JP2001226823A - Polyurethane elastic fiber and method of producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the polyurethane elastic fiber product that has excellent elastic properties without losing bulkiness even at a low temperature and shows excellent appearance, fitting properties, wearing properties, wearing feeling and the like. SOLUTION: This invention provides an elastic fiber that is made of a polyurethaneurea mainly prepared from polyol, diisocyanate and diamine wherein the polyol characteristically comprises a tetrahydrofuran-ethylene oxide and/or propylene oxide random copolymer, and also a method for producing the same.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyurethane elastic fiber having excellent elastic properties without settling even at a low temperature, and having both good elongation and recovery, and a method for producing the same.

[0002]

2. Description of the Related Art Elastic fibers are widely used for elastic clothing such as legwear, innerwear, and sportswear and for industrial materials because of their excellent elasticity.

As such elastic fibers, polyurethane elastic fibers are used, which are disclosed in JP-A-63-235320, JP-A-5-239177 and JP-A-2-1-1.
No. 9511 discloses a technique for spinning a copolymer of tetrahydrofuran and 3-methyltetrahydrofuran, and a polyurethane polymer comprising an organic diisocyanate and a diamine compound.

[0004]

However, the polyether polyurethane elastic fiber exhibits excellent rubber elasticity at room temperature, but the rubber elasticity decreases when the environmental temperature decreases, and the knitting process is performed in a low temperature environment in winter. Is performed, the size of the knitted product fluctuates due to a temperature change, and there is a problem that the finished product is not uniform.

At a low temperature, for example, at a temperature of 0 ° C. or less, the rubber elasticity is impaired. Therefore, it may be used as a material for aquaculture knitting or the like which may be used under the freezing condition. could not.

Accordingly, there has been a demand for an improvement in the elastic recovery characteristics (cold resistance) of polyether polyurethane elastic fibers at low temperatures.

Further, in the prior art, when elastic fibers are used in clothes or the like, the appearance quality, the fit, the wearability, and the feeling of wearing are not improved.

The present invention is a product which has not been obtained by conventional techniques, has excellent elastic properties without settling even in a low temperature environment, and is excellent in appearance quality, fit, wearability, wear feeling, etc. And a method for producing the same.

[0009]

Means for Solving the Problems The polyurethane elastic fiber of the present invention employs the following means to solve the above-mentioned problems.

That is, a polyurethane urea whose main constituent is a polyol, a diisocyanate and a diamine, wherein the polyol contains a random copolymer of tetrahydrofuran and ethylene oxide and / or propylene oxide. Fiber.

The method for producing a polyurethane elastic fiber of the present invention employs the following means in order to solve the above-mentioned problems.

That is, a polyurethaneurea solution containing a polyurethaneurea as a solute composed mainly of a polyol, a diisocyanate and a diamine as a main component, containing a random copolymer of tetrahydrofuran and ethylene oxide and / or propylene oxide is spun. This is a method for producing a polyurethane elastic fiber.

[0013]

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

The polyurethane elastic fiber of the present invention is a polyurethane urea whose main constituent is a polyol, diisocyanate and diamine.

The method for synthesizing polyurethane urea 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, typical structural units constituting the polyurethane urea of the present invention will be described.

The polyol used in the present invention has excellent cold resistance and high elongation, and from the viewpoint of obtaining a material having high recovery, tetrahydrofuran (hereinafter referred to as T).
A so-called random copolymer in which HF) and ethylene oxide and / or propylene oxide are arranged irregularly is used.

In the present invention, when a block copolymer is used, the resulting polyurethane elastic fiber has remarkable water absorption, and thus has a problem that the physical properties at the time of water absorption are reduced.

That is, the polyol used in the present invention is also expressed as a copoly (alkylene ether) glycol selected from poly (tetramethylene-co-ethylene ether) glycol and poly (tetramethylene-co-1,2-propylene ether) glycol. Can be done.

In the poly (tetramethylene-co-ethylene ether) glycol, ethylene ether is contained in an amount of 15 to 37 mol% based on the total alkylene ether.
It is preferably contained, more preferably 20 to 35 mol%.

Further, poly (tetramethylene-co-1,2)
-Propylene ether) glycol;
Propylene ether is preferably contained in an amount of 15 to 30 mol% based on all alkylene ethers.

Further, the polyol used in the present invention may be composed of only a random copolymer, may be copolymerized with another polyol, or may be further mixed with another polyol. It may be.

As other polyols, excellent cold resistance,
Poly (1,4-tetramethylene glycol) (hereinafter abbreviated as PTMG), Patent No. 261513, from the viewpoint of obtaining a material having high extensibility and high recoverability.
No. 1, diol containing a neopentyl group in the main chain, polycarbonate diol disclosed in JP-A-2-289616, etc., JP-A-5-9851
No. 1, the ester-based diols disclosed in
It is preferable to use 4-butanediol, 1,6-hexanediol, polycaprolactonediol, polyethylene ether glycol, polypropylene ether glycol, a copolymerized polyol of neopentylene oxide and tetrahydrofuran, or the like. And such another polyol may be one kind, or may be two or more kinds.

In the present invention, the molar fraction of ethylene oxide and / or propylene oxide units is 5
It is preferably in the range of 90%.

The weight average molecular weight of the polyol used in the present invention is preferably in the range of 1,000 or more and 6000 or less from the viewpoint of elongation, strength, heat resistance and the like when formed into a yarn.

More preferably, the range is from 1300 to 4500. By using a polyol having a molecular weight in this range, an elastic yarn having well-balanced mechanical properties can be obtained.

Next, the diisocyanate used in the present invention is
For example, 5-isocyanate-1- (isocyanatomethyl) -1,3,3-trimethylcyclohexane, 1-
Isocyanate-4-[(4-isocyanatophenyl) methyl] benzene, 1-isocyanate-2-
[(4-Isocyanate-phenyl) methyl] benzene, 1,1′-methylenebis (4-isocyanatocyclohexane), 4-methyl-1,3-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate (hereinafter abbreviated as MDI) ), 2,4-tolylene diisocyanate (hereinafter abbreviated as TDI), 1,4-
Aromatic diisocyanates such as diisocyanate benzene, xylylene diisocyanate, and 2,6-naphthalenedi isocyanate are particularly preferable for synthesizing polyurethane having high heat resistance and strength.

Further, as an alicyclic diisocyanate, for example, methylene bis (cyclohexyl isocyanate)
(Hereinafter abbreviated as H ₁₂ MDI), isophorone diisocyanate, methylcyclohexane 2,4-diisocyanate, methylcyclohexane 2,6-diisocyanate,
Preferred are cyclohexane 1,4-diisocyanate, hexahydroxylylene diisocyanate, hexahydrotolylene diisocyanate, octahydro 1,5-naphthalenediisocyanate, and the like. Aliphatic diisocyanates are preferably used particularly for suppressing yellowing of polyurethane yarns.

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

The ratio of the molar amounts of such diisocyanates is:
From the viewpoint of the strength characteristics of the obtained polyurethane elastic fiber,
It is preferable that the diisocyanate is in the range of 1.2 or more and 2.3 or less with respect to the polyol 1.

Next, a diamine is used as the chain extender used in the present invention.

As the diamine, it is preferable to use at least one of those having a hydroxyl group and an amino group in the molecule, such as a low molecular weight diamine and ethanolamine.

As the low molecular weight diamine, for example, hydrazine, ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 2-methyl-1,5-
Pentanediamine, 1,2-diaminobutane, 1,3-
Diaminobutane, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, 2,2-dimethyl-1,3-diaminopropane, 1,3-diamino-2,
2-dimethylbutane, 2,4-diamino-1-methylcyclohexane, 1,3-pentanediamine, 1,3-cyclohexanediamine, bis (4-aminophenyl) phosphine oxide, hexamethylenediamine, 1,3
-It is preferable to use cyclohexyldiamine, hexahydrometaphenylenediamine, 2-methylpentamethylenediamine, bis (4-aminophenyl) phosphine oxide and the like. In particular, ethylenediamine is preferably used from the viewpoint of obtaining a material having excellent elongation and elastic recovery. It is also preferable to add a triamine compound capable of forming a crosslinked structure, such as diethylenetriamine, to these chain extenders to such an extent that the effect is not lost.

The polyurethane elastic fiber of the present invention may be used as a UV absorber, an antioxidant, a gas-resistant stabilizer, etc., as a so-called BHT or "Sumilyzer" manufactured by Sumitomo Chemical Co., Ltd.
Hindered phenol drugs such as GA-80, various benzotriazole drugs such as "tinuvin", phosphorus drugs such as "Sumilyzer" P-16 manufactured by Sumitomo Chemical Co., Ltd., Various kinds of hindered amines such as "tinuvin", inorganic pigments such as titanium oxide, zinc oxide and carbon black, metal soaps such as magnesium stearate, silver, zinc and their compounds Including disinfectants, deodorants, also lubricants such as silicone, mineral oil,
It is also preferable that various antistatic agents such as barium sulfate, cerium oxide, betaine, phosphoric acid and the like are contained, and that they are reacted with a polymer.

In order to further enhance the durability 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 preferable to use a light stabilizer such as "Sumisorb" 300 # 622 manufactured by Sumitomo Chemical Co., Ltd.

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

Knits are usually knitted at relatively low elongation, so for applications such as tricot knits, the unload power in the low elongation region (eg, 30% elongation, 60% elongation) is important. From the viewpoint of becoming, the unload power at 30% elongation of the polyurethane elastic fiber of the present invention is preferably 0.006 dN / tex or more, and the unload power at 60% elongation is 0.012.
It is preferably at least dN / tex. The polyurethane elastic fiber of the present invention preferably has a residual strain at -5 ° C. of 90% or less, more preferably 50% or less, and even more preferably 26% or less.

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

In the present invention, it is preferable to first prepare a polyurethaneurea solution.

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

In the present invention, a polyurethane urea containing a random copolymer of tetrahydrofuran and ethylene oxide and / or propylene oxide, a diisocyanate and a diamine as main components is used.

Among these, in particular, the weight average molecular weight of the polyol is in the range of 1,000 to 6,000, and the diamine as a chain extender includes hydrazine, ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 2-methyl -1,5-pentanediamine, 1,2
-Diaminobutane, 1,3-diaminobutane, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, 2,2-dimethyl-1,3-diaminopropane, 1,3-diamino-2, 2-dimethylbutane, 2,
4-diamino-1-methylcyclohexane, 1,3-pentanediamine, 1,3-cyclohexanediamine, bis (4-aminophenyl) phosphine oxide, hexamethylenediamine, 1,3-cyclohexyldiamine, hexahydrometaphenylenediamine, 2-methylpentamethylenediamine, bis (4-aminophenyl)
It is at least one selected from the group consisting of phosphine oxides, and the diisocyanate is preferably a polyurethaneurea synthesized in a solution using MDI as a main raw material.

Such polyurethane urea is, for example, D
It can be obtained by synthesizing the above-mentioned raw materials in MAC, DMF, DMSO, NMP or the like or a solvent containing these as main components.

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 react to give a polyurethane urea,
A method in which a polyol and MDI are first subjected to a melt reaction, and thereafter, the reactant is dissolved in a solvent and reacted with the above-described diamine to obtain a polyurethaneurea can be employed as a particularly preferable method.

In synthesizing such polyurethane urea, 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, N-ethylmorpholine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyl -1,3-propanediamine, N, N, N ',
N'-tetramethylhexanediamine, bis-2-dimethylaminoethyl ether, N, N, N ', N', N '
-Pentamethyldiethylenetriamine, tetramethylguanidine, triethylenediamine, N, N'-dimethylpiperazine, N-methyl-N'-dimethylaminoethyl-piperazine, N- (2-dimethylaminoethyl) morpholine, 1-methylimidazole, , 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 preferably used. As the organic metal catalyst, tin octoate, dibutyl tin dilaurate, lead dibutyl octoate and the like can be preferably used.

Further, in the present invention, it is preferable to use a chain terminator in order to control the molecular weight of the polyurethane and the viscosity of the polyurethane spinning solution.

As such a chain terminator, n-butanol,
Diethylamine, cyclohexylamine, n-hexylamine and the like are preferred.

It is preferable that the chain terminator is usually used as a mixture with a chain extender.

Small amounts of trifunctional substances such as diethylenetriamine and glycerol can also be used to control polymer viscosity.

The concentration of the polyurethaneurea 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, it is preferable to add the various additives described above to the polyurethane urea solution. As a method of adding the additive to the polyurethane urea solution, any method can be adopted. As a typical method, it is preferable to adopt a method using a static mixer, a method using stirring, or the like.

Here, the additives are preferably added in the form of a solution. If it is a solution, it can be uniformly added to the polyurethaneurea solution.

In the present invention, a polyurethane urea solution is spun to obtain a polyurethane elastic fiber. The spinning method may be any of a wet method, a dry method, and a melting method.

From the viewpoint of increasing the spinning speed, spinning is preferably performed by a dry method. In dry spinning, at least two gas supply units are provided, and a gas suction unit is used to form a fiber by discharging a polyurethane solution from a spinneret to a spinning cylinder provided between the gas supply units. The temperature of the gas supplied from the gas supply unit provided at the lower part of the spinning cylinder is set to 6
The temperature is preferably set to 0 ° C. or lower from the viewpoint of eliminating yarn unevenness.

During spinning, the speed ratio between the godet roller and the winder is preferably determined according to the purpose of use of the yarn.

In the present invention, winding is preferably performed with the speed ratio between the godet roller and the winder being 1.1 or more and 1.8 or less.

The spinning speed is 300 m / min or more and 800
It is preferably at most m / min.

[0059]

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 method of quantifying stress relaxation, strength, elongation, residual strain, and heat setting property in the present invention will be described. [Stress relaxation, strength, elongation, residual strain] Stress relaxation, strength,
For elongation and residual strain, use polyurethane yarn with Instron 45.
It was obtained by performing a tensile test using a 02 type tensile tester.

The stress relaxation, strength and elongation were measured at 22 ° C., and the residual strain was measured at -5 ° C.

These are defined below.

A 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 was held for 30 seconds. The stress after holding for 30 seconds was defined as (G2).

When the stress is set to 0, the sample length is (L
2).

The polyurethane yarn was further 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) Residual strain (%) = 100 × ((L2) − (L1)) /
(L1) Elongation (%) = 100 × ((L3) − (L1)) / (L
1) [Unload power] Using an Instron 4502 type tensile tester, a 5 cm sample was pulled at a tensile speed of 50 cm / min.
00% elongation was repeated 5 times.

The 30% elongation and 60%
The unload power was measured at two points of% elongation. Measurement is 2
Performed at 2 ° C. [Heat setting property] The sample yarn was treated for free with steam at 100 ° C for 10 minutes, then treated for free with boiling water at 100 ° C for 2 hours, and dried at room temperature for one day. Next, the yarn (length = (L
4)) was elongated by 100% (length = 2 × (L4)). 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 the length (L5) was measured.

Heat setting property (%) = 100 × ((L5) −
(L4)) / (L4) [Example 1] The ratio of THF to ethylene oxide was 70.
A dimethylacetamide solution (38% by weight) of a polyurethaneurea consisting of a polyol ("Tetoxynol" manufactured by Sanyo Chemical Industries, Ltd.), which is a random copolymer having a molecular weight of 3300 and a molecular weight of 3300, was used as a sample solution. . The obtained solution is discharged into a nitrogen gas at a drying atmosphere temperature of 380 ° C., and is subjected to dry spinning at a speed of 540 m / min with a speed ratio of a godet roller and a winder of 1.42, thereby producing a 20 dtex, monofilament yarn. I got The spinnability was good.

Table 1 shows the elongation, strength, stress relaxation, heat setting property and residual strain measured at -5 ° C. of the yarn.

[0074] A product having excellent elastic properties without settling even at a low temperature and having excellent extensibility and recoverability was obtained.

[0075]

[Table 1]

[Example 2] A dimethylacetamide solution (39% by weight) of polyurethaneurea composed of polyol, MDI and ethylenediamine, which is a random copolymer having a ratio of THF / propylene oxide of 70/30 and a molecular weight of 3000, was prepared as a sample solution. And The obtained solution is discharged into a nitrogen gas at a drying atmosphere temperature of 380 ° C., and the speed ratio between the godet roller and the winder is set to 1.42 and 540 m.
By dry spinning at a speed of / min, a yarn of 20 dtex and monofilament was obtained. The spinnability was good.

Table 1 also shows the elongation, strength, stress relaxation, heat setting property, and residual strain measured at -5 ° C. of the yarn.

[0078] A product having excellent elastic properties without settling even at a low temperature, and having excellent extensibility and recoverability was obtained.

[Example 3] A random copolymer having a ratio of THF to ethylene oxide of 90/10 and a molecular weight of 3300 ("Tetraxinol" manufactured by Sanyo Chemical Industries, Ltd.), MDI and ethylenediamine Polyurethane urea dimethylacetamide solution (3
9% by weight) was used as a sample solution. The obtained solution is discharged into a nitrogen gas at a drying atmosphere temperature of 380 ° C., and is subjected to dry spinning at a speed of 540 m / min with a speed ratio of a godet roller and a winder of 1.42, thereby producing a 20 dtex, monofilament yarn. I got The spinnability was good.

Table 1 also shows the elongation, strength, stress relaxation, heat setting property, and residual strain measured at -5 ° C. of this yarn.

An elastic material having excellent elastic properties without settling even at a low temperature and excellent in elongation and recovery was obtained.

Example 4 811 parts of THF (11.26 parts) was obtained by the method described in JP-A-1-98624.
Mol) and 25 g (0.28 mol) of 1,4-butanediol were charged into a pressure reactor, and BF ₃ -THF complex 6.6 was added.
g of ethylene oxide in the presence of 0.8 g of water and 0.8 g of water.
4.2 g were reacted. Filtration and the like were performed by the method described in the above publication, and the obtained polyol was 620 g. TH
The addition rate of F was 54%.

The resulting polyol had a ratio of THF / ethylene oxide of 70/30 and a weight average molecular weight of 33/33.
The number average molecular weight was 2,100.

The polyol and MDI are reacted so that the molar ratio of diisocyanate (capping ratio) to the polyol is 1.64 to form capped (isocyanate-terminated) glycol, which is dissolved in DMAc and chain-extended. A sample solution (38% by weight) was formed using ethylenediamine as an agent and diethylamine as a chain stopper. As additives, E.I. I. duPont de N
“Methac” manufactured by emours and Company
rol (R) 2462B "(2.2% by weight) and EI.
duPont de Nemours and Com
“Methacryl (R) 2390D” manufactured by Pany
(0.9% by weight) was added to the sample solution.

The sample solution was discharged into a nitrogen gas at a drying atmosphere temperature of 380 ° C., and the spinning was performed at a speed of 540 m / min with a speed ratio of a godet roller and a winder of 1.42, whereby two filaments of 20 dtex were obtained. Yarn was obtained. The spinnability was good.

The yarn has an elongation of 530% and a strength of 0.9c.
N / dtex, stress relaxation 16%, heat setting 45
%, The residual strain measured at −5 ° C. was 19%.

[0087] A product having excellent elastic properties without settling even at a low temperature and excellent in extensibility and recovery was obtained.

Example 5 A polyol was prepared in the same manner as described in Example 4, except that propylene oxide was used instead of ethylene oxide.

The resulting polyol had a ratio of THF / propylene oxide of 70/30 and a weight average molecular weight of 3
000, and the number average molecular weight was 1,900.

The polyol and MDI are reacted (capping ratio 1.64) to form a capped (isocyanate-terminated) glycol, which is dissolved in DMAc. Ethylenediamine is used as a chain extender, and diethylamine is used as a chain stopper. Sample solution using (39% by weight)
Was formed. The same additives as in Example 4 were used.

The sample solution was discharged into a nitrogen gas at a drying atmosphere temperature of 380 ° C., and the spinning was performed at a speed of 540 m / min with a speed ratio of a godet roller and a winder of 1.42, whereby two filaments of 20 dtex were obtained. Yarn was obtained. The spinnability was good.

This yarn has an elongation of 514% and a strength of 0.9c.
N / dtex, stress relaxation 19%, heat setting property 41
%, The residual strain measured at −5 ° C. was 23%.

[0093] A product having excellent elastic properties without settling even at a low temperature and having excellent extensibility and recovery was obtained.

Example 6 The same sample solution as in Example 4 was prepared except that the concentration was 35% by weight. The obtained sample solution was dry-spun at a speed of 650 m / min using an 8-hole die, thereby obtaining 49.6 dtex.
A filament yarn was obtained.

The obtained yarn had an elongation of 30% and an unload power of 0.007 dN / tex.
% Unload power at 0.014 dN / t
ex and the elongation at break was 610%.

Example 7 Tetrahydrofuran (TH
F) 79.5 parts by weight, ethylene oxide (EO) 20
Parts by weight and 0.5 parts by weight of water were mixed and kept in the tank at ambient temperature. The solution is applied at 45-50 psi (310-3
100 gal kept at 50 ° C. under nitrogen of 45 KPa)
(379 liters) of continuous stirred reactor.
The reactor was cooled to about 800 lbs (363 Kg) in THF.
It contained 0 lbs (23 Kg) of Tonsil KO montmorillonite clay catalyst (Sud Chemical). Incoming and outgoing rates were 100 lbs (45 Kg) per hour. After the reaction has reached equilibrium, the resulting solution is 3
0 to 40% by weight of THF, 50% by weight of THF / EO copolymer, 6 to 9% by weight of cycloether oligomeric by-product
(OCE)) and up to 1% by weight of dioxane and water. The resulting solution was filtered to remove the catalyst and transferred to a still heated to 120 ° C. under a pressure of 400 mmHg to remove most of the THF. The concentrated product is heated to 95 ° C., and the amount of OCE is reduced to about 2-3.
Under reduced pressure (10-15mmHg) to reduce to weight%
Amberlyst A-15 (Rohm & Haa
s) ion-exchange resin. The obtained copolymerized alkylene ether was dried at 95 ° C. and 10 to 15 mmHg. The resulting product is 97-98% by weight of poly (tetramethylene-co-
Ethylene ether) 2 to 2.7% by weight of OCE, 0.0
It contained less than 5% by weight of THF, water and dioxane.
As a result of proton NMR, the copolymerized ether was 50 mol% in ethylene ether. The number average molecular weight calculated from the hydroxyl value determined by acetic anhydride / pyridine titration of the copolymerized polyether was about 1750. The same raw materials, catalysts and resins were used for other series of poly (tetramethylene-co-ethylene ether) glycols, but in a 1 liter continuous glass reactor in a nitrogen atmosphere at 50-70 ° C. under normal pressure. Made with

Polyurethane urea is a series of poly (tetramethylene-co-ethylene ether) glycols and MDI
Is dissolved in DMAc (so that the polymer concentration of the final solution is about 25% by weight), and ethylenediamine and 1,3-cyclohexanediamine are mixed at a molar ratio of 80/20. The mixture was subjected to chain extension and the reaction was stopped with diethylamine. The total isocyanate content of the prepolymer is S.P. Siggia "Q
authentic Organic Analyses
is via Functional Group ”, 3
rd Edition, Wiley & Sons, Ne
w York, pp. 559-561 (1963). The molar ratio of diisocyanate to polyether glycol is changed according to the molecular weight of polyether glycol,
The range was 1.68 to 1.85. Small changes in the molecular weight of the copolymerized polyether glycol had little effect on the properties of the polyurethaneurea. The solution contained 0.5% by weight of Santowhite powder (1,1-bis (2-methyl-4-hydroxy-5-t) based on the final solution weight.
-Butylphenyl) -butane). 5 mil
(0.013 cm) thick film using a doctor knife to form a Mylar polyester film (EI duP).
ont de Nemours and Compan
y) and dried overnight. Myla
r at 150 ° C. for 10 minutes.
Conditioned in boiling water for 0 minutes. A 4 mil (0.01 cm) wide, 5.1 cm long sample cut from the film was peeled from Mylar and a tensile test was performed at 22 ° C. on an Instron tester. Sample is 50cm /
It was stretched at a rate of minutes to an elongation of 200% and relaxed. The stretching and relaxation cycle was 5 cycles. The unload power (stress) at the fifth cycle is dN at two points (30% and 60% elongation: the unload power at each point is referred to as UP (30) and UP (60)).
It was measured in units of / tex. The elongation at break was measured by pulling at the sixth cycle. The residual strain is also 0 to 2 for 5 cycles.
It was measured on samples that had undergone a 00% elongation, relaxation cycle.

The residual strain was calculated using the following equation.

Residual strain = 100 × (La−Lb) / Lb where Lb and La are the lengths of the sample held without tension before and after the elongation and relaxation cycles of 5 cycles. Three samples were measured for each level, and the average was taken. Table 2 shows the physical properties of the film. Poly (tetramethylene-co-ethylene ether) glycol (molar ratio: about 70/30, number average molecular weight: 2223), MDI (2.
65% by weight NCO), a film similarly prepared from polyurethane urea chain-extended with hydrazine had an elongation at break of 739%, a residual strain of 12%, and a UP (60) 0.0
14dN / tex, UP (30) 0.008dN / te
x.

The standard deviation of the unload power is 0.000
2. When the ethylene ether content in the copolymerized polyether glycol exceeded 37 mol%, the unload power at low elongation was low, the elongation at break was low, and the residual strain tended to be high. If it is lower than 15 mol%, the effect of ethylene ether on unload power decreases, and the elongation at break tends to decrease.

[0101]

[Table 2]

Comparative Example 1 PTMG having a molecular weight of 2100,
A dimethylacetamide solution of polyurethane urea (39% by weight) comprising MDI and ethylenediamine was added to a godet roller and a winder at a speed ratio of 1.40 to 540 m /
Dry spinning was performed at a speed of 20 minutes to obtain a 20 dtex, monofilament yarn. Table 1 also shows the elongation, strength, stress relaxation, heat setting property, and residual strain measured at −5 ° C. of the yarn.

[0103]

According to the present invention, the elastic properties are not impaired even at a low temperature, it has excellent low-temperature properties without settling, has good elongation and recovery properties, and has a good heat setting property. A polyurethane elastic fiber can be obtained.
When the polyurethane elastic fiber of the present invention is used for clothes and the like, it is possible to obtain a fiber excellent in fit, appearance quality, wearability, and wear feeling. 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, Tightening materials for wetsuits, bras, girdle, gloves, socks and other various textile products, tightening materials for preventing leakage of sanitary items such as paper diapers, tightening materials for waterproof materials, imitation bait, artificial flowers, electrical insulation, wiping cloth It can be applied to various uses such as a printer, a copy cleaner, and a gasket.

Claims (7)

[Claims] 1. Polyurethane urea whose main constituent is a polyol, diisocyanate and diamine,
A polyurethane elastic fiber, characterized in that the polyol contains a random copolymer of tetrahydrofuran and ethylene oxide and / or propylene oxide. 2. The polyurethane elastic fiber according to claim 1, wherein the molar fraction of ethylene oxide and / or propylene oxide units is in the range of 5 to 90%. 3. The polyol has a molecular weight of 1,000 or more and 60 or more.
3. The polyurethane elastic fiber according to claim 1, wherein the polyurethane elastic fiber is in a range of not more than 00. 4. The polyurethane elastic fiber according to claim 1, wherein the residual strain at -5 ° C. is 90% or less. 5. The polyurethane elastic fiber according to claim 1, wherein the unload power at 30% elongation is 0.006 dN / tex or more. 6. A method of spinning a polyurethaneurea solution containing a polyurethaneurea as a solute containing a polyol, a diisocyanate and a diamine as a main component, containing a random copolymer of tetrahydrofuran and ethylene oxide and / or propylene oxide. Of producing polyurethane elastic fibers. 7. The method for producing a polyurethane elastic fiber according to claim 6, wherein the spinning method is dry.