JPH11200147A - Polyurethane yarn and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a polyurethane yarn having moderate elongation, high heat-setting properties and setting properties to some extent capable of providing especially excellent appearance grade, fitness, wearability, feeling of wearing of clothes, etc., when used in the clothes, etc. SOLUTION: This polyurethane yarn is a spandex yarn containing a main constituent component composed of a polyurethaneurea and further contains polyvinylpyrrolidone and/or its copolymer. The value of K of the polyvinylpyrrolidone and/or its copolymer is >=20 and <=70. The yarn contains >=0.5 and <=15 wt.% polyvinylpyrrolidone and/or its copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyurethane yarn. More specifically, the present invention relates to a polyurethane urea-based spandex yarn and a method for producing the same, and when used for clothing, etc., polytanure which can make the appearance quality, fit, wearability, wear feeling, etc. of clothes particularly excellent. The present invention relates to a yarn and a method for producing the yarn.

[0002]

2. Description of the Related Art Polyurethane yarns are widely used in legwear, innerwear, sportswear, etc. due to their excellent elasticity.

[0003] In order to make the most of these characteristics, polyurethane yarns have become more and more occupied in fabrics. A typical example is the so-called zokki in the stocking market. By using Zokki, all of the appearance quality, fit, wearability, and wearing feeling of the stockings could be better than the conventional knitted products.

That is, the higher the mixing ratio of the polyurethane yarn, the better the quality. And
This is not limited to stockings.
However, in these circumstances, there are still problems that are not completely solved, such as pressure and size. That is, when the mixing ratio of the polyurethane yarn is high, the contact pressure is likely to be slightly high and the size is likely to be small.

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

[0006] 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 higher-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 such a purpose at present. 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 (hereinafter abbreviated as PVP) is added to a polyurethane yarn to improve whiteness retention.

By the way, PVP and its copolymer are easily dissolved in water or a polar solvent. Therefore, when a solution in which such a substance is dissolved is subjected to wet coagulation,
There is also a possibility that PVP and the like are eluted into the coagulation bath.

Further, when the coagulating liquid is water-based, PVP
However, there is a problem that water absorbs moisture and hinders drying of the wet-coagulated yarn.

In the case of wet spinning, there are also problems that productivity is low and that thin yarn is difficult to spin due to resistance of a coagulation bath.

[0012]

However, according to the prior art, when used for clothes and the like, it is possible to make the appearance and the like of the clothes and the like particularly excellent in fitting quality, wearability and wearability. A polyurethane yarn and a method for producing the same could not be obtained.

[0013] That is, an object of the present invention is to provide a garment or the like having an appearance quality, fit, wearability, etc.
It is an object of the present invention to obtain a polyurethane yarn having a suitable elongation, high heat setting property and a certain degree of setting property, which can make the feeling of wearing particularly excellent.

[0014]

The polyurethane yarn of the present invention has the following structure to solve the above-mentioned problems. That is, the main component is a polyurethane urea spandex yarn containing polyvinylpyrrolidone and / or its copolymer, and the K value of the polyvinylpyrrolidone and / or its copolymer is 20 or more and 70 or less. It is a polyurethane thread characterized by these.

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

That is, polyvinylpyrrolidone having a K value of 20 or more and 70 or less and / or a copolymer thereof is
A method for producing a spandex yarn, comprising adding to a polyurethane urea solution and performing dry spinning.

[0017]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in more detail.

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

The polyurethane used in the present invention consists of diamine extension. The synthesis method is not particularly limited. That is, it is a polyurethane urea mainly synthesized from a polyol, a diisocyanate and a diamine. In addition, a polyurethane using ethanolamine as a chain extender may be used. Further, trifunctional or higher polyfunctional glycols or isocyanates may be used without impairing the effects of the present invention.

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

Representative polyols used in the present invention include polyether glycols, polyester glycols, and polycarbonate diols.

In particular, when flexibility and elongation of the yarn are required, it is preferable to use a polyether glycol. As polyether glycols,
For example, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol (hereinafter, referred to 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-dimethylTHF, Patent No. 2615131 Polyols having side chains on both sides disclosed in the above-mentioned publications can be used as typical examples. These polyether-based glycols may be used alone or as a mixture or copolymer of two or more.

When abrasion resistance and light resistance are particularly required for the polyurethane yarn, butylene adipate, polycaprolactone diol, polyester polyol having a side chain disclosed in JP-A-61-26612, etc. Polyester glycols such as those described above, 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 molecular weight of the polyol used in the present invention is preferably one having a number average molecular weight of 1 based on elongation, strength, heat resistance and the like when formed into a yarn.
It is preferably from 000 to 8,000. More preferably, it 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 alicyclic diisocyanates, 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, as the chain extender used in the present invention, at least one of those having a hydroxyl group and an amino group in the molecule such as low molecular weight diamine and ethanolamine is used.

Preferred low molecular weight diamines include, for example, ethylenediamine, 1,2-propanediamine,
1,3-propanediamine, hexamethylenediamine,
1,4-cyclohexyldiamine, 1,3-cyclohexyldiamine, hexahydrometaphenylenediamine,
2-methylpentamethylenediamine, bis (4-aminophenyl) phosphine oxide and the like can be used. One or more of these can be selected and used. Particularly preferred is ethylenediamine. By using ethylenediamine, a yarn excellent in elongation, elastic recovery, and heat resistance can be produced.

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 molecular weight of the elastic yarn of the present invention is preferably from 40,000 to 150,000 as a number average molecular weight. Within this range, fibers having particularly high durability and strength can be obtained.

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

Particularly preferred as the yarn of the present invention are, among such yarns, a diol and a diisocyanate, and the melting point on the high temperature side is 250 ° C. or more and 300 ° C.
It is the following. The melting point on the high-temperature side in the present invention is 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. When the melting point on the high temperature side is 250 ° C. or more and 300 ° C. or less, the yarn of the present invention has no practical problems including the process passability and is excellent in heat setting property. Using a polyol having a molecular weight of 1500 or more and 6000 or less,
DI and has a high-temperature melting point of 250
Polyurethane yarn having a temperature of not less than 300 ° C. and not more than 300 ° C. has particularly high elongation.
It is preferable because there is no practical problem and the heat setting property is excellent.

The melting point of the polyurethane yarn on the high temperature side is 2
In order to make the temperature between 50 ° C. and 300 ° C. or less, it is preferable to conduct a test in advance and select the ratio of diisocyanate to polyol and diamine.

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

The K value of PVP and a copolymer thereof used in the present invention is 20 or more and 70 or less.

In the present invention, the K value is a value calculated from the viscosity equation of Fikenscher. When the K value is 20 or more and 70 or less, production of the polyurethane yarn becomes particularly easy. Further, it is easy to make the characteristics of the produced polyurethane yarn the target characteristics. Further, in practical use, dropping of PVP can be substantially prevented.

The required content of PVP and its copolymer in the polyurethane yarn varies depending on the target characteristics of the polyurethane yarn and particularly the K value.

Therefore, it is preferable that the K value and the PVP content are appropriately selected according to the target characteristics of the yarn.

The preferred content of PVP and its copolymer is from 0.1% by weight to 10% by weight. When the polyurethane yarn contains at least one of PVP and a copolymer thereof, although the cause is unknown, heat setting property and mechanical setting property are improved, but elongation and stress relaxation are improved. And other properties are not adversely affected.
Even if at least one of P and its copolymer is present in the yarn, the unexpected surprising phenomenon that the yarn does not fibrillate and is not different from conventional polyurethane yarn in use at all is used. Express.

It is particularly preferable that the content of at least one of PVP and its copolymer be 0.1 to 0.2.
5 to 15% by weight. If the amount is less than 0.5% by weight, no effect tends to be obtained, and if it exceeds 15% by weight, the elongation tends to decrease.

When the content of at least one of PVP and its copolymer is in the range of 0.5% by weight or more and 15% by weight or less, the setting property, stress relaxation, strength, elongation and heat setting property are particularly high. Become good. Particularly preferred is 1% by weight or more and 12% by weight or less.

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 copolymer compound used for synthesizing the copolymer of PVP is not particularly limited, but 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 and the like can be used. These copolymers may be either block copolymers or random copolymers.

The fineness, cross-sectional shape and the like of the polyurethane yarn according to the present invention are not particularly limited. For example, the cross section of the yarn may be circular or flat.

There is no problem even if the polyurethane yarn of the present invention contains various stabilizers and pigments. For example, hindered phenolic agents such as so-called BHT and Sumitomo Chemical's "Sumilyzer" GA-80 as light and antioxidants, and various "tinuvins"
Benzotriazoles, Sumitomo Chemical's "Sumilyzer" P-16 and other phosphorus-based drugs, various "tinuvins" and other hindered amine-based drugs, as well as titanium oxide, zinc oxide and carbon black. Inorganic pigments and other metal soaps such as magnesium stearate, as well as bactericides containing silver, zinc and these compounds, deodorants, silicones, lubricants such as mineral oil, barium sulfate, cerium oxide, It does not matter if it contains various antistatic agents such as betaine or phosphoric acid, or reacts with the polymer.

In order to further increase the durability especially against light and various types of nitric oxide, a nitric oxide supplement such as
HN-150 manufactured by Nippon Hydrazine, a thermal oxidation stabilizer such as "Sumilyzer" GA-80 manufactured by Sumitomo Chemical, and a light stabilizer such as "Sumisorb" 300 # 62 manufactured by Sumitomo Chemical.
It is effective to use 2 or the like.

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

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

In the present invention, any method may be used for producing the solute polyurethane or the 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 polyurethane particularly suitable for the present invention, those described above can be used.

Among these, particularly preferred polyurethane is a polyol whose molecular weight is in the range of 2,500 to 6,000, and diamines which are chain extenders include ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, and hexane. Methylenediamine, 1,4-cyclohexyldiamine, 1,3-cyclohexyldiamine and at least one selected from the group consisting of 2-methylpentamethylenediamine, and the diisocyanate is MDI
Is a polyurethane solution which is synthesized in a solution using as a main raw material, and whose melting point on the high temperature side of the polyurethane is 250 ° C. or more and 300 ° C. or less.

Such polyurethane is, for example, DMA
It can be obtained by synthesizing the above raw materials in C, DMF, DMSO, NMP or the like or a solvent containing these as main components. For example, a method in which a polyol and MDI are first melt-reacted, and then, the reactant is dissolved in a solvent and reacted with the above-described diamine to form a polyurethane may be employed as a particularly preferable method.

As a typical method for adjusting the high-temperature side melting point of the polyurethane to 250 ° C. or more and 300 ° C. or less, a method of controlling the types and ratios of polyol, MDI, and diamine is preferably employed. When the molecular weight of the polyol is high, it is preferable to relatively increase the proportion of MDI. When the molecular weight of the polyol is 1500 or more, to make the melting point on the high temperature side 250 ° C. or more, (MDI
(Mol number of polyol) / (mol number of polyol) = 1.3 or more.

Hereinafter, (mol number of MDI) / (mol number of polyol) is referred to as CR value.

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 methods include a static mixer method,
A method by stirring or the like can be used.

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.

It should be noted that the addition of at least one of PVP and its copolymer may increase the solution viscosity.

The addition to the polyurethane solution is as described above.
For example, it may be added at the same time as chemicals and pigments such as a light resistance inhibitor and an antioxidant.

Next, at least one of the added PVP and its copolymer has a K value of 20 or more and 70 or less. If the ratio is out of this range, there is a problem that spinning becomes unstable and a polyurethane yarn having desired characteristics cannot be obtained.

The dry spinning method in the present invention is not particularly limited, and any method can be adopted.

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, and therefore, it is preferable to determine the setting according to the intended 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 set to 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.

[0068]

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 quantitative 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 speed 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).

A sixth time, the polyurethane yarn was stretched 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] PTMG and MDI having a molecular weight of 1600 were converted to CR.
The mixture was charged to a container to a value of 1.6 and reacted at 80 ° C. for 4 hours. Then, the reaction product was dissolved in dimethylacetamide, and then ethylenediamine and diethylamine were added to the solution to obtain a polyurethane solution. . Solution concentration is about 35
% By weight. 2000g of this solution PVP manufactured by Kanto Chemical
140 g of a dimethylacetamide solution (35% by weight) of (K = 30) was added and stirred for 2 hours to obtain a sample solution. The resulting solution was dry-spun at a speed of 540 m / min with a speed ratio of a godet roller and a winder of 1.20 to obtain a 40 denier yarn. Table 1 shows the elongation, strength, setting property, stress relaxation, heat setting property, PVP content, and melting point of this yarn.

The obtained yarn had a high heat setting property. When the Zocchi pantyhose was knitted, the size of the Zocchi pantyhose was larger than that of the conventional Zocchi pantyhose, and the wearing pressure was not higher than that of the conventional product. [Example 2] The same polyurethane solution 200 as in Example 1
To 0 g, 180 g of the PVP of Example 1 was added and stirred for 2 hours to obtain a sample solution. The resulting solution was dry-spun at a speed of 540 m / min with a speed ratio of a godet roller and a winder of 1.2 to obtain a yarn of 40 denier. 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 3] The same polyurethane solution 200 as in Example 1
PVP (G) obtained by copolymerizing 10% of N-butenyl-2,4-di (1-butenyl) -2-pyrrolidone manufactured by ISP with 0 g.
140 g of a dimethylacetamide solution (ANEX P-904) (35% by weight) was added and stirred for 2 hours to obtain a sample solution. The resulting solution was dry-spun at a speed of 540 m / min with a speed ratio of a godet roller and a winder of 1.20 to obtain a 40 denier yarn.
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. [Comparative Example 1] The properties of a yarn obtained by spinning the same polyurethane solution as in Example 1 under the same conditions as in Example 1 except that PVP was not contained are shown in the table. The yarn had a low heat setting property. [Comparative Example 2] A polyurethane solution containing PVP was prepared in the same manner as in Example 2, and spinning was performed using a test wet spinning machine in which the coagulating liquid was water. However, even if the spinning speed was reduced to 200 m / min, thread breakage occurred. No polyurethane yarn could be obtained.

[0083]

[Table 1] ★

[0084]

The polyurethane yarn of the present invention is an elastic yarn having a high heat resistance and a high heat setting property. Therefore, when used for clothes, etc., the polyurethane yarn excellent in fitting property, appearance quality, wearability, feeling of wear, etc. Obtainable. Because of these excellent properties, in addition to use alone, in combination with various fibers, for example, socks, stockings, circular knitting, tricots, swimwear, ski pants, work clothes,
Tightening materials for various textiles such as fireworks clothing, clothes, golf trousers, wet suits, brassiere, girdle, gloves and socks;
It can be applied to various uses such as artificial flowers, electric insulating materials, wiping cloths, copy cleaners and gaskets.

Claims (3)

[Claims] A main component is a polyurethane urea spandex yarn, comprising polyvinylpyrrolidone and / or a copolymer thereof, wherein the polyvinylpyrrolidone and / or its copolymer has a K value of 20.
A polyurethane yarn having a size of 70 or more and 70 or less. 2. The polyurethane yarn according to claim 1, wherein the polyurethane yarn contains 0.5 to 15% by weight of polyvinylpyrrolidone and / or a copolymer thereof. 3. A method for producing a spandex yarn, comprising adding a polyvinylpyrrolidone having a K value of 20 or more and 70 or less and / or a copolymer thereof to a polyurethane urea solution and dry spinning.