JP5258266B2 - Polyurethane urea elastic fiber and method for producing the same - Google Patents

Description

  The present invention relates to a polyurethane urea elastic fiber used for the purpose of imparting stretch properties to an ester interwoven knitted circular knitted fabric and the like, and a method for producing the same, and more particularly, to a polyurethane urea elastic fiber having heat resistance and a method for producing the same. Is.

  Polyurethane urea elastic fibers have excellent elongation characteristics and excellent recovery properties that are not found in other synthetic fibers, and are knitted with nylon fibers, cotton, etc., in a wide range of fields such as foundations, pantyhose, and socks. Have been used. Among them, in recent years, the demand for composite fabric materials composed of polyester fibers and polyurethane urea elastic fibers, which are typical general-purpose synthetic fibers, has been increasing rapidly in the outer clothing field and sports clothing field. However, unlike nylon fibers, which are generally dyed at a dyeing temperature around 100 ° C., polyester fibers are dyed at a liquid heat temperature of around 130 ° C.

  On the other hand, polyurethane urea elastic fibers used by knitting do not have sufficient heat resistance compared to other synthetic fibers, and even if knitted fabrics of polyester fibers and polyurethane urea elastic fibers are dyed under normal dyeing conditions. In many cases, the product value is lost because the breaking strength is lowered, the properties such as elongation recovery properties are lowered, or the film is thermally cut. This is particularly noticeable in thin fabrics using yarns with a fine fineness such as 22 decitex, and in particular, there has been a problem of repeated dyeing for color matching. Therefore, the liquid heat temperature at the time of dyeing is generally not performed at a temperature exceeding 130 ° C. However, disperse dyes used for dyeing polyester fibers are often dyed at high temperature, so if the dyeing temperature is lowered, dyeing to polyester fibers will be insufficient, resulting in poor reproducibility of dyeing. was there. For this reason, use special disperse dyes that have excellent dyeability to polyester near 120 ° C, use polyester fibers that can be dyed at low temperatures, or repeat dyeing to perform color matching, etc. The method has been carried out.

Therefore, it is strongly desired to improve the heat resistance of the polyurethane urea elastic fiber.
In general, polyurethaneurea elastic fibers have urea groups by adding organic diamine to a so-called prepolymer in which organic diols are linked by an excess molar diisocyanate compound and reacting amino groups with isocyanate groups. Form a hard segment. Since this hard segment serves as a cross-linking point for the entire polymer, it greatly affects the heat resistance of the polyurethaneurea elastic fiber. The heat resistance has been improved by strengthening the hard segment, and the heat resistance has been improved by increasing the molecular weight of the polymer (see Patent Documents 1 to 4).
However, when these methods are used, there is a problem that the processability in dough processing deteriorates because the setability for adjusting the width by heat in the process such as width adjustment of the dough in the processing process is reduced. Or the viscosity of the polyurethane urea solution suddenly rises over time, causing problems such as difficulty in spinning. difficult. Accordingly, polyurethane urea elastic fibers that can be repeatedly dyed at 130 ° C. or higher have been desired for circular knitted fabrics by ester knitting.

Japanese Patent No. 3352105 Japanese Patent Laid-Open No. 05-078569 JP-T-2003-504477 JP 2000-290836 A

  The present invention is less susceptible to yarn breakage even when a knitted fabric of polyester fibers and polyurethane urea elastic fibers is repeatedly dyed at a high temperature of 130 ° C. or higher, and is capable of stretching recovery and heat setting of conventional polyurethane urea elastic fibers. It was made for the purpose of eliminating the drawbacks of the prior art described above without impairing the above.

（式中、Ｒ ₁ は炭素原子数２〜８の直鎖状または分岐状アルキレン基、Ｒ ₂ は炭素原子数
６〜１５の脂環族アルキレン基、炭素原子数１〜４の直鎖状または分岐状アルキレン基あるいはジアルキレン置換フェニレン基またはメタンジフェニレン基である。）
［２］両末端アミン化合物の含有量が片末端アミン化合物に対して４０ｍｏｌ％等量以上２００ｍｏｌ％等量未満であることを特徴とする上記［１］に記載のポリウレタンウレア弾性繊維。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that, even when a polyurethane urea elastic fiber containing both terminal amine compounds and having a specific specific viscosity is subjected to a high-temperature dyeing treatment, the stretch recovery property, The inventors have found that the heat setting property is excellent and have reached the present invention.
That is, the present invention is as follows.
[1] A compound represented by the following formula (5), and at least one bi-terminal amine compound selected from ethylenediamine and 1,2-propylenediamine, and having a specific viscosity η _{SP, 2} / C before liquid heat treatment Is 0.8 or more and 2.2 or less, and the specific viscosity difference Δη _SP / C represented by the following formula (1) is 0.5 or more and 3.0 or less , and after processing assumption processing (B) A polyurethane urea elastic fiber having a heat set rate represented by the following formula (3) of 70% or more .
Δη _SP / C = η _{SP, 1} / C-η _{SP, 2} / C (1)
Δη _SP / C: Specific viscosity difference η _{SP, 1} / C: Specific viscosity after liquid heat treatment at 130 ° C. for 30 minutes η _{SP, 2} / C: Specific viscosity before liquid heat treatment
Thermal setting rate (%) = [(I−I ₀ ) / (I ₁ −I ₀ )] × 100 (3)
I ₀ : Initial sample length (mm)
I ₁ : Sample length when performing liquid heat treatment (mm)
I: Sample length (mm) that is in a relaxed state after liquid heat treatment
Assumed processing (B): A polyurethane urea elastic fiber is subjected to a dry heat treatment at 190 ° C. for 1 minute, a liquid heat treatment at 130 ° C. for 30 minutes, and a dry heat treatment at 170 ° C. for 1 minute in a 100% stretched state.

Wherein R ₁ is a linear or branched alkylene group having 2 to 8 carbon atoms, and R ₂ is the number of carbon atoms.
They are a 6-15 alicyclic alkylene group, a C1-C4 linear or branched alkylene group, a dialkylene substituted phenylene group, or a methane diphenylene group. )
[2] The polyurethane urea elastic fiber according to the above [1], wherein the content of both terminal amine compounds is 40 mol% or more and less than 200 mol% equivalents relative to the one terminal amine compound.

[3] The polyurethaneurea elastic fiber according to the above [1] or [2], wherein the strength retention after the assumed processing (A) shown below is 70% or more.
Process assumed treatment (A): A polyurethane urea elastic fiber is subjected to a dry heat treatment at 190 ° C. for 1 minute in a 50% stretched state, followed by a liquid heat treatment at 130 ° C. for 60 minutes.
[4] In any one of the above [1] to [3], 200% R / S represented by the following formula (2) after the processing assumption process (B) shown below is 90% or more. The polyurethane urea elastic fiber described.
200% R / S = 200% stress (out) / 200% stress (return) (2)
200% stress (outward): Repeated 300% extension, the third 200% outward stress (g)
200% stress (return): 300% stretch repetition, third 200% return stress (g)
Assumed processing (B): A polyurethane urea elastic fiber is subjected to a dry heat treatment at 190 ° C. for 1 minute, a liquid heat treatment at 130 ° C. for 30 minutes, and a dry heat treatment at 170 ° C. for 1 minute in a 100% stretched state.

[ 5 ] The method for producing a polyurethane urea elastic fiber according to any one of the above [1] to [ 4 ], wherein an amine compound at both ends is added and dry spinning is performed.

  Since the polyurethaneurea elastic fiber of the present invention has heat resistance, it can be knitted with polyester, can be repeatedly dyed at a high temperature of 130 ° C. or higher, and does not impair the stretch characteristics of the polyurethaneurea elastic fiber. In addition, it is possible to produce a polyurethane urea elastic fiber that is less likely to cause yarn breakage during dyeing and can be repeatedly dyed for color matching during processing. Further, the polyurethane urea elastic fiber in the present invention can be easily produced in the production process, has high heat resistance, and has good processability.

Hereinafter, the present invention will be described in detail.
The polyurethane urea elastic fiber of the present invention has a specific viscosity η _{SP, 2} / C before liquid heat treatment of 0.8 or more and 2.2 or less, and a specific viscosity difference Δη _SP / C represented by the following formula (1). Is 0.5 or more and 3.0 or less.
Δη _SP / C = η _{SP, 1} / C-η _{SP, 2} / C (1)
Δη _SP / C: Specific viscosity difference η _{SP, 1} / C: Specific viscosity after liquid heat treatment at 130 ° C. for 30 minutes η _{SP, 2} / C: Specific viscosity before liquid heat treatment Specific viscosity is measured by the method described below. It is an index of polymer molecular weight. If the specific viscosity before liquid heat treatment is 0.8 or more and 2.2 or less, the setability for performing the width alignment with heat in the process such as the width alignment of the dough in the processing step is excellent. If it is less than 0.8, thermal cutting is likely to occur in the dry heat process step of the processing process. On the other hand, if it exceeds 2.2, the setting property for performing the width adjustment by heat in the process such as the width adjustment of the dough in the processing step is deteriorated, so that the processability in the dough processing deteriorates.
The specific viscosity difference is an index of fluctuation of the polymer molecular weight due to the liquid heat treatment. If the specific viscosity difference Δη _SP / C represented by the above formula (1) is 0.5 or more and 3.0 or less, thermal cutting at the time of repeated dyeing is suppressed, and the heat setting property necessary for adjusting the width of the fabric is obtained. It can be done under normal processing conditions. If it is less than 0.5, thermal cutting may occur during dyeing. If it exceeds 3.0, the setting property for performing the width adjustment with heat in the process such as the width adjustment of the dough in the processing step is deteriorated, so that the processability in the dough processing is deteriorated.

  Furthermore, the polyurethane urea elastic fiber of the present invention preferably has a strength retention after processing assumed treatment (A) measured by a method described later of 70% or more in order to cope with repeated dyeing. If it is less than 70%, thermal cutting may occur during dyeing. Such a polyurethane urea elastic fiber is excellent in suppressing the decrease in the fabric power during the processing and dyeing treatment of the knitted fabric of the elastic fiber and the ester and in suppressing the occurrence of defects in the fabric.

Further, the polyurethane urea elastic fiber of the present invention has a 200% R / S of 90% or more after the assumed processing (B) measured by the method described later in order to maintain the fabric performance after repeated dyeing and heat setting. It is preferable that Here, 200% R / S is an index indicating the stretch recovery property of the knitted fabric of polyurethane urea elastic fiber and ester. If it is 90% or more, the power and stretch recovery property of the fabric are excellent. If it is less than 90%, the commercial value may be lost due to a decrease in properties such as elongation recovery.
Furthermore, the polyurethane urea elastic fiber of the present invention preferably has a heat set rate of 70% or more after the assumed processing (B). Such a polyurethane urea elastic fiber is preferable because the heat setting property required for adjusting the width of the fabric can be performed under normal processing conditions. If it is less than 70%, the setting property for performing the width adjustment by heat in the process such as the width adjustment of the dough in the processing step is deteriorated, so that the processability in the dough processing is deteriorated.

Further, the present invention will be described in detail.
The polyurethane urea elastic yarn of the present invention is prepared by adding an amine solution having a single-end amine compound and a bi-terminal amine compound to an isocyanate-terminated prepolymer prepared by a substantially linear polymer diol and a bi-terminal isocyanate compound. These are obtained by dry-spinning, wet-spinning, reactive spinning, or melt-spinning of a polyurethaneurea polymer having a urethane group and a urea group in the molecule, obtained by reacting in one or more stages. Particularly preferred is dry spinning from the viewpoint of easy processability and physical properties such as elongation characteristics.

  The polymer diol component of the prepolymer in the present invention includes polytetramethylene glycol, polycarbonate diol, polypropylene glycol, polybutylene adipate diol, polycaprolactone diol, and a copolymer having a repeating unit represented by the following formula (3) or (4). A copolymerized diol characterized by containing a polymerized diol is used. The number average molecular weight of these glycols is preferably a polyether diol having a number average molecular weight of 300 to 10,000 or a copolymerized diol, and particularly preferably polytetramethylene glycol (PTMG) having a number average molecular weight of 1000 to 2500. It is.

As examples of the both-end isocyanate component constituting the polyurethane prepolymer, many examples of compounds including the following compound groups are known. For example, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyl ether diisocyanate, 4,4′-diphenylpropane diisocyanate and the like can be mentioned. Preferably, it is a diisocyanate compound having a benzene ring, and 4,4′-diphenylmethane diisocyanate (MDI) is particularly preferable.
As the above-mentioned one-end amine compound polymerized with an isocyanate-terminated prepolymer adjusted with a polymer diol and a both-end isocyanate compound, examples of compounds containing the following compounds are known. For example, diethylamine, n-butylamine, monoethanolamine and the like can be mentioned. Preference is given to diethylamine.
Moreover, as both-end amine compounds, for example, ethylenediamine, 1,2-propylenediamine, dodecamethylenediamine, hexamethylenediamine, nonamethylenediamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, triethylenediamine, There are trimethylenediamine and the like. In addition, ethylenediamine, 1,2-propylenediamine, dodecamethylenediamine, hexamethylenediamine, nonamethylenediamine, o-phenylenediamine, m-phenylenediamine, Examples thereof include a compound (5) represented by the following structural formula having a urea bond obtained by reacting p-phenylenediamine, diaminophenylmethane, triethylenediamine, trimethylenediamine and the like. A mixture of these diamines may also be used. Preferred are ethylenediamine and 1,2-propylenediamine.

（式中、Ｒ₁ は炭素原子数２〜８の直鎖状または分岐状アルキレン基、Ｒ₂ は炭素原子数６〜１５の脂環族アルキレン基、炭素原子数１〜４の直鎖状または分岐状アルキレン基あるいはジアルキレン置換フェニレン基またはメタンジフェニレン基である。）

(Wherein R ₁ is a linear or branched alkylene group having 2 to 8 carbon atoms, R ₂ is an alicyclic alkylene group having 6 to 15 carbon atoms, a straight chain having 1 to 4 carbon atoms, or A branched alkylene group, a dialkylene-substituted phenylene group, or a methanediphenylene group.)

The polyurethaneurea elastic fiber of the present invention is characterized in that both end amine compounds are contained. Containing indicates a state in which unreacted both terminal amine compounds remain in the fiber. By containing both terminal amine compounds, the effect of increasing the molecular weight during processing can be exhibited by the aminolysis reaction, which is an exchange reaction between the one terminal amine compound and the both terminal amine compounds.
As a method of containing both terminal amine compounds, a method of preparing by adding an excessive amount of both terminal amine compounds in a mixed solution of both terminal amine compounds and one terminal amine compounds to be polymerized with the polyurethane prepolymer, or polymerization Thereafter, the amine compounds at both ends may be added directly in the step before spinning.
Moreover, as a both-end amine compound which expresses the performance of this invention, what kind of thing may be used as long as it produces the above-mentioned specific viscosity difference (DELTA) (eta) _SP / C. The same compound as the both-end amine compound to be polymerized with the prepolymer or another compound may be used. For example, ethylenediamine, 1,2-propylenediamine, dodecamethylenediamine, hexamethylenediamine, nonamethylenediamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, triethylenediamine, trimethylenediamine and the like can be mentioned. In addition, ethylenediamine, 1,2-propylenediamine, dodecamethylenediamine, hexamethylenediamine, nonamethylenediamine, o-phenylenediamine, m-phenylenediamine, Examples include the compound (5) having the above-described urea bond obtained by reacting p-phenylenediamine, diaminophenylmethane, triethylenediamine, trimethylenediamine and the like. A mixture of these diamines may also be used. The above having a urea bond in which primary amines such as ethylenediamine and 1,2-propylenediamine are reacted at both ends of both end isocyanate components such as 4,4′-diphenylmethane diisocyanate from the standpoint of stability of stock solution and heat resistant performance The compound (5) is preferred.

Specifically, N, N ′-(methylenedi-4,1-phenylene) bis [2- (2-methylethylamino) -urea] represented by the following compound (6) is desirable from the viewpoint of heat resistance.

In the method of adding an excessive amount of both terminal amine compounds to the mixed solution of both terminal amine compounds and one terminal amine compounds to be polymerized and reacted with the polyurethane prepolymer, in the obtained polyurethane urea elastic fiber in consideration of reactivity and the like. It is necessary to set the polymer design, raw materials and reaction conditions so that the amine compounds at both ends remain. As an example, a method may be used in which a plurality of both-end amine compounds having different reactivities are mixed, and only a highly reactive compound contributes to the polymerization reaction by adjusting the polymerization conditions, and the less-reactive both-end amine compounds remain in the polymer. Examples thereof include a method of adding a large excess of both types of both-end amine compounds and terminating the reaction when the molecular weight reaches the design value to leave a part of both-end amine compounds.
On the other hand, if it is the method of adding both terminal amine compounds to the polyurethane urea after superposition | polymerization, the quantity contained in a polyurethane urea elastic fiber will be easy to adjust, and it is more preferable. In this case, the addition amount of the both-end amine compound may be added in excess of the one-end amine compound charge amount in the polyurethane prepolymer. The polyurethane urea elastic yarn having heat resistance according to the present invention can be suitably produced by adding it in excess of less than the amount. If the amount is less than 40 mol% equivalent to the one-terminal amine compound in the polyurethane prepolymer, the increase in the specific viscosity after the liquid heat treatment is small, and the effect may not be sufficiently exhibited. Moreover, when 200 mol% equivalent amount or more of both terminal amine compounds are added, a sudden increase in viscosity of the polymerization stock solution occurs, which may affect the spinning stability.

Moreover, the polyurethane urea elastic fiber of the present invention contains hydrotalcite having stearic acid attached to the surface, whereby yarn breakage during processing such as dyeing can be suppressed.
Surfactants such as sulfosuccinic acid-based metal salts, α-olefin sulfonates, α-sulfo fatty acid methyl ester salts, sodium lauryl sulfate and the like are contained in the polyurethane urea elastic fiber in an amount of 0.1 to 5% by weight. As a result, yarn breakage can be further suppressed, and processing at a temperature of 130 ° C. or higher can be performed on the ester knitted circular knitted fabric. As the surfactant, any compound may be used as long as it is as described above, but a sulfosuccinic acid metal salt is preferable because it has a high effect of improving the breaking strength.

For the polyurethane urea elastic fiber, an organic or inorganic compounding agent having a specific chemical structure used for a known polyurethane urea elastic fiber, for example, a benzophenone compound, a benzotriazole compound, or a binder amine is used. UV absorbers such as compound compounds, antioxidants such as binderd phenol compounds, inorganic fine particles such as barium sulfate, magnesium oxide, magnesium silicate, calcium silicate, zinc oxide, magnesium stearate, calcium stearate, polytetrafluoro An anti-sticking agent such as ethylene or organopolysiloxane can also be contained.
The fineness of the polyurethane urea elastic fiber in the present invention is preferably 11 dtex or more and 310 dtex or less for circular knitting and warp knitting.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
Measurement methods and evaluation methods are as follows.
<Heat treatment method>
Using a high-temperature high-pressure dyeing machine (NISSEN CORPORATION TYPE 12LMP-E), heat treatment was performed by the following methods. FIG. 1 shows a method for attaching to a metal frame.
1. Assumed processing (A): Processing conditions of sample for measuring strength retention rate (i) Dry heat treatment at 190 ° C. for 1 minute A test sample yarn having a to-be-processed part I ₀ = 50 mm is set in a metal frame under no elongation. The film was stretched by 50% and fixed at a portion to be treated I ₁ = 75 mm. Dry heat treatment was performed for 1 minute with a pin tenter heated to 190 ° C. together with the metal frame. The metal frame taken out from the pin tenter was allowed to cool at room temperature.
(Ii) Liquid heat treatment at 130 ° C. for 30 minutes The liquid frame after the treatment of (i) was immersed in ion-exchanged water in a pot inside the dyeing machine and subjected to liquid heat treatment. The treatment condition was that the temperature was raised from 80 ° C. at 2.0 ° C./min, kept at 130 ° C. for 30 minutes, and then cooled. The test sample yarn was removed from the metal frame taken out from the dyeing machine, relaxed to a free state, air-dried in an atmosphere at a temperature of 20 ° C. and a humidity of 65 wt% for 12 hours or more, and then the strength was measured.

2. Assumed processing (B): 200% R / S, heat setting rate, processing conditions of sample for measurement (i) Dry heat treatment at 190 ° C. for 1 minute A test sample with a part to be processed I ₀ = 75 mm under no elongation in a metal frame The yarn was set, stretched 100%, and fixed at the portion to be treated I ₁ = 150 mm. Dry heat treatment was performed for 1 minute with a pin tenter heated to 190 ° C. together with the metal frame. The metal frame taken out from the pin tenter was allowed to cool at room temperature.
(Ii) Liquid heat treatment at 130 ° C. for 30 minutes. A liquid heat treatment at 130 ° C. for 30 minutes was performed in the same manner as described above. Without removing the test sample yarn from the metal frame taken out from the dyeing machine, the whole metal frame was air-dried and subjected to the following heat treatment.
(Iii) Dry heat treatment at 170 ° C. for 1 minute The metal frame on which the test sample yarn that had been air-dried after the treatment of (ii) was set was subjected to a dry heat treatment for 1 minute with a pin tenter heated to 170 ° C. as it was.
In the state where the metal frame taken out from the pin tenter is allowed to cool to room temperature, after measuring the heat setting rate shown below, remove the test sample yarn from the metal frame, relax in a free state, temperature 20 ° C, humidity After being left for 12 hours or more in an atmosphere of 65 wt%, the following 200% R / S measurement was performed.

3. Processing conditions of specific viscosity measurement sample About 2 g of test sample yarn was sampled and immersed in ion-exchanged water in a pot inside the dyeing machine under non-stretched condition. The treatment condition was that the temperature was raised from 80 ° C. at 2.0 ° C./min, kept at 130 ° C. for 30 minutes, and then cooled. The test specimen taken out from the dyeing machine was air-dried for 12 hours or more in an atmosphere of a temperature of 20 ° C. and a humidity of 65 wt%, and then measured according to the specific viscosity (η _SP / C) measurement method shown below.

<Measurement method of specific viscosity η _SP / C>
Specific viscosity (η _SP / C);
Specific viscosity was measured as an evaluation of polymer molecular weight. In a 200 ml Erlenmeyer flask, add 0.2 g of the sample before or after the liquid heat treatment and 100 ml of new petroleum ether, and slowly stir for 5 minutes. The petroleum ether in the Erlenmeyer flask is replaced with fresh petroleum ether, and after stirring for another 5 minutes, the sample is removed from the Erlenmeyer flask and air-dried for 3 hours. Accurately evaluate the weight (W1) of this test sample. In order to obtain a 0.5 wt% dimethylacetamide (DMAc) solution, dimethylacetamide is added to a 50 ml sample bottle containing the test sample, and the weight (W2) is accurately measured and dissolved to obtain the concentration C of the test sample solution. . The flow time of the solvent and the test sample solution was measured in a constant temperature water bath at 25 ° C. using an Ostwald viscometer. The specific viscosity was determined by the following formula (7).

(Η _SP / C) = {(t−t ₀ ) / t ₀ } / C (7)
t: Flow velocity of test sample solution (seconds)
t ₀ : Flowing speed of solvent (DMAc) (second)
C: Test yarn concentration (wt%) (W1 / W2 × 100)
Moreover, specific viscosity difference (DELTA) (eta) _SP / C was calculated | required by following Formula.
Δη _SP / C = η _{SP, 1} / C-η _{SP, 2} / C (1)
Δη _SP / C: Specific viscosity difference η _{SP, 1} / C: Specific viscosity after liquid heat treatment at 130 ° C. for 30 minutes η _{SP, 2} / C: Specific viscosity before liquid heat treatment

<Strength retention>
The measurement was performed with a tensile tester UTM-III-100 manufactured by Oriente Tech Co., Ltd. under conditions of a temperature of 20 ° C. and a humidity of 65 wt%. Set the sample before or after heat treatment to the test machine with a gripping interval of 50 mm, pull it until it breaks at a deformation rate of 1000% / min, and set the stress (strength) and elongation (elongation% relative to before elongation) at break. It was measured. In addition, the measured value made the ratio (%) of the breaking strength after the heat processing with respect to the breaking strength before the heat treatment according to the following formula (8) as the strength retention.
Strength retention (%) = (after TS / before TS) × 100 (8)
After TS: Breaking strength after heat treatment (cN)
Before TS: Breaking strength before heat treatment (cN)

<Measurement method of 200% R / S>
The measurement was performed with a tensile tester UTM-III-100 manufactured by Oriente Tech Co., Ltd. under conditions of a temperature of 20 ° C. and a humidity of 65 wt%. The test piece was heat-treated on a test machine, set at a spacing of 50 mm, and stretched 300% at a deformation rate of 1000% / min. The test was repeated three times. The ratio was 200% R / S.
200% R / S = 200% stress (out) / 200% stress (return) (2)
200% stress (outward): Repeated 300% extension, the third 200% outward stress (g)
200% stress (return): 300% stretch repetition, third 200% return stress (g)

<Heat set rate measurement method>
After the processing assumption process (B), the sample length of the metal frame in which the test sample yarn is set is gradually narrowed, and the length I when the yarn is in a relaxed state is measured. The ratio (%) with respect to the length before the heat treatment indicated by is the heat set rate. Here, I ₀ and I ₁ are values at the time of liquid heat treatment (I ₀ = 75 mm, I ₁ = 150 mm).
Thermal setting rate (%) = [(I−I ₀ ) / (I ₁ −I ₀ )] × 100 (3)
I ₀ : Initial sample length (mm)
I ₁ : Sample length when performing liquid heat treatment (mm)
I: Sample length (mm) that is in a relaxed state after liquid heat treatment

<Thread breakability evaluation method>
Using a 4-neck circular knitting machine (24 gauge, 30 inch, manufactured by Otsuki), supply polyethylene terephthalate fiber 84T / 36f to 4ch and polyurethane urea elastic fiber to 4ch to produce a knitted circular knitted fabric. After the dry heat setting, a refining process was performed, and the liquid heat dyeing process was repeated three times with a liquid dyeing machine at a dyeing temperature of 130 ° C. and 135 ° C. for one dyeing time of 45 minutes. This fabric was evaluated on the inspection machine by the number of locations where the polyurethane urea elastic fiber was broken and perforated with a width of 180 cm and a length of 200 cm on the inspection machine. It was confirmed using a microscope that the polyurethane urea elastic fiber was broken.

[Examples 1 to 3]
2200 g of polyoxytetramethylene glycol having a number average molecular weight of 1800 is dissolved in 1400 g of dimethylacetamide and reacted with 480 g of 4,4′-diphenylmethane diisocyanate under stirring in a dry nitrogen atmosphere at 50 ° C. for 2 hours. A polyurethane prepolymer solution was obtained. The obtained polyurethane prepolymer solution was cooled in a water bath at 15 ° C. and dissolved in 1900 g of dimethylacetamide to dilute the polyurethane prepolymer solution. On the other hand, 40.28 g of ethylenediamine and 5.82 g of diethylamine were dissolved in dry DMAc and added to the polyurethane prepolymer solution at 30 ° C. to obtain a polyurethane urea solution having a concentration of 30% by weight and a viscosity of 4500 poise at 30 ° C. It was.

As an antioxidant, 1% by weight of a condensation product of p-cresol having a molecular weight of about 2300, dicyclopentadiene and isobutene is added to the polymer solid content as an antioxidant, and the mixture is stirred and mixed in a nitrogen atmosphere at 50 ° C. for 3 hours. did. 60 mol% equivalent (Example 1) and 80 mol% equivalent (Example 2) of the compound (6) described above with respect to diethylamine in the polymer stock solution with respect to the one-end amine compound in this polyurethane prepolymer. ), 120 mol% equivalent (Example 3) was added and stirred and mixed in a nitrogen atmosphere at 10 ° C. for 3 hours to prepare a spinning polymer stock solution. Immediately after defoaming this with a vacuum pump, it was discharged from a hole orifice into a dry spinning machine maintained at 310 ° C., spinning, drying, false twisting, oiling, and 800 m / min. Thus, a polyurethane urea elastic fiber having a winding fineness of 22 dtex and 2 filaments was obtained.
The specific viscosity measurement results of the obtained elastic fiber are shown in Table 1, fiber properties are shown in Table 2, and thread breakage evaluation is shown in Table 3.

[Example 4]
In Examples 1 to 3, compound (6) was added in an amount equal to 60 mol% with respect to the one-terminal amine compound in the polyurethane prepolymer, and hydrotalcite having stearic acid attached to the surface was converted to polyurethane urea polymer. 3 wt% was added, and 0.5 wt% of sulfosuccinic acid di-2-ethylhexyl ester sodium salt (manufactured by CYTEC) was added, and the mixture was stirred and mixed in a nitrogen atmosphere at 50 ° C. for 3 hours to prepare a polymer solution for spinning. . Using this polymer stock solution, a yarn having a fineness of 22 dtex and 2 filaments was obtained in the same manner as in Examples 1 to 3.
The specific viscosity measurement results of the obtained elastic fiber are shown in Table 1, fiber properties are shown in Table 2, and thread breakage evaluation is shown in Table 3.

[Example 5]
In Examples 1 to 3, yarns having a fineness of 22 dtex and 2 filaments were obtained in the same manner as in Examples 1 to 3 except that 20 mol% of the compound (6) was added in an equivalent amount.
The specific viscosity measurement results of the obtained elastic fiber are shown in Table 1, fiber properties are shown in Table 2, and thread breakage evaluation is shown in Table 3.

[Comparative Example 1]
In Examples 1 to 3, an attempt was made to spin in the same manner as in Examples 1 to 3 except that 200 mol% of the compound (6) was added in an equivalent amount. Many yarn breaks occurred during spinning, and the product could not be collected.

[Comparative Example 2]
In Examples 1 to 3, yarns having a fineness of 22 dtex and 2 filaments were obtained in the same manner as in Examples 1 to 3 except that both end amine compounds were not added.
The specific viscosity measurement results of the obtained elastic fiber are shown in Table 1, fiber properties are shown in Table 2, and thread breakage evaluation is shown in Table 3.

[Comparative Example 3]
Example 15 of Patent Document 1 was additionally tested by the following method.
400 g of PTMG having a number average molecular weight of 1830 and 87 g of MDI were reacted with stirring in a nitrogen gas atmosphere at 70 ° C. for 3 hours to obtain an intermediate polymer having a terminal isocyanate group. Next, the mixture was cooled to room temperature, and dry dimethylacetamide was added to obtain an intermediate polymer solution having a concentration of 40% by weight. Next, a dimethylacetamide solution containing 7.28 g of ethylenediamine and 1.11 g of diethylamine was added to the vigorously stirred intermediate polymer solution to obtain a polyurethane urea solution having a concentration of 30% by weight. Next, 5% by weight of a condensation product of p-cresol having a molecular weight of about 2300, dicyclopentadiene and isobutene as an antioxidant was added to the polymer and mixed with stirring. Further, a dimethylacetamide solution containing 3.02 g (50 mol%) of compound (6) was added, mixed and degassed to obtain a spinning composition liquid having a concentration of 30% by weight and a viscosity of 3400 poise / 30 ° C. This was supplied through an orifice to a dry spinning machine maintained at a hot air temperature of 270 ° C., and spinning, drying, false twisting, and oiling were carried out to obtain a yarn having a winding fineness of 22 dtex and 2 filaments at 800 m / min.
The specific viscosity measurement results of the obtained elastic fiber are shown in Table 1, fiber properties are shown in Table 2, and thread breakage evaluation is shown in Table 3.

  Since the polyurethane urea elastic fiber of the present invention is excellent in the processability at the time of dyeing with an ester interwoven knitted circular knitted fabric, an inner using a composite fabric material composed of polyester fibers and polyurethane elastic fibers, which are typical general-purpose synthetic fibers. It can be suitably used in the clothing field, outer clothing field and sports clothing field.

It is a figure which shows the attachment method to the metal frame at the time of performing heat processing.

Claims (5)

It contains a compound represented by the following formula (5), and at least one both-end amine compound selected from ethylenediamine and 1,2-propylenediamine, and has a specific viscosity η _{SP, 2} / C of 0. 8 or more, or 2.2 or less, and the following formula (1) specific viscosity difference .DELTA..eta _SP / C indicated by 0.5 or more and 3.0 or less, the following equation after the processing contemplated process (B) ( 3. A polyurethaneurea elastic fiber, wherein the heat set rate shown in 3) is 70% or more .
Δη _SP / C = η _{SP, 1} / C-η _{SP, 2} / C (1)
Δη _SP / C: Specific viscosity difference η _{SP, 1} / C: Specific viscosity after liquid heat treatment at 130 ° C. for 30 minutes η _{SP, 2} / C: Specific viscosity before liquid heat treatment
Thermal setting rate (%) = [(I−I ₀ ) / (I ₁ −I ₀ )] × 100 (3)
I ₀ : Initial sample length (mm)
I ₁ : Sample length when performing liquid heat treatment (mm)
I: Sample length (mm) that is in a relaxed state after liquid heat treatment
Assumed processing (B): A polyurethane urea elastic fiber is subjected to a dry heat treatment at 190 ° C. for 1 minute, a liquid heat treatment at 130 ° C. for 30 minutes, and a dry heat treatment at 170 ° C. for 1 minute in a 100% stretched state.

(Wherein R ₁ is a linear or branched alkylene group having 2 to 8 carbon atoms, R ₂ is an alicyclic alkylene group having 6 to 15 carbon atoms, a straight chain having 1 to 4 carbon atoms, or A branched alkylene group, a dialkylene-substituted phenylene group, or a methanediphenylene group.)   The polyurethane urea elastic fiber according to claim 1, wherein the content of both terminal amine compounds is 40 mol% or more and less than 200 mol% equivalents relative to the one terminal amine compound. The polyurethane urea elastic fiber according to claim 1 or 2, wherein the strength retention after the processing assumed treatment (A) shown below is 70% or more.
Process assumed treatment (A): A polyurethane urea elastic fiber is subjected to a dry heat treatment at 190 ° C. for 1 minute in a 50% stretched state, followed by a liquid heat treatment at 130 ° C. for 60 minutes. The polyurethane urea elastic fiber according to any one of claims 1 to 3, wherein 200% R / S represented by the following formula (2) after the assumed processing (B) shown below is 90% or more. .
200% R / S = 200% stress (out) / 200% stress (return) (2)
200% stress (outward): Repeated 300% extension, the third 200% outward stress (g)
200% stress (return): 300% stretch repetition, third 200% return stress (g)
Assumed processing (B): A polyurethane urea elastic fiber is subjected to a dry heat treatment at 190 ° C. for 1 minute, a liquid heat treatment at 130 ° C. for 30 minutes, and a dry heat treatment at 170 ° C. for 1 minute in a 100% stretched state. The method for producing a polyurethane urea elastic fiber according to any one of claims 1 to 4 , wherein both end amine compounds are added and dry spinning is performed.

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