JP2001140127A - Polyurethane fiber and dimensionally stable stretch fabric - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyurethane fiber material having high heat setting property and small heat shrinkage and an elastic fabric product excellent in dimensional stability. SOLUTION: The average number of urea bond units per molecule obtained by reacting the following compounds (a) and (b) is 4 to 4.
A polyurethane fiber, characterized in that a urethane urea compound containing 40 is added and contained in an amount of 1 to 15% by weight based on the polyurethane polymer fiber. (A) a nitrogen-containing compound containing a monofunctional amine of either a primary amine or a secondary amine, a hydroxyl group, and at least one selected from a tertiary nitrogen and a heterocyclic nitrogen; (b) an organic diisocyanate This urethane fiber is useful for producing a stretchable fabric having excellent dimensional stability.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyurethane fiber having excellent heat setting properties and a method for producing the same. Further, the present invention relates to a stretchable fabric having excellent dimensional stability obtained by using the same.

[0002]

2. Description of the Related Art Polyurethane fibers obtained by subjecting an isocyanate-terminated prepolymer synthesized with a polyalkylene ether glycol and an excess of organic diisocyanate to chain extension with a linking agent such as a diamine or a low molecular weight diol are known as polyurethane fibers.
BACKGROUND ART In the form of a fabric cross-woven with a polyamide fiber, a polyester fiber, or the like, it is used as a stretchable material in clothing in various fields such as foundations, socks, pantyhose, swimwear, sportswear, and leotard.

In a polyurethane fiber, a hard segment comprising a linking agent forms a hydrogen-bonding physical crosslink to exhibit its excellent elastic function. However, in the case of fabric products in which polyurethane fibers are mixed, there are fields in which mold stopping properties are particularly required, for example, circular knitting fields for legs such as zokki pantyhose and tights, warp knitting for inner sports such as brassiere, girdle and swimwear. In the field, in the field of outer fabrics such as bottom, etc., when the fabric is processed, the fabric in which the polyurethane fibers are interwoven is once heat-set,
Shrinkage due to heat received in a later step or shrinkage of the final product with time occurs. That is, the final product may be difficult to finish as the product requires in design, or may be a final product that is difficult to wear. In addition, there is a problem that the edge of the fabric is easily curled (a phenomenon of curling round and round), making it difficult to sew.

[0004] For this reason, conventionally, it is necessary to set many times or to set at a higher temperature in order to suppress a desired width or shrinkage with time, resulting in a decrease in production efficiency, deterioration in heat efficiency, There has been a problem that the thermal deterioration of the polyurethane fiber will be in the future. Among polyurethane fibers,
Polyurethane polyurea fibers using a diamine as a linking agent are more resistant to thermal degradation, but have poorer dimensional stability due to thermal shrinkage.

On the other hand, polyetherester fibers (polyesters obtained by copolymerizing a polyalkylene ether glycol component) are also known as well as polyurethane fibers. These fibers have excellent heat-setting properties and good dimensional stability of the product fabric, but have the drawback that the elastic recovery is clearly inferior to polyurethane fibers and the stretching function is low, such as high stretching fatigue. For example, when used as a practical garment, it has a problem of lack of durability such as a moderate wearing feeling and keeping it.

[0006] In particular, the polyetherester fiber is not only insufficient in elasticity as an elastic fiber, but also has a large stress change with respect to elongation, and tends to feel pressure on body movement. In addition, due to poor thermal durability, elastic fibers in the fabric may be sagged or broken in fields where processing is performed at high temperatures such as stretch outers or where color matching is difficult such as foundation and re-dyeing is required. Doing so will spoil the aesthetics of the product.

In order to improve the heat setting property of polyurethane fibers having an elastic function, JP-A-3-97915 discloses a polyurethane urea elastomer based on a polyether obtained by chain-extending an isocyanate-terminated prepolymer with a specific mixed diamine. JP-A-8-13824 proposes a polyurethane fiber obtained by polymerizing a diamine, a monoamine, and a prepolymer at a specific ratio. JP-A-7-
JP 150147 discloses a polyrethan fiber to which a specific alkali metal salt is added at a low concentration.

In Japanese Patent Application Laid-Open No. Hei 7-316922, a specific polyacrylonitrile-based polymer, a specific polyurethane polymer, a specific styrene-maleic anhydride is used for the purpose of improving the heat setting property without impairing the elastic function of the polyurethane fiber. Any of thermoplastic heavy bodies 1 to 14 of the copolymer
Disclosed are polyurethane urea elastic fibers to which weight percent is added and a method for producing the same. However, in each of the above-mentioned attempts, although the effect of improving the heat setting property of the polyurethane fiber is observed, the effect of the improvement is not sufficiently satisfactory, and the elastic function of the polyurethane fiber is sacrificed or thread breakage occurs. In some cases, difficult and stable spinning is difficult.

[0009]

An object of the present invention is to solve the above-mentioned problems of the prior art, namely, a polyurethane fiber having a high heat setting property and a small heat shrinkage, and a polyurethane fiber realizing an excellent elastic function. Is to provide a method of manufacturing the same. A more specific object of the present invention is to provide an elastic garment product that has good mold stopping properties, excellent elasticity, excellent dimensional stability during processing, and little shrinkage with time.

[0010]

Means for Solving the Problems The present inventor has found that by adding a specific urethane urea compound to a polyurethane polymer, a polyurethane fiber having a high heat setting property, a small heat shrinkage property and an excellent elastic function can be obtained stably. It has been found that it can be manufactured through a spinning process. The present inventor has also found that a stretchable fabric in which a polyurethane fiber to which the above specific urethane urea compound is added is remarkably excellent in dimensional stability.

That is, the present invention provides the following (a) and (b)
Reacts and the average number of urea bond units per molecule is 4 to
A polyurethane fiber comprising a urethane urea compound containing 40 urea compounds in an amount of 1 to 15% by weight based on the polyurethane polymer. (A) a nitrogen-containing compound containing a monofunctional amine of either a primary amine or a secondary amine, a hydroxyl group, and at least one selected from tertiary nitrogen and heterocyclic nitrogen (b) organic diisocyanate The urethane urea compound used in the present invention contains (a) a monofunctional amine of either a primary amine or a secondary amine, a hydroxyl group, and a tertiary nitrogen or a heterocyclic nitrogen in the molecular skeleton. A urethane urea compound obtained by reacting at least one selected nitrogen-containing compound with (b) an organic diisocyanate. The average number of urea bond units, that is, the molecular weight of the urethane urea compound is adjusted by adjusting the molar ratio of (a) and (b).

When the reaction is carried out in a molar amount of (a) <(b) to form an isocyanate terminal, it is necessary to block the isocyanate terminal using a third component having one active hydrogen. As the third component, a mono- or di-alkyl monoamine and an alkyl mono-alcohol are preferable. Also,
When (a) molar amount> (b) molar amount, the isocyanate group reacts quickly with the monofunctional amine in the nitrogen-containing compound to form a urea bond, and reacts slowly with the hydroxyl group to form a urethane bond. To form a hydroxyl group at the end. The hydroxyl terminal may or may not be blocked,
It is preferable to block with an organic monoisocyanate.

The resulting urethane urea compound has a tertiary nitrogen skeleton (including a partial skeleton of heterocyclic nitrogen) represented by the following formula (1) and a urea bonding unit represented by the following formulas (2) and (3). Including. However, when the reaction molar ratio of (a) / (b) is less than 2 or when an alkyl monoalcohol or an organic monoisocyanate is reacted at the terminal, a urethane bond represented by the following formula (4) is also included. become.

[0014] (A) used in the preparation of the urethane urea compound referred to in the present invention, selected from a monofunctional amine of either a primary amine or a secondary amine, a hydroxyl group, a tertiary nitrogen, and a heterocyclic nitrogen As the nitrogen-containing compound containing at least one of the above, N-n-butyl- (2-aminoethyl)-
N- (2-hydroxyethyl) amine, Nn-butyl- (3-aminopropyl) -N- (3-hydroxypropyl) amine, Nt-butyl- (4-aminobutyl)
-N- (4-hydroxybutyl) amine, N-isobutyl- (2-aminoethyl) -N- (2-hydroxyethyl) amine, N-isobutyl- (3-aminopropyl)
-N- (3-hydroxypropyl) amine, N-1,
1-dimethylpropyl- (2-aminoethyl) -N-
(2-hydroxybutyl) amine, N- (hydroxyalkyl) -piperazine derivatives such as N- (2-hydroxyethyl) piperazine, N- (2-hydroxyethyl) -2-methylpiperazine, N- (3-hydroxypropyl) ) N- (hydroxyalkyl) -N ′-(aminoalkyl) -piperazine derivatives such as 2-ethylpiperazine, for example, N- (2-hydroxyethyl) -N′-
(2-aminoethyl) -piperazine, N- (3-hydroxypropyl) -N ′-(2-aminopropyl) -piperazine, piperidine derivative, for example, N-amino-4-
Pyrrolidone derivatives such as (2-hydroxyethyl) piperidine and N- (2-aminoethyl) -4- (2-hydroxyethyl) piperidine, for example, N-amino-4- (2-
(Hydroxyethyl) -2-pyrrolidone, N- (3-aminopropyl) -4- (3-hydroxypropyl) -2-
And pyrrolidone. Preferred nitrogen-containing compounds are N- (hydroxyalkyl) -piperazine derivatives,
N- (hydroxyalkyl) -N ′-(aminoalkyl) -piperazine derivatives, particularly N- (2-hydroxyethyl) piperazine, are preferred. These can be used alone or as a mixture.

As the organic diisocyanate (b) used for preparing the urethane urea compound of the present invention, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 3-methylhexane-1,6-
Diisocyanate, 3,3′-dimethylpentane-1,
5-diisocyanate, 1,3- and 1,4-cyclohexylene-diisocyanate, 4,4'-dicyclohexylmethane-diisocyanate, m- and p-xylylene diisocyanate, α, α, α ', Α'-Tetramethyl-p-xylylene diisocyanate, 4,4'-diphenylmethane-diisocyanate, isophorone diisocyanate, 2,4-tolylene diisocyanate, and the like. Preferably, isophorone diisocyanate,
Alicyclic diisocyanates such as 4,4'-dicyclohexylmethane-diisocyanate are preferred. These can be used alone or as a mixture.

The mono- or dialkylmonoamine (c) used for preparing the urethane urea compound of the present invention is a monoamine having an alkyl group having 1 to 10 carbon atoms, such as isopropylamine, n-butylamine, t-butylamine, and the like. -Butylamine, diethylamine, 2-ethylhexylamine, diisopropylamine, di-n-butylamine, di-t-butylamine, di-isobutylamine, di-2-ethylhexylamine and the like. Further, the alkyl chain may contain a tertiary nitrogen atom or an oxygen atom. For example, 3-dibutylamino-propylamine, 3-diethylamino-propylamine, 3-ethoxypropylamine, 3- (2-ethylhexyl) Oxy) propylamine. These can be used alone or as a mixture.

The alkyl monoalcohol (c) used for preparing the urethane urea compound of the present invention is a monoalcohol having an alkyl group having 1 to 10 carbon atoms, such as methanol, ethanol, 2-propanol, 2-methyl-2-propanol, 1-butanol,
2-ethyl-1-hexanol, 3-methyl-1-butanol and the like can be mentioned. These can be used alone or as a mixture. The above mono- or dialkylamines and alkyl alcohols can be used alone or as a mixture, but it is preferable to use them alone.

The organic monoisocyanate (c) used for preparing the urethane urea compound of the present invention includes n
-Butyl isocyanate, phenyl isocyanate, 1
-Naphthyl isocyanate, p-chlorophenyl isocyanate, cyclohexyl isocyanate, m-tolyl isocyanate, benzyl isocyanate, m-nitrophenyl isocyanate and the like. These can be used alone or as a mixture. However, it cannot be mixed with the above-mentioned mono- or dialkylamine and alkyl alcohol. Mono- or dialkylamines, compounds in which the active hydrogens of the alkyl alcohols are blocked by organic monoisocyanates not only reduce the effective amount of the urethane urea compound of the present invention, but also cause the compound to bleed out in the processing of polyurethane fibers. It causes scum to stain the knitting machine and dyeing tub.

(C) used in the preparation of the urethane urea compound of the present invention is selected from the three as described above,
It is a compound having a function of blocking the terminal (hydroxyl group or isocyanate group) of the urethane urea compound obtained from (a) and (b). In particular, if the terminal of the isocyanate group remains in the urethane urea compound, the spinnability such as thread breakage of the polyurethane fiber is deteriorated, so that the terminal group must be blocked.

The urethane urea compound of the present invention needs to contain an average of 4 to 40 urea binding units represented by the following formulas (5) and (6) in one molecule. When the average number of urea bonding units is less than 4, not only the heat setting property of the polyurethane fiber is not sufficient and the heat shrinkage becomes large, but also the urethane urea compound bleeds out in a processing step and causes a scum that stains a knitting machine and a dyeing bath. Become. When the average number of urea bond units exceeds 40,
The urethane urea compound precipitates in the undiluted polyurethane spinning solution, causing spun yarn breakage, or lowering the breaking strength and breaking elongation of the polyurethane fiber, thereby impairing the elastic function. The preferred number of urea bonding units is 8 to 30 in one molecule of the urethane urea compound.

The average number of urea bond units present per molecule of the urethane urea compound of the present invention can be adjusted by the molar ratio of (a), (b) and (c) during the preparation. Assuming that the average number of urea bonds is X, the reaction molar ratio of (a) / (b) can be represented by X / (X-1) to obtain a urethane urea compound having a desired average number of urea bond units. Can be. The reaction temperature is preferably from 20 to 80C. The reaction is preferably carried out in an amide polar solvent in which the polyurethane polymer is dissolved, for example, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, or the like. When a solvent that does not dissolve the polyurethane polymer is used, a solid content is taken out after the reaction, dissolved in a solvent in which the polyurethane polymer is dissolved, and added to the polyurethane polymer.

As an example of a method for synthesizing a urethane urea compound, 10 mol of N- (2-hydroxyethyl) piperazine is used as (a), 9 mol of isophorone diisocyanate as (b), and n-butyl as (c). 2 mol of alcohol is reacted at 60 ° C. for 2 hours to form a 60% by weight dimethylacetamide solution. The reaction is carried out by dropping isophorone diisocyanate and phenyl isocyanate dropwise into N- (2-hydroxyethyl) piperazine dissolved in dimethylacetamide, but the reaction method is not limited thereto. Other known methods can be used. At this time, the average number of urea bond units existing per molecule is 10.

The polyurethane fiber of the present invention can be obtained by dry spinning a spinning solution obtained by adding a urethane urea compound dissolved in an amide polar solvent to a polyurethane polymer solution,
Alternatively, it can be obtained by blending a urethane urea compound with a polyurethane polymer and melt-spinning. The addition can be performed at any stage from the completion of the polymerization of the polyurethane polymer to the spinning.

The amount of the urethane urea compound added to the polyurethane fiber of the present invention is such that the heat setting property and heat shrinkability required for the polyurethane fiber and the dimensional stability required for the product fabric can be sufficiently satisfied, and excellent elasticity can be obtained. Any amount that does not impair the function may be used, and is preferably 1 to 15% by weight based on the polyurethane polymer forming the fiber. If the amount of the urethane urea compound is less than 1% by weight, the effect of heat setting property is small. If the content exceeds 15% by weight, the effect of heat setting is saturated and spinning stability is reduced due to breakage of the spun yarn, and elastic functions such as strength, elongation and elastic recovery are impaired. More preferably, it is 2 to 10% by weight.

A known heat setting property improving technique can also be used in combination. For example, at least one thermoplastic polymer selected from a polyacrylonitrile-based polymer, a polyurethane polymer, and a styrene-maleic anhydride copolymer described in JP-A-7-316922 may be simultaneously contained. In this case, the total addition amount of the thermoplastic polymer and the urethane urea compound of the present invention is preferably 15% by weight or less, and the addition amount of the thermoplastic polymer preferably does not exceed the addition amount of the urethane urea compound.

Polyurethane fibers based on polyurethane urea polymers are segmented polymers having urethane bonds and urea bonds. Among them, urea bonds form extremely strong hydrogen bonding physical crosslinks in the matrix structure of the fibers. Form a crystalline domain. Therefore, while exhibiting an excellent elasticity function at normal temperature, the hydrogen bond is hard to be broken even at high temperature, so that it has heat resistance, but is hardly heat-set. The urethane urea compound having the number of urea bond units specified in the present invention is excellent at room temperature because the urea bond in the polyurethane urea fiber to which it is added produces a strong hydrogen bond and assimilate with the crystalline domain in the fiber. It becomes a polyurethane fiber exhibiting an elastic function. The urethane urea compound has an effect of lowering the glass transition temperature of the crystalline domain of the urethane urea polymer forming the fiber. It becomes a polyurethane fiber with excellent setting properties. If the amount of the urethane urea compound added to the polyurethane urea fiber is too small, the heat setting effect will be insufficient. vice versa,
If the addition amount is too large, the heat setting effect will be sufficiently satisfactory, but the glass transition temperature of the crystalline domain of the polyurethane urea fiber will be too low, and a heat flow will occur at a high temperature during spinning, and spinning stability cannot be ensured. Instead, the elastic function is impaired.

Hereinafter, a production example of the polyurethane fiber of the present invention based on a polyurethane urea polymer will be described. The polyurethane urea polymer has hydroxyl groups at both ends and is produced from a polymer glycol having a number average molecular weight of 600 to 5,000, an organic diisocyanate, a chain extender of a diamine compound, and an end blocking agent of a monoamine compound.

As the polymer glycol, various diols consisting of substantially linear homo- or copolymers, for example,
Examples thereof include polyester diol, polyether diol, polyester amide diol, polyacryl diol, polythioester diol, polythioether diol, polycarbonate diol, a mixture thereof, and a copolymer thereof. Preferred are polyalkylene ether glycols, for example, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, polyoxypentamethylene glycol, copolymerized polyether comprising a tetramethylene group and a 2,2-dimethylpropylene group Glycol, a copolymerized polyether glycol comprising a tetramethylene group and a 3-methyltetramethylene group, or a mixture thereof. Among them, polytetramethylene ether glycol, which exhibits excellent elasticity, and a copolymerized polyether glycol comprising a tetramethylene group and a 2,2-dimethylpropylene group are preferred.

As the organic diisocyanate, for example,
Among the aliphatic, alicyclic and aromatic diisocyanates, any of those which are soluble or liquid in an amide polar solvent under the reaction conditions can be applied. For example, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 2,4- and 2,6-tolylene diisocyanate, m- and p-xylylene diisocyanate, α, α, α ′, α '-Tetramethyl-xylylene diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-dicyclohexyl diisocyanate, 1,3- and 1,4-cyclohexylene diisocyanate, 3- (α- (Isocyanatoethyl) phenyl isocyanate, 1,6-hexamethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, a mixture thereof, or a copolymer thereof. Preferably, it is 4,4'-diphenylmethane diisocyanate.

Examples of the diamine compound of the chain extender include ethylenediamine, 1,2-propylenediamine,
1,3-diaminocyclohexane, 1,3-bis (aminomethyl) cyclohexane, 2-methyl-1,5-pentadiamine, hexamethylenediamine, triethylenediamine, m-xylylenediamine, piperazine, o-,
m- and p-phenylenediamine, JP-A-5-1558
No. 41, a diamine having a urea group or a mixture thereof. Preferably, ethylenediamine alone, 1,2-propylenediamine, 1,3-
At least one selected from the group consisting of diaminocyclohexane, 1,3-bis (aminomethyl) cyclohexane and 2-methyl-1,5-pentadiamine is 5 to 40 mol%
It is an ethylenediamine mixture contained.

As the monoamine compound of the terminal stopper,
For example, isopropylamine, n-butylamine, t-
Butylamine, monoalkylamines such as 2-ethylhexylamine, or diethylamine, diisopropylamine, di-n-butylamine, di-t-butylamine,
Examples thereof include dialkylamines such as di-isobutylamine and di-2-ethylhexylamine, which can be used alone or in combination. Also, 1,1-dimethylhydrazine can be used as a mixture with the monoamine compound.

The polyurethaneurea polymer can be prepared by using a known polyurethaneurea-forming reaction technique. For example, an intermediate polymer having an isocyanate group at a terminal is first prepared by reacting an excess molar amount of an organic diisocyanate with a polyalkylene ether glycol having a number average molecular weight of 600 to 5,000 in an amide polar solvent. Next, this intermediate polymer is dissolved in an amide-based polar solvent, and a chain extender is reacted with a terminal terminator to obtain a polyurethane urea polymer.

The polyurethane fiber of the present invention is obtained by adding the urea compound of the present invention to a polyurethane urea polymer in an amount of 1 to 1
The spinning solution containing 5% by weight is manufactured by applying a wet spinning method or a dry spinning method. In the spinning dope, in addition to the addition of the urethane urea compound of the present invention, further, polyurethane fibers, an organic or inorganic compounding agent useful for the polyurethane composition, for example, an ultraviolet absorber, an antioxidant, a light stabilizer,
Gas-resistant anti-coloring agents, coloring agents, matting agents, lubricants and the like can be added simultaneously or sequentially. For production of a polyurethane fiber which exhibits an excellent elasticity function and is excellent in productivity, it is preferable to apply a dry spinning method.

The larger the decitex per single yarn of the polyurethane fiber is, the more advantageous the heat setting property is. Preferably, it is 5 to 33 dtex per single yarn. This is not limited to polyurethane fibers, but can be applied to all types of elastic fibers.However, the magnitude of the heat setting effect is derived from the large relaxation of the orientation of crystal parts in the fibers. It is considered that the orientation is large at less than 5 dtex, and the orientation relaxation is small at more than 33 dtex, but the crystal size is large but the crystal flow during heat setting becomes difficult to occur.

The polyurethane fibers of the present invention may be added to polydimethylsiloxane, polyester-modified silicon, polyether-modified silicon, amino-modified silicon, mineral oil, mineral fine particles such as silica, colloidal alumina, talc, etc. Oils such as solid waxes at room temperature, such as higher aliphatic carboxylic acids, higher aliphatic alcohols, paraffins, polyethylene, etc., such as magnesium stearate and calcium stearate, may be used alone or in any combination as needed.

The polyurethane fibers of the present invention are rarely woven alone, and are made of natural fibers such as cotton, silk,
Wool and the like, synthetic fibers such as polyamide fibers such as N6 and N66, polyester fibers such as polyethylene terephthalate, polytrimethylene terephthalate and polytetramethylene terephthalate, cation dyeable polyester fibers and the like, regenerated fibers such as copper ammonia rayon and viscose rayon Semi-synthetic fibers, such as acetate and promix, are cross-knitted or woven in a bare state with mating fibers, or coated with these fibers, cross-twisted and processed yarns are cross-knitted to give a fabric. .

The mixing ratio of the polyurethane fibers in the fabric is 0.1%.
5 to 40% by weight. When the mixing ratio is less than 0.5% by weight, the stretchability of the polyurethane fiber is inferior to the fabric texture, so that the stretchability cannot be sufficiently exhibited or the stretch recovery is poor. When the mixing ratio exceeds 40% by weight,
At the time of dyeing, the dye distribution ratio collapses, hindering the color development of the mating fiber, deteriorating the quality of the fabric, causing problems such as too high power as the fabric and thick fabric.

Fabrics using the polyurethane fiber of the present invention include various types of stretch foundations such as swimwear, girdle, brassiere, intimate products, underwear, sock mouth rubber, tights, pantyhose, waistband, body suit, spats, and stretch. It can be used for sportswear, stretch outerwear, bandages, supporters, medical wear, stretch lining, disposable diapers and the like.

Hereinafter, various evaluation methods for performance evaluation and a method of preparing pantyhose will be described. [1] Measurement of breaking strength and breaking elongation Tensile tester (UTM-III-1 manufactured by Orientec Co., Ltd.)
A test yarn having a sample length of 5 cm is pulled at a speed of 50 cm / min under an atmosphere of 20 ° C. and 65% RH using a 00 type, and the breaking strength (cN) and the breaking elongation (%) are measured. [2] Heat resistance evaluation method A 14 cm test yarn was stretched by 50% to 21 cm, pressed against a stainless steel hot column having a surface temperature of 190 ° C. (hot column contact portion about 1 cm), and cut until the test yarn was cut. Measure the number of seconds. The longer the number of seconds, the higher the heat resistance, the smaller the set in high-temperature dyeing, high-temperature setting, and re-dying of the fabric, and the occurrence of thread breakage is reduced. [3] Method of evaluating heat setting property A test yarn having an initial length of 5 cm is placed in a pressurized steam atmosphere at 120 ° C. for 15 seconds under 100% elongation, and then dried in a dryer at 120 ° C. for 30 seconds. Then, in an atmosphere of 50 ° C.,
Let the time shrink. Furthermore, the yarn length (Lcm) is read after standing at 20 ° C. and a 65% RH atmosphere for 16 hours. In addition,
Leaving at 50 ° C. is a process for accelerating shrinkage with time. The heat setting rate (%) is calculated by the following equation (7). The higher the heat setting rate, the better the mold stopping properties and dimensional stability of the fabric.

[0040] [4] Preparation of pantyhose Polyamide elastic fiber (Leona 11 manufactured by Asahi Kasei Corporation)
A decitex / 5 filament) and the test yarn are covered (draft rate: 2.7, twist number: 1600 T / m, single cover S twist, two Z twists), and a knitting machine (Nagata Sim)
Plex KT-6 type, 400 gauge) and knit a total course 2500 zocchi pantyhose. After presetting the knitted fabric at 50 ° C, 45 ° C at 95 ° C
Stain for minutes. After the fix treatment and the softening agent treatment, the stainless steel last was set on the pressurized steam at 120 ° C. for 15 seconds while covering the knitted fabric, and dried at 120 ° C. for 30 seconds.
The knitted fabric was pulled out from the last to create pantyhose. [5] Evaluation of dimensional stability of pantyhose The length Y ₀ (cm) of the leg portion of the pantyhose prepared in [4] is measured. 5 washing at a temperature of 50 ° C
Measure the length Y (cm) after performing the cycle. The dimensional shrinkage of the pantyhose is calculated by the following equation (8). The smaller the dimensional shrinkage, the better the dimensional stability.

[0041]

[0042]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. Example 1 1,500 g (parts by weight, the same applies hereinafter) of polytetramethylene ether glycol having a number average molecular weight of 2,000 and 312 g of 4,4′-diphenylmethane diisocyanate were stirred at 60 ° C. for 90 minutes in a stream of nitrogen gas. The reaction was continued to obtain a polyurethane prepolymer having an isocyanate group. Next, after cooling to room temperature, 2,600 g of dry dimethylformamide was added and dissolved to obtain a polyurethane prepolymer solution.
On the other hand, 23.4 g of ethylenediamine and 3.7 g of diethylamine were dissolved in 1,400 g of dry dimethylformamide, and the prepolymer solution was added thereto at room temperature, and a polyurethaneurea polymer solution having a viscosity of 240 Pa · s (30 ° C.) was added. Obtained.

N- (2) was added to the polymer solution thus obtained.
-Hydroxyethyl) piperazine, 4,4'-diphenylmethane diisocyanate, and 6% by weight of a urethane urea compound having 12 urea bond units composed of phenyl isocyanate were added to obtain a spinning dope. This spinning stock solution was dry-spun at a spinning speed of 720 m / min and a hot air temperature of 240 ° C. to produce a polyurethane fiber of 17 dtex / one filament. [Examples 2 to 5] A urea compound 1 having an average number of urea bonding units of 10 consisting of N- (2-hydroxyethyl) piperazine, isophorone diisocyanate and phenyl isocyanate instead of the urethane urea compound of Example 1
0% by weight, 10% by weight of an urethane urea compound having an average number of urea bonding units of 10 consisting of N- (2-aminoethyl) -N '-(3-hydroxypropyl) piperazine, isophorone diisocyanate, and t-butylamine; -(2
-Aminoethyl) -N '-(3-hydroxypropyl)
10% by weight of a urethane urea compound comprising piperazine, isophorone diisocyanate and n-butanol and having an average number of urea bonding units of 10, N-isobutyl- (2-aminoethyl) -N- (2-hydroxyethyl) amine, isophorone A polyurethane fiber was spun in the same manner as in Example 1 by adding 8% by weight of a urea compound having an average number of urethane urea bonding units of 8 comprising diisocyanate and phenyl isocyanate. [Comparative Examples 1 to 3] Polyurethane fibers were produced in the same manner as in Example 1, except that the amount of the urethane urea compound added was 0% by weight, 0.2% by weight, and 20% by weight. [Comparative Example 4] Polyurethane fibers were spun in the same manner as in Example 1 except that 10% by weight of the urethane urea compound of Example 2 adjusted to have 50 urea bond units was added. The production of fibers was virtually impossible. Comparative Example 5 Instead of the urethane urea compound of Example 1, 10% by weight of the polyurethane polymer described in Example 4 of JP-A-7-316922 was added to produce polyurethane fibers.

Tables 1 and 2 show the evaluation results of the breaking strength, breaking elongation, heat resistance and heat setting rate of the polyurethane fibers obtained in Examples 1 to 5 and Comparative Examples 1 to 5. From Tables 1 and 2, it can be seen that the polyurethane urea elastic fiber of the present invention has a high heat setting property and has excellent strength, elongation and heat resistance.

[0045]

[Table 1]

[0046]

[Table 2]

Examples 6 and 7, Comparative Examples 6 and 7 Using the polyurethane fibers obtained in Examples 1 and 3 and Comparative Examples 1 and 5, a zocchi panty containing 18% by weight of a polyurethane fiber was used. Created stockings. Table 3 shows the evaluation results of the length and the heat shrinkage of these zokki panty kings. The pantyhose obtained from the polyurethane fibers prepared in Examples 1 and 3 has a good heat setting property, a large finished heat shrinkage rate, a small dimensional shrinkage rate of the product, and extremely excellent dimensional stability. I understand.

[0048]

[Table 3]

[0049]

The polyurethane fiber of the present invention has a high heat setting property and has excellent strength, elongation and heat resistance. Therefore, the fabric obtained by using the polyurethane fiber of the present invention can provide a fabric having good mold-stopping property during processing and excellent dimensional stability with little temporal shrinkage, and can be used in rounds such as pantyhose, socks and tights. It is an elastic fiber suitable for the production of any kind of elastic clothing such as knitted fabrics, foundations, warp knitting of swimwear and the like, and outer fabrics. The polyurethane fiber of the present invention is particularly suitable for the production of pantyhose, weft or warp stretch fabric.

Claims (9)

[Claims] 1. A urethane urea compound having an average number of urea bonding units per molecule of 4 to 40 obtained by reacting the following (a) and (b) is used in an amount of 1 to 15 wt. % Polyurethane fiber. (A) a nitrogen-containing compound containing a monofunctional amine of either a primary amine or a secondary amine, a hydroxyl group, and at least one selected from tertiary nitrogen and heterocyclic nitrogen (b) organic diisocyanate Nart 2. Both ends of a urethane urea compound are mono or dialkyl monoamine, alkyl mono alcohol,
The polyurethane fiber according to claim 1, wherein the polyurethane fiber is blocked with one kind selected from the group of organic monoisocyanates. 3. The method of claim 1, wherein the nitrogen-containing compound is N- (hydroxyalkyl) -piperazine, N- (hydroxyalkyl)-
The polyurethane fiber according to claim 1, wherein the polyurethane fiber is at least one selected from N ′-(aminoalkyl) -piperazine. 4. A polyurethane polymer having a number average molecular weight of 6
An intermediate polymer having an isocyanate group at the terminal by reacting an excess mole of organic diisocyanate with a polyalkylene ether glycol of 00 to 5,000, and a polyurethaneurea polymer obtained by reacting a diamine compound with a monoamine compound. The polyurethane fiber according to any one of claims 1 to 3, wherein: 5. A polyalkylene ether glycol having a number average molecular weight of 600 to 5,000 is reacted with an excess mole of organic diisocyanate to react an intermediate polymer having an isocyanate group at a terminal with a diamine compound and a monoamine compound. For the resulting polyurethane urea polymer,
An amide-based polarity comprising 1 to 15% by weight of a urethane urea compound having an average number of urea bond units per molecule of 4 to 40 obtained by reacting the following (a), (b) and (c): A method for producing a polyurethane fiber, comprising dry spinning a polyurethane urea spinning solution dissolved in a solvent. (A) a monofunctional amine of either a primary amine or a secondary amine, a hydroxyl group, and N- (hydroxyalkyl) -piperazine, N- (hydroxyalkyl) -N ′
A nitrogen-containing compound containing at least one selected from the group consisting of-(aminoalkyl) -piperazine; (b) an organic diisocyanate; and (c) a mono or dialkyl monoamine, an alkyl monoalcohol, or an organic monoisocyanate.
seed 6. The reaction of the following (a) and (b) to produce a urethane urea compound containing an average number of urea bond units of 4 to 40 per molecule, from 1 to 1 based on the polyurethane polymer.
Polyurethane fibers obtained by dry spinning a spinning dope containing 5% by weight have a mixing ratio of 0.5 with a fiber selected from at least one selected from the group consisting of synthetic fibers other than polyurethane fibers, regenerated fibers, semi-regenerated fibers, and natural fibers. A stretchable fabric having excellent dimensional stability, characterized in that the fabric is a mixed fabric knitted at 40 to 40% by weight. (A) a nitrogen-containing compound containing a monofunctional amine of either a primary amine or a secondary amine, a hydroxyl group, and at least one selected from tertiary nitrogen and heterocyclic nitrogen (b) organic diisocyanate Nart 7. The nitrogen-containing compound is N- (hydroxyalkyl) -piperazine, N- (hydroxyalkyl)-
At least one selected from N '-(aminoalkyl) -piperazines, wherein the average number of urea binding units per molecule of the urethane urea compound is 4 to 40, and both ends of the urethane urea compound are as follows: The stretchable fabric excellent in dimensional stability according to claim 6, wherein the stretchable fabric is closed in (c). (C) 1 selected from the group consisting of mono- or dialkylmonoamines, alkylmonoalcohols, and organic monoisocyanates
seed 8. A polyurethane fiber having a number average molecular weight of 60.
From an intermediate polymer having an isocyanate group at a terminal by reacting an excess mole of an organic diisocyanate with a polyalkylene ether glycol of 0 to 5,000, and a polyurethaneurea polymer obtained by reacting a diamine compound and a monoamine compound, The stretchable fabric excellent in dimensional stability according to claim 6 or 7, wherein the fabric is cross-knitted in a state where the polyurethane fiber is covered or twisted with the mixed fiber. 9. The polyurethane fiber has a number average molecular weight of 60.
From an intermediate polymer having an isocyanate group at a terminal by reacting an excess mole of an organic diisocyanate with a polyalkylene ether glycol of 0 to 5,000, and a polyurethaneurea polymer obtained by reacting a diamine compound and a monoamine compound, The stretchable fabric excellent in dimensional stability according to claim 6 or 7, wherein the polyurethane fiber is inserted in a bare state and cross-woven with the mixed fiber.