° C. or lower.

Such polyurethane is, for example, DMA
C, DMF, DMSO, NMP, or the like, or a solvent containing these as a main component, can be obtained by synthesizing the above-mentioned raw materials.

For example, the so-called one-shot method in which each raw material is charged and dissolved in such a solvent and heated to an appropriate temperature to cause a polyurethane to be reacted, or a polyol and MDI are first melt-reacted, and thereafter, the polyurethane is melted. 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.

As a typical method for adjusting the melting point on the high temperature side of the polyurethane to 180 ° C. or more and 250 ° C. or less, a method of controlling the types and ratios of polyol, MDI, and diol is preferably employed. When the molecular weight of the polyol is high, it is preferable to relatively increase the proportion of MDI. Similarly, when the molecular weight of the diol is high, a polyurethane having a high melting point on the high temperature side can be obtained by relatively reducing the proportion of the polyol.

In the case where the polyol has a molecular weight of 2500 or more, the melting point on the high temperature side can be adjusted to 180 ° C. or more by (MDI
It is preferable to proceed the polymerization at a ratio of (mol number of) / (mol number of polyol) = 2 or more.

When synthesizing such a polyurethane,
An amine catalyst or an organometallic catalyst may be used alone or in combination of two or more. Typical examples thereof include amine catalysts such as N, N-dimethylcyclohexylamine, N, N-dimethylbenzylamine, triethylamine, N-methylmorpholine,
Ethylmorpholine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethyl-1,3-propanediamine, N, N, N ', N'-tetramethylhexane Diamine, 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,
N'-trimethylaminoethylethanolamine, N-
Methyl-N ′-(2-hydroxyethyl) piperazine,
2,4,6-tris (dimethylaminomethyl) phenol, N, N-dimethylaminohexanol, triethanolamine and the like can be used. Further, as the organic metal catalyst, tin octoate, dibutyl tin dilaurate, lead dibutyl octoate and the like can be used.

The concentration of the polyurethane solution thus obtained is not particularly limited, but is usually preferably in the range of 30% by weight to 80% by weight.

In the present invention, at least one of PVP and its copolymer is added to the polyurethane solution. As a method of adding at least one of PVP and its copolymer to the polyurethane solution, any method can be adopted. Typical examples thereof include a method using a static mixer and a method using stirring.

Here, it is preferable that at least one of the added PVP and its copolymer is added in the form of a solution. If it is a solution, it can be uniformly added to the polyurethane solution. The addition to the polyurethane solution may be carried out simultaneously with the above-mentioned chemicals and pigments, such as, for example, a light-resistant agent and an antioxidant.

Next, it is preferable that at least one of the added PVP and its copolymer has a K value of 20 or more and 70 or less. By using at least one of PVP and its copolymer having such a value, spinning can be stabilized and a polyurethane yarn having desired properties can be obtained.

Further, more preferred PVP and its copolymer are those synthesized using isopropyl alcohol as a solvent. The reason is as described above.

The dry spinning method is not particularly limited, and any method can be used.

Next, 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. Therefore, it is preferable to determine the setting according to the purpose of use of the yarn.

That is, it is preferable that the speed ratio between the godet roller and the winder is 1.15 or more and 1.65 or less. When a yarn having particularly high setting property and low stress relaxation is required, the ratio is more preferably 1.15 or more and 1.40 or less, and the ratio is wound to 1.15 or more and 1.35 or less. Is more preferable.

On the other hand, when a yarn having low setting property and high stress relaxation is required, the ratio is preferably 1.25 or more and 1.65 or less, and the ratio is preferably set to 1.35 or more and 1.65 or less. It is more preferable to take.

The spinning speed is preferably 450 m / min or more from the viewpoint of increasing the strength.

The spinning speed is 450 m from the viewpoint of operability.
/ Min to 2,000 m / min.

In the present invention, in particular, from the viewpoint of stably spinning yarns of various finenesses, that is, from the viewpoint of stably spinning from thin to thick yarn, the drying atmosphere temperature is set to the melting point on the high temperature side of polyurethane. Higher temperatures are preferred.

The drying atmosphere temperature in the present invention means the temperature of the gas at the entrance to the spinning machine when the gas for drying is sent below the spinneret.

[0079]

EXAMPLES The present invention will be described in more detail with reference to Examples. However, the present invention is not limited by these examples.

The setting property, stress relaxation, strength, elongation, heat setting property and PVP quantification method in the present invention will be described. [Set property, stress relaxation, strength, elongation] The setting property, stress relaxation, strength, and elongation were measured by using polyurethane yarn with Instron 45.
It was obtained by performing a tensile test using a 02 type tensile tester.

These are defined below.

A 5 cm (L1) sample was subjected to 300% elongation five times at a pulling rate of 50 cm / min. The stress at this time was defined as (G1).

Next, the length was held for 30 seconds. The stress after holding for 30 seconds was defined as (G2).

Next, the length of the sample when the elongation was recovered and the stress became 0 was defined as (L2).

Further, the polyurethane yarn was stretched for the sixth time until it was cut.

The stress at break was (G3), and the sample length at break was (L3).

The above characteristics were obtained 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] Yarn is free and steamed at 100 ° C for 10 minutes.
The mixture was then treated for 2 hours with free boiling water at 100 ° C. and dried at room temperature for one day. Next, the yarn (length = (L
5)) was elongated by 100% (length = 2 × (L5)). The length was treated with steam at 115 ° C. for 1 minute. Further, at the same length, dry heat treatment at 130 ° C, and at the same length,
It was left at room temperature for one day.

Next, the stretched state of the yarn was removed, and its length (L6) was measured.

Heat setting property = 100 × ((L6) − (L
5)) / (L5) [Quantitative method of PVP] 1 g of a yarn sample was placed in a Soxhlet extractor using dichloromethane as a solvent, and at least one of PVP and a copolymer thereof was extracted.

After distilling off the solvent, 20 ml of methanol was added.
The residue was dissolved and analyzed by high performance liquid chromatography. For quantification, a calibration curve was prepared in advance with a solution of PVP and its copolymer whose concentration was determined and used.
The content was determined by the following equation.

Content (% by weight) = (sample peak area / calibration curve peak area) × calibration curve sample amount / yarn sample weight [Example 1] Polyethylene dimethylacetamide solution consisting of PTMG, MDI and ethylene glycol having a molecular weight of 2100 (39% by weight) 2000 g of Kanto Chemical's PVP (K = 30) in dimethylacetamide solution (40
6%) and stirred for 2 hours to obtain a sample solution. The resulting solution is discharged from a die into a gas having a dry atmosphere temperature of 380 ° C., and is spin-dried at a speed of 540 m / min with a speed ratio of a godet roller and a winder of 1.40 to obtain 18 denier monofilament. Yarn was obtained.

The spinnability was good. Table 1 shows the elongation, strength, setting property, stress relaxation, heat setting property, PVP content, and melting point of this yarn. The knitting of the Zokki Pantyhose using this yarn resulted in a Zokki Pantyhose having a larger dimension than the conventional Zokki Pantyhose, and a wearing pressure which was not higher than that of the conventional product and was excellent in wearability and wearing feeling. [Example 2] The same polyurethane solution 196 as in Example 1
A sample solution was prepared by adding 19.9 g of a dimethylacetamide solution (40% by weight) of PVP (K = 30) manufactured by Kanto Chemical Co., Ltd. to 7 g, and stirring for 2 hours. The obtained solution was discharged into a gas at the same dry atmosphere temperature as in Example 1, and the speed ratio between the godet roller and the winder was 1.40 and 540 m /
By dry spinning at a speed of 1 minute, an 18 denier monofilament yarn was obtained. The spinnability was good.

The elongation, strength, setting property, stress relaxation, heat setting property, PVP content and melting point of the yarn are shown in Table 1.
Shown in The knitting of the Zokki Pantyhose using this yarn resulted in a Zokki Pantyhose having a larger dimension than the conventional Zokki Pantyhose, and a wearing pressure which was not higher than that of the conventional product and was excellent in wearability and wearing feeling. [Example 3] The same polyurethane solution 203 as in Example 1
8 g of PVP (G) obtained by copolymerizing 10% of N-butenyl-2,4-di (1-butenyl) -2-pyrrolidone manufactured by ISP.
63.0 g of a dimethylacetamide solution (ANEX P-904) (40% by weight) was added and stirred for 2 hours to obtain a sample solution. The resulting solution was discharged into a gas at the same dry atmosphere temperature as in Example 1, and was subjected to dry spinning at a speed of 540 m / min with a speed ratio of a godet roller and a winder of 1.40 to obtain 18 denier monofilament. Yarn was obtained. The spinnability was good. Table 1 shows the elongation, strength, setting property, stress relaxation, heat setting property, PVP content and melting point of the yarn. The knitting of the Zokki Pantyhose using this yarn resulted in a Zokki Pantyhose having a larger dimension than the conventional Zokki Pantyhose, and a wearing pressure which was not higher than that of the conventional product and was excellent in wearability and wearing feeling. [Example 4] The same polyurethane solution 198 as in Example 1
PVP copolymerized with 3 g of vinyl acetate manufactured by ISP
61.3 g of a dimethylacetamide solution (40% by weight) of (S-630) was added, and the mixture was stirred for 2 hours to obtain a sample solution. The resulting solution was discharged into a gas at the same dry atmosphere temperature as in Example 1, and was subjected to dry spinning at a speed of 540 m / min with a speed ratio of a godet roller and a winder of 1.40 to obtain 18 denier monofilament. Yarn was obtained. The spinnability was good. Table 1 shows the elongation, strength, setting property, stress relaxation, heat setting property, PVP content and melting point of the yarn. The knitting of the Zokki Pantyhose using this yarn resulted in a Zokki Pantyhose having a larger dimension than the conventional Zokki Pantyhose, and a wearing pressure which was not higher than that of the conventional product and was excellent in wearability and wearing feeling. Example 5 2011 g of a polyurethane dimethylacetamide solution (40% by weight) composed of PTMG, MDI and 1,4-butanediol having a molecular weight of 2900, a dimethylacetamide solution (40% by weight) of PVP (K = 30) manufactured by Kanto Chemical Co., Ltd. Was added and stirred for 2 hours to obtain a sample solution. The resulting solution was discharged into a gas at the same dry atmosphere temperature as in Example 1, and was subjected to dry spinning at a speed of 540 m / min with a speed ratio of a godet roller and a winder of 1.40 to obtain 18 denier monofilament. Yarn was obtained. The spinnability was good. Table 1 shows the elongation, strength, setting property, stress relaxation, heat setting property, PVP content and melting point of the yarn. The knitting of the Zokki Pantyhose using this yarn resulted in a Zokki Pantyhose having a larger dimension than the conventional Zokki Pantyhose, and a wearing pressure which was not higher than that of the conventional product and was excellent in wearability and wearing feeling. Example 6 Modified PTMG having a molecular weight of 3500, which is a copolymer of THF and 3-MeTHF, MDI and 1,
1,792 g of a polyurethane dimethylacetamide solution (40% by weight) composed of 4-butanediol
(Weight%) and 16.6 g of a dimethylacetamide solution (40 weight%) of PVP (S-630) obtained by copolymerizing vinyl acetate manufactured by ISP, and stirred for 2 hours to obtain a sample solution. The resulting solution was discharged into a gas at the same dry atmosphere temperature as in Example 1, and was subjected to dry spinning at a speed of 540 m / min with a speed ratio of a godet roller and a winder of 1.40 to obtain 18 denier monofilament. Yarn was obtained. The spinnability was good. Elongation, strength, setting, stress relaxation, heat setting, PV
Table 1 also shows the P content and the melting point. The knitting of the Zokki Pantyhose using this yarn resulted in a Zokki Pantyhose having a larger dimension than the conventional Zokki Pantyhose, and a wearing pressure which was not higher than that of the conventional product and was excellent in wearability and wearing feeling. Example 7 180 kg of the same polyurethane dimethylacetamide solution (39% by weight) as in Example 1 Kanto Chemical's PVP (K = 30) dimethylacetamide solution (4
0% by weight) and stirred for 2 hours to obtain a sample solution. The obtained solution is discharged from a die into a gas having a dry atmosphere temperature of 420 ° C., and five discharge yarns are joined by a temporary twisting method, and the speed ratio between the godet roller and the winder is set to 1.32 and 540 m / m. Dry spinning at a speed of minutes resulted in a 70 denier yarn.

The spinnability was good. Table 1 shows the elongation, strength, settability, stress relaxation, heat setting, PVP content and melting point of this yarn. [Example 8] The same polyurethane solution 198 as in Example 1
To 3 g, 61.3 g of a dimethylacetamide solution (40% by weight) of BASF-manufactured PVP ("Rubiscol" K30 Special Grade, hereinafter abbreviated as K30SP) polymerized using isopropyl alcohol as a polymerization solvent was added, and 2 g was added.
By stirring for a time, a sample solution was obtained. The obtained solution was discharged into a gas at the same dry atmosphere temperature as in Example 1,
540 when the speed ratio between the godet roller and the winder is 1.40
By dry spinning at a speed of m / min, an 18 denier monofilament yarn was obtained. The spinnability was good. Table 1 shows the elongation, strength, setting property, stress relaxation, heat setting property, PVP content and melting point of the yarn.
The knitting of the Zokki Pantyhose using this yarn resulted in a Zokki Pantyhose having a larger dimension than the conventional Zokki Pantyhose, and a wearing pressure which was not higher than that of the conventional product and was excellent in wearability and wearing feeling. Comparative Example 1 Dry spinning of a polyurethane dimethylacetamide solution (39% by weight) comprising PTMG, MDI and ethylene glycol having a molecular weight of 2100 at a speed of 540 m / min with a speed ratio of a godet roller and a winder of 1.40. As a result, an 18-denier monofilament yarn was obtained. Table 1 also shows the elongation, strength, setting properties, stress relaxation, and heat setting properties of this yarn. Comparative Example 2 A polyurethane dimethylacetamide solution (40% by weight) composed of PTMG, MDI and 1,4-butanediol having a molecular weight of 2900 was used at a speed of 540 m / min with a speed ratio of a godet roller and a winder of 1.40. By dry spinning, an 18-denier monofilament yarn was obtained. Table 1 also shows the elongation, strength, setting properties, stress relaxation, and heat setting properties of this yarn. [Comparative Example 3] A dimethylacetamide solution (39% by weight) of the polyurethane of Example 7 before addition of PVP was dry-spun in the same manner as in Example 7, but the yarn swayed sharply in the spinning cylinder. The yarn could not be wound.

[0096]

[Table 1] ★

[0097]

The polyurethane yarn of the present invention is an elastic yarn having unprecedented characteristics.
A product excellent in fit, appearance quality, wearability, feeling of wear, and the like can be obtained. Because of these excellent properties, in addition to being used alone, in combination with various fibers, for example, socks, stockings, circular knits, tricots, swimwear, ski pants, work clothes, smoke suits, clothes, golf pants, Wet suits, brassiere, girdle, gloves, socks and other textile products, tightening materials for sanitary products such as paper diapers, etc. It can be applied to various uses such as a printer, a copy cleaner, and a gasket.

Further, the dry spinnability is improved, and a yarn which could not be obtained conventionally can be obtained.

Claims (13)

[Claims] 1. A polyurethane yarn, wherein the main components of the polyurethane are a polyol, a diisocyanate and a diol, and the polyvinyl yarn contains polyvinylpyrrolidone and / or a copolymer thereof. 2. The polyurethane yarn according to claim 1, wherein the content of polyvinylpyrrolidone and / or a copolymer thereof is from 0.1% by weight to 10% by weight. 3. The polyurethane yarn according to claim 1, wherein the K value of the polyvinylpyrrolidone and / or a copolymer thereof is 20 or more and 70 or less. 4. The polyurethane yarn according to claim 1, wherein the melting point on the high temperature side is 180 ° C. or higher and 250 ° C. or lower. 5. The method according to claim 1, wherein the polyurethane is ethylene glycol,
At least one diol selected from the group consisting of 1,3 propanediol and 1,4 butanediol, a polyol having a molecular weight of 2500 or more and 6000 or less, and diphenylmethane diisocyanate are synthesized in a solution as main raw materials. The polyurethane yarn according to claim 1. 6. The polyurethane yarn according to claim 1, wherein the polyvinylpyrrolidone and / or its copolymer is synthesized using isopropyl alcohol as a solvent. 7. A polyurethane yarn produced by synthesizing a polyurethane in a solution using polyol, diisocyanate and diol as main raw materials, adding polyvinylpyrrolidone and / or a copolymer thereof to the solution, and performing dry spinning. Method. 8. The method according to claim 7, wherein the K value of the polyvinylpyrrolidone and / or its copolymer is from 20 to 70. 9. The method for producing a polyurethane yarn according to claim 7, wherein the melting point of the high-temperature side of the polyurethane is 180 ° C. or higher and 250 ° C. or lower. 10. A main raw material comprising at least one diol selected from the group consisting of ethylene glycol, 1,3 propanediol and 1,4 butanediol, a polyol having a molecular weight in the range of 2,500 to 6,000, and diphenylmethane diisocyanate. The method for producing a polyurethane yarn according to any one of claims 7 to 9, wherein the polyurethane is synthesized in a solution. 11. The solution according to claim 7, wherein polyvinylpyrrolidone and / or a copolymer thereof is contained in the solution in an amount of 0.1% by weight or more and 10% by weight or less.
The method for producing a polyurethane yarn according to any one of claims 10 to 10. 12. The method for producing a polyurethane yarn according to claim 7, wherein polyvinylpyrrolidone and / or a copolymer thereof are synthesized using isopropyl alcohol as a solvent. 13. The method according to claim 7, wherein the drying atmosphere temperature is higher than the melting point of the polyurethane on the high temperature side.