JPH11200148A - Polyurethane elastic fiber and elastic fabric using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject elastic fiber capable of providing a fabric excellent in dyeability, color fastness and thermoformability and capable of manifesting a good appearance, shape retaining properties and elastic recovery properties by adding a specific amount of a polyvinylpyrrolidone having a prescribed number-average molecular weight to a specified polyurethane polymer. SOLUTION: This elastic fiber is obtained by adding (B) 0.1-15 pts.wt. polyvinylpyrrolidone having 5,000-500,000 number-average molecular weight to (A) 100 pts.wt. polyurethane polymer prepared by reacting a polymer diol having 500-5,000 number-average molecular weight and hydroxyl groups at both ends with an organic diisocyanate and a chain extender having polyfunctional active hydrogen atoms and further preferably adding (C) 1-15 pts.wt. thermoplastic urethane resin which is a reactional product of a mixture of (i) a low-molecular diol having a 2-10C straight-chain or branched alkylene group or hydrogen groups at both ends of a bivalent alicyclic hydrocarbon group with (ii) a polymeric diol having 400-3,000 number-average molecular weight in 1-99 molar ratio of (i)/(ii) with an organic diisocyanate and having 10,000-40,000 average molecular weight thereto.

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 and an elastic fabric comprising the fiber, and more particularly to a method for improving the thermoformability of the polyurethane elastic fiber, eliminating the curl of the product cloth, and improving the workability in sewing the product. At the same time, improving the dyeability and dyeing fastness of polyurethane elastic fiber, so that the peeling quality of the fabric at the time of wearing and contracting and the shape retention even when washing clothes and pantyhose made of the fabric using it The present invention relates to a good high-productivity fabric.

[0002]

2. Description of the Related Art A polyurethane polymer elastic fiber obtained from an organic diisocyanate, a polymer diol and a chain extender having a polyfunctional active hydrogen atom is generally called spandex (registered trademark) and has a moderate rubber elasticity. And have excellent properties. For this reason, cross-woven fabrics that have been mixed and knitted, cross-woven and dyed with various fibers such as polyester and polyamide have been used more and more widely as various stretch material fabrics in recent years. However, polyurethane elastic fibers generally have low thermoformability and poor dimensional stability of the fabric width in the dyeing process and poor shape retention of the product.
In addition, the fabric may be curled and the operability of sewing on clothing products may be difficult. There is also a method of improving the thermoformability by exposing a material having a low thermoformability to a high temperature for a long time, but in this case, there is a problem that the polyurethane is thermally deteriorated and the elastic recovery property is greatly reduced.

Further, in recent years, high heat resistant polyurethane elastic fibers for polyester cross-knitting and weaving have been developed in which the physical properties are less reduced by heat deterioration even at high temperature dyeing, but in this case, there is a problem that the thermoformability is further reduced. Therefore, there is a strong demand for the appearance of polyurethane elastic fibers having good thermoformability and less curl of the fabric while maintaining high heat resistance during dyeing of the polyurethane polymer itself. In addition, polyurethane elastic fibers are generally harder to dye than other fiber materials, and are knitted and woven with other fiber materials. Polyurethane elastic fibers which are not sufficiently dyed are exposed from the mixed and woven fabric. This has been pointed out as a problem called "peeling", in which elastic fibers are seen in a whitish streak on the surface of the fabric, which greatly reduces the commerciality of the fabric.

In the prior art, attempts have been made to improve the thermoformability and dyeability of polyurethane elastic fibers. For example, with respect to thermoformability,
No. 0 and JP-A-3-97915 propose to improve the thermoformability by modifying the polyurethane polymer by using a specific mixed diamine as the polymer chain extender diamine. Also, Japanese Patent Application Laid-Open No. Hei 7-150417
JP-A-7-88620 discloses a method of adding a specific alkali metal salt to a polyurethane polymer, and JP-A-7-88620 discloses a method of blending a thermoplastic polymer with polyurethane to improve thermoformability. Although improvements in moldability have been proposed, none of them is yet satisfactory.

Regarding the dyeability of polyurethane, Japanese Patent Application Laid-Open No. 51-80392 discloses that an N-vinylpyrrolidone monomer and a water-insoluble vinyl monomer are added to a polyurethane elastomer for the purpose of improving the dyeability of a leather-like material. A method for graft copolymerization is disclosed. However, since this polymer is a three-part graft copolymer of an N-vinylpyrrolidone monomer, a water-insoluble vinyl monomer and polyurethane, the polymer is partially cross-linked and branched, so that the It was found that it was extremely difficult to produce yarn breakage frequently in the spinning cylinder and was not suitable for fibers. In addition, according to this method, N-vinylpyrrolidone has a degree of polymerization having a number average molecular weight of 3000 or more and a molecular weight distribution (MWD = MW /
MN) was also difficult to obtain a product of 2.5 or less.

Further, Japanese Patent Publication No. 37-8972 discloses that
A melt composition of a polyurethane made of 1,4 butanediol bischloroformate and hexamethylenediamine and polyvinylpyrrolidone is disclosed. However, this melt composition is also disadvantageous because polyvinylpyrrolidone lowers the heat resistance of the polyurethane. In addition, stable spinning is difficult due to frequent thread breakage in the spinning cylinder during melt spinning, and a fiber long enough to be used for physical property measurement cannot be obtained, which is not suitable for an elastic fiber for clothing use. I understood that. Also, Japanese Patent Publication No. 47-48895 and Japanese Patent Application Laid-Open No. 62-860.
No. 47 discloses a stabilizing effect of a mixed composition of a polyurethane containing tertiary amine nitrogen and a long-chain synthetic elastic polyurethane with light and smog,
No suggestion is made of polyurethane elastic fibers. That is, as a polyurethane elastic fiber, there is no known polyurethane elastic fiber having excellent thermoformability and dyeability at the same time, and at the same time sufficiently satisfying spinning properties, elastic recovery properties, and heat resistance that are sufficiently stable for use in clothing, and a fabric thereof. .

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art, that is, to enhance the thermoformability of polyurethane elastic fiber, eliminate curling of the product cloth, and improve the sewing of the product. It facilitates the workability of the fabric, and at the same time improves the dyeability and color fastness of the polyurethane elastic fiber, so that it can be used to wash the clothes and pantyhose made of the fabric that is used when the fabric is stretched when worn and stretched. It is an object of the present invention to provide a fabric having high formability and good shape retention. In other words, according to the present invention, polyurethane knitting of polyurethane elastic fibers, thermoforming of dyed and woven fabrics, dyeing, and the like do not degrade the elastic recovery characteristics due to thermal degradation of polyurethane elastic fibers, and give a good product appearance. An object of the present invention is to provide interwoven fabric.

[0008]

DISCLOSURE OF THE INVENTION The present inventors have found that a polyurethane elastic fiber cross-knitted fabric excellent in thermoformability by minimizing thermal deterioration during thermoforming of polyurethane elastic fibers useful mainly for clothing. As a result of diligent research to produce a polyurethane polymer, by combining the polyurethane polymer with specific polyvinylpyrrolidone and polyvinylpyrrolidone with a specific thermoplastic urethane resin and a tertiary nitrogen-containing polyurethane, the thermoformability of polyurethane elastic fiber The present inventors have found that a polyurethane elastic fiber having good thermoformability, good dyeing properties, and having the necessary elastic properties as an elastic fiber required for clothing can be obtained, thereby completing the present invention.

That is, the present invention provides (a) a number average molecular weight of 50
Polyurethane polymer 10 obtained by reacting a polymer diol having hydroxyl groups at both terminal groups of 0 to 5000 with an organic diisocyanate and a chain extender having a polyfunctional active hydrogen atom
(B) number average molecular weight of 5,000 to 50
This is a polyurethane elastic fiber to which 0.1 to 15 parts by weight of polyvinylpyrrolidone is added.

Further, (a) a number average molecular weight of 500 to 500
(B) a number average molecular weight of 5,000 to 100 parts by weight of a polyurethane polymer obtained by reacting a polymer diol having hydroxyl groups at both terminal groups with an organic diisocyanate and a chain extender having a polyfunctional active hydrogen atom. 500,000 polyvinylpyrrolidone contains 0.1 to 15 parts by weight and (c) a linear or branched alkylene group having 2 to 10 carbon atoms or 2
Molar ratio of low molecular weight diol (A) having hydrogen groups at both ends of divalent alicyclic hydrocarbon group to high molecular weight diol (B) having a number average molecular weight of 400 to 3,000 (A) / (B) = 1-9
1 to 15 parts by weight of a thermoplastic urethane resin having a number average molecular weight of 10,000 to 40,000, which is a reaction product of the mixture of Example No. 9 and an organic diisocyanate and whose terminal is a hydrogen group and whose urethane group concentration is 3 meq / g or more, is added. It is a polyurethane elastic fiber.

Further, (a) a number average molecular weight of 500 to 500
(B) a number average molecular weight of 5,000 to 100 parts by weight of a polyurethane polymer obtained by reacting a polymer diol having hydroxyl groups at both terminal groups with an organic diisocyanate and a chain extender having a polyfunctional active hydrogen atom. 500,000 polyvinylpyrrolidone contains 0.1 to 15 parts by weight and (d) a reduced viscosity in which a terminal is a hydrogen group formed from a tertiary nitrogen-containing diol represented by the following general formula (1) and an organic diisocyanate. Is a polyurethane elastic fiber to which 0.5 to 10 parts by weight of a tertiary nitrogen-containing polyurethane of 0.02 to 0.7 is added.

[0012]

Embedded image (In the formula, R ₁ and R ₂ each represent a linear or branched alkylene group having 1 to 5 carbon atoms, and R ₃ represents a linear or branched alkyl group having 1 to 10 carbon atoms.)

Further, (a) a number average molecular weight of 500 to 500
(B) a number average molecular weight of 5,000 to 100 parts by weight of a polyurethane polymer obtained by reacting a polymer diol having hydroxyl groups at both terminal groups with an organic diisocyanate and a chain extender having a polyfunctional active hydrogen atom. 500,000 polyvinylpyrrolidone is 0.1 to 15 parts by weight, (c) a linear or branched alkylene group having 2 to 10 carbon atoms, or
The molar ratio (A) / (B) of a low molecular weight diol (A) having hydrogen groups at both ends of a divalent alicyclic hydrocarbon and a high molecular weight diol (B) having a number average molecular weight of 400 to 3,000 = 1-9
9 and a reaction product of the organic diisocyanate (C), the terminal is a hydrogen group, and the urethane group concentration is 3 meq /
g of at least 1 to 15 parts by weight of a thermoplastic urethane resin having a number average molecular weight of 10,000 to 40,000 and (d) a terminal formed from a tertiary nitrogen-containing diol represented by the following general formula (1) and an organic diisocyanate. Is a polyurethane elastic fiber to which 0.5 to 10 parts by weight of a tertiary nitrogen-containing polyurethane having a reduced viscosity of 0.02 to 0.7, which is a hydrogen group, is added.

[0014]

Embedded image (In the formula, R ₁ and R ₂ each represent a linear or branched alkylene group having 1 to 5 carbon atoms, and R ₃ represents a linear or branched alkyl group having 1 to 10 carbon atoms.)

Further, there is provided an elastic fabric comprising the polyurethane elastic fibers of the present invention. The elastic fiber of the present invention preferably has the following physical properties of elasticity in order to be suitable for clothing use. That is, the elongation at break is 300% or more,
Preferably, the stress at 500% or more and the elongation at 300% is 0.2 to 0.8 g / denier and the elastic fiber is 5%.
After immersion in boiling water for 1 hour under 0% elongation, 300% of the elastic fiber after being exposed for 60 seconds in an atmosphere of dry heat of 120 ° C.
It is a polyurethane elastic fiber having a ratio (R / S) of the forward stress (S) of 200% elongation and the return stress (R) after repeating the elongation three times of 0.1 to 0.8.

The polyurethane elastic fiber of the present invention comprises a substantially linear isocyanate-terminated prepolymer consisting of a high molecular weight diol having a number average molecular weight of 500 to 5,000 and an organic diisocyanate, and a polyfunctional active hydrogen atom. A specific polyvinylpyrrolidone of the present invention is added to a polyurethane polymer obtained by reacting a chain extender having the same with a terminal stopper having a monofunctional active hydrogen atom within a range that does not adversely affect the spinnability. The addition can be made during or after the polymerization of the polyurethane, and it is preferable to add it after the polymerization. The elastic fiber of the present invention can be obtained by a usual method of dry spinning, melt spinning and wet spinning. In the point that the polymer is hardly thermally degraded during thermoforming and retains the physical properties as elastic fibers for clothing,
Particularly preferred is a polyurethane urethane elastic fiber obtained by dry spinning a polyurethane urea polymer having a urethane group and a urea group in the polymer structure.

The high molecular weight diol which is one of the raw materials of the polyurethane polymer of the present invention is a substantially linear polymer having a molecular weight of 500 to 5,000 having hydroxyl groups at both ends, for example, polyoxyethylene. Homopolyether diols such as glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, polyoxypentamethylene glycol or copolymerized polyether diols composed of two or more oxyalkylenes having 2 to 6 carbon atoms; adipic acid , Sebacic acid, maleic acid,
One or more dibasic acids such as itaconic acid, azelaic acid, malonic acid and ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol,
2,2-dimethyl-1,3-propanediol, 1,4
-Butanediol, 1,3-butanediol, hexamethylene glycol,

Diethylene glycol, 1,10-decanediol, 1,3-dimethylolcyclohexane, 1,
Polyester diol obtained from one or more glycols such as 4-dimethylolcyclohexane;
Or, polylactone diols such as polyester amide diol, polyester ether diol, poly-ε-caprolactone diol, polyvalerolactone diol, and the like, polycarbonate diol, and the like. Preferred are polyoxytetramethylene glycol, copolymerized poly (tetramethylene neopentylene) ether diol, and copolymerized poly (tetramethylene-2-methylbutylene) ether diol.

As the organic diisocyanate, for example,
Among the aliphatic, alicyclic, and aromatic diisocyanates, any of those that are soluble or liquid under the reaction conditions can be applied. For example, methylene-bis (4-phenyl isocyanate), methylene-bis (3-methyl-4-phenyl isocyanate), 2,4-tolylene diisocyanate,
2,6-tolylene diisocyanate, m- and p-xylylene diisocyanate, α, α, α ′, α′-tetramethyl-xylylene diisocyanate, m- and p-phenylene diisocyanate, 4,4′-dimethyl-1 ,
3-xylylene diisocyanate, 1-alkylphenylene-2,4 and 2,6-diisocyanate, 3- (α
-Isocyanatoethyl) phenyl isocyanate,

2,6-diethylphenylene-1,4-diisocyanate, diphenyl-dimethylmethane-4,4
-Diisocyanate, diphenyl ether-4,4'-
Diisocyanate, naphthylene-1,5-diisocyanate, 1,6-hexamethylene diisocyanate, methylene-bis (4-cyclohexyl isocyanate),
Examples thereof include 1,3- and 1,4-cyclohexylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. Preferably, it is methylene-bis (4-phenyl isocyanate).

Examples of the chain extender having a polyfunctional active hydrogen atom include hydrazine, polyhydrazine, and linear or branched aliphatic, alicyclic and aromatic active hydrogen having 2 to 10 carbon atoms. Compounds having an amino group such as ethylenediamine, 1,2 propylenediamine, diamines such as diamines having a urea group described in JP-A-5-155841, hydroxylamine, water and the like, and low-molecular weight glycols such as , Ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, hexamethylene glycol, diethylene glycol , 1,10-decanediol, 1,3-dimethylolcyclohexa , 1,4-dimethylol cyclohexane. Preferably, ethylene diamine,
1,2 Propylenediamine.

As the terminal terminator having a monofunctional active hydrogen atom, for example, dialkylamine such as diethylamine is used. These chain extenders and terminal stoppers may be used alone or in combination of two or more. The polyvinylpyrrolidone used in the present invention has a number average molecular weight of 50.
When it is mixed with a polyurethane polymer dissolved in a polar solvent and spun at a rate of 100,000 to 500,000, any one of dimethylacetamide, dimethylformamide, and dimethylsulfoxide usually used as a solvent for the polyurethane polymer is used. It is preferable to dissolve 5 parts by weight or more with respect to 100 parts by weight of the polar solvent. Preferably, it dissolves in the polar solvent in an amount of 8 parts by weight or more. When the number average molecular weight of polyvinylpyrrolidone is less than 5,000, the spun elastic fibers are colored yellow. Further, polyvinylpyrrolidone is eluted in the dyeing bath during the dyeing step, and the dyeing property and the effect of heat setting are undesirably reduced. When the number average molecular weight of polyvinylpyrrolidone exceeds 500,000, the viscosity of the spinning dope becomes extremely high, and it is difficult to maintain a stable and constant spinning dope discharge pressure, so that long-term stable production cannot be performed.

The more preferred number average molecular weight of polyvinylpyrrolidone is 8,000 to 300,000. If it is out of this range, it is usually used in the pantyhose field.
Spinning of fine denier of 0 denier or less is difficult and yarn breakage frequently occurs in the spinning cylinder. Further, when the molecular weight distribution (MWD) of the polyvinylpyrrolidone used is larger than 2.0, the elastic recovery of the polyurethane elastic fiber is reduced, and when the fabric using the same is worn, the pressure of the fabric is as short as possible. After several tens of minutes, a change in the pressure drop occurs. Therefore, the preferred MWD is preferably 2.0 or less. More preferably, it is 1.8 or less, particularly preferably 1.6 or less. The content of polyvinylpyrrolidone used in the present invention in the elastic fiber is in the range of 0.1 to 15 parts by weight based on 100 parts by weight of the polyurethane polymer.

Within this range, the higher the content of polyvinylpyrrolidone, the better the thermoformability, and thermoforming at a temperature lower than the normal temperature becomes possible. However, 0.
If the addition is less than 1 part by weight, the effects of thermoforming and dyeing properties are insufficient, and if it is more than 15 parts by weight, heat resistance is reduced and yarn breakage frequently occurs during spinning, or elastic fiber It adversely affects physical properties such as elongation at break and elastic recovery, and frequently causes yarn breakage during cross-knitting and weaving. Also, the elastic recovery characteristics of the fabric using it are low, and the commercial value of the fabric is also reduced,
It is not preferred as an elastic fiber for clothing use. The preferred addition amount is 2 to 12 parts by weight, more preferably 3 to 10 parts by weight.
Parts by weight.

The polyvinylpyrrolidone used in the present invention is usually added to a polyurethane polymer obtained by reacting a polyurethane prepolymer with a chain extender, either as a powder or as previously dissolved uniformly in the above-mentioned polar solvent. However, it is also possible to add them in advance to each of these agents or to add them during polymerization using conditions that do not react with the polyurethane polymer. Polyurethane composition of the present invention, dimethylacetamide, dimethylformamide, dimethylsulfoxide, a spinning solution dissolved in a polar solvent such as dimethyl sulfoxide, the discharge pressure is increased during the spinning process, no occurrence of thread breakage is observed, for a long time Stable spinning can be performed.

The polyurethane elastic fiber to which the specific polyvinylpyrrolidone is added according to the present invention contains polyethylene terephthalate, polytrimethylene terephthalate, polytetramethylene terephthalate as a twine and polytetramethylene glycol and ethylene glycol as diol components as main components. Copolymerized polyterephthalate and their cationic dyeable polyester fibers, polyamides such as nylon 6, nylon 66, synthetic fibers such as acrylic, polypropylene and polyvinyl alcohol, regenerated cellulose fibers, regenerated protein fibers, semi-synthetic fibers, cotton, silk,
Along with natural fiber materials such as wool, also covering, plying,
Interlaced composite fibers, circular knitted fabrics, flat knitted fabrics, warp knitted fabrics, and various types of fabrics can be very stably formed without thread breakage.

It is possible to produce a high-quality fabric which is excellent in dyeability and has good color fastness to washing, friction, sweat and water as compared with a fabric using conventional polyurethane elastic fibers. As a result of further study, surprisingly, as a result of further study of the dyeing properties, the number average molecular weight was 5,000.
It is possible to significantly improve the dyeability and dyeing fastness of the polyurethane fiber of the present invention by using up to 500,000 polyvinylpyrrolidone and a tertiary nitrogen-containing urethane having a specific structure in combination. Was found. Dyes that can be used in the present invention include acid dyes, gold-containing dyes, mordant / acid dyes, direct dyes, reactive dyes, basic dyes, vat dyes, sulfur dyes, azoic dyes, disperse dyes, and cationic dyes. . Particularly preferred are acid dyes, gold-containing dyes, mordant / acid dyes, direct dyes and reactive dyes.

Further, the thermoformability is good without lowering the elastic recovery property, and the curl of the cloth can be suppressed without lowering the elastic recovery property. 0.1 to 1 of polyvinylpyrrolidone
5 parts by weight, a low molecular weight diol (A) having a hydrogen atom at both terminals of a linear or branched alkylene group having 2 to 10 carbon atoms or a divalent alicyclic hydrocarbon group, and a number average molecular weight of 400
Molar ratio (A) with high molecular weight diol (B) up to 3,000
/ (B) = a reaction product of a mixture of 1 to 99 and an organic diisocyanate (C), wherein the terminal is a hydrogen group and the urethane group concentration is 3 meq / g or more, and the number average molecular weight is 1000
It has been found that the addition of 1 to 15 parts by weight of a thermoplastic urethane resin of 0 to 40,000 in combination with the polyurethane polymer of the present invention has a synergistic effect of remarkably improving thermoformability.

If the amount of the thermoplastic urethane resin is less than 1 part by weight, the effect is not sufficient. If the amount is more than 15 parts by weight, the heat resistance is greatly reduced, and not only stable spinning becomes difficult, but also it is difficult to obtain. It was found that the obtained fiber had a large elastic recovery property and thus was not suitable for use in clothing. Here, examples of the low molecular diol (A) of the thermoplastic urethane resin include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 2,3-butanediol, -Methyl-1,3
-Propanediol, 2,2-dimethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol,

2-methyl-1,6-hexanediol,
1,8-octanediol, 2-ethyl-1,6-hexanediol, 2-methyl-2-butyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, diethylene glycol, , 10-decanediol, 1,3-cyclohexanediol, 1,4
-Cyclohexanediol, 1,3-dimethylolcyclohexane, 1,4-dimethylolcyclohexane, 4,
A single compound such as 4′-dicyclohexanedimethylmethanediol or a combination of these two compounds is exemplified. Of these, preferred low molecular weight diols (A) include 1,4-butanediol alone and a combination of 1,4-butanediol and 1,3-propylene glycol.

Examples of the polymer diol (B) include polyoxytetramethylene glycol, a mixture of several kinds of polyoxytetramethylene glycols having different number average molecular weights, a mixture of polyoxytetramethylene glycol and polyoxypropylene glycol, Copolymerized poly (oxytetramethylene / oxyneopentylene) diol, copolymerized poly (oxytetramethylene / oxy-2-methylbutylene) diol, or a mixture of two or more thereof. Preferred examples of the organic diisocyanate (C) include methylene-bis (4-phenylisocyanate),
P-xylylene diisocyanate, isophorone diisocyanate alone or in combination.

Here, the thermoplastic urethane resin is reacted with at least one of the above-mentioned low molecular weight diols (A), at least one high molecular diol (B), and at least one organic diisocyanate. A thermoplastic urethane resin and a thermoplastic urethane resin obtained by mixing a plurality of them, and these can be used together with the polyurethane polymer of the present invention and polyvinylpyrrolidone. Furthermore, a specific tertiary nitrogen-containing urethane having a terminal hydrogen group obtained by reacting an N, N-bis (hydroxyalkylene) alkylamine represented by the following general formula (1) with an organic diisocyanate: By using 0.5 to 10 parts by weight together with the polyvinylpyrrolidone used in the present invention, remarkable improvement in dyeability and color fastness was observed. However, if the amount is less than 0.5 part by weight, the effect of improving the dyeability is not sufficient. If the amount is more than 10 parts by weight, the elastic recovery of the fiber is greatly reduced, and the color fastness is also lowered, which is not suitable for clothing use. I understand.

[0033]

Embedded image (In the formula, R ₁ and R ₂ each represent a linear or branched alkylene group having 1 to 5 carbon atoms, and R ₃ represents a linear or branched alkyl group having 1 to 10 carbon atoms.)

When the number of carbon atoms of R ₁ , R ₂ and R ₃ is more than the above, dyeing performance becomes insufficient when used in combination with polyvinylpyrrolidone. Preferred as the diol used in the present invention are N, N-bis (2-hydroxyethyl) -methylamine, N, N-bis (2-hydroxyethyl) -ethylamine, N, N-bis (2-
(Hydroxyethyl) -propylamine, N, N-bis (2-hydroxyethyl) -isopropylamine,
N-bis (2-hydroxyethyl) -butylamine,
N, N-bis (2-hydroxyethyl) -tbutylamine, N, N-bis (2-hydroxyethyl) -pentylamine, N, N-bis (2-hydroxyethyl) -heptylamine, N, N-bis (2-hydroxyethyl)-
Octylamine, N, N-bis (2-hydroxypropyl) -methylamine,

N, N-bis (2-hydroxypropyl)
-Ethylamine, N, N-bis (2-hydroxypropyl) -propylamine, N, N-bis (2-hydroxypropyl) -isopropylamine, N, N-bis (2-
(Hydroxypropyl) -butylamine, N, N-bis (2-hydroxypropyl) -t-butylamine,
N-bis (2-hydroxypropyl) -pentylamine, N, N-bis (2-hydroxyethyl) -t amylamine, N, N-bis (2-hydroxypropyl) -t
Amylamine, N, N-bis (2-hydroxypropyl) -heptylamine, N, N-bis (2-hydroxypropyl) -octylamine, N, N-bis (2-hydroxyethyl) -1,1-dimethylpropyl Amine,
N, N-bis (2-hydroxypropyl) -1,1-dimethylpropylamine and the like can be mentioned.

In a particularly preferred N, N-bis (hydroxyalkylene) alkylamine, R ₃ is an ethyl group, a butyl group, a t-butyl group, a pentyl group, a t-amyl group, R ₁ , R
₂ is N, N-bis (hydroxyalkylene) alkylamine selected from 2-hydroxyethyl and 2-hydroxypropyl. Examples of the organic diisocyanate include aliphatic, alicyclic, and aromatic diisocyanates, for example, m- and p-xylylene diisocyanate, α, α, α ′, α′-tetramethyl-xylylene diisocyanate. Isocyanate, 4,4'-dimethyl-1,3-xylylene diisocyanate, 1,6-hexamethylene diisocyanate, methylene-bis (4-cyclohexyl isocyanate), 1,3- and 1,4-cyclohexylene diisocyanate, trimethylene Diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate,

There may be mentioned isophorone diisocyanate. Preferably, isophorone diisocyanate, methylene-bis (4-cyclohexane isocyanate) alone or a mixture thereof is used. N, N-bis (hydroxyalkylene) alkylamine and organic diisocyanate are catalyzed by N, N-bis (hydroxyalkylene) alkylamine in the presence or absence of dibutyltin dilaurate, in a solvent or in bulk, from organic diisocyanate. Also, a specific tertiary nitrogen-containing urethane having a hydrogen terminal at the terminal obtained by reacting in an excess molar ratio can be obtained.

This particular tertiary nitrogen-containing urethane is
In 100 ml of a dimethylacetamide solution at a temperature of 25 ° C,
It preferably has a molecular weight corresponding to a reduced viscosity of 0.02 to 0.7 at a concentration of 0.5 g. Here, the reduced viscosity is obtained from an equation defined by (η _n -1) / C. η _n is the value obtained by dividing the viscosity of the dilute solution of the polymer by the viscosity of the solvent measured at the same temperature, and
It is the concentration expressed in grams of polymer per ml.
If the reduced viscosity is too low, it will easily fall off in the dyeing step, and if the reduced viscosity is too high, the elastic recovery will be reduced. A particularly preferred range of the reduced viscosity is 0.05 to 0.4.

Furthermore, a specific amount of polyvinylpyrrolidone having a number average molecular weight of 5,000 to 500,000, a tertiary nitrogen group-containing urethane having a specific structure and a terminal hydrogen group, and / or a specific thermoplastic urethane resin is used in combination. Further, the dyeability and the color fastness are good, the thermoformability is good without lowering the elastic recovery, and the curl of the fabric can be suppressed without lowering the elastic recovery. The most suitable polyurethane elastic fiber can be obtained in the field.

The polyurethane elastic fibers to which the specific polyvinylpyrrolidone is added according to the present invention include polyethylene terephthalate, polytrimethylene terephthalate, polytetramethylene terephthalate, and a copolymer containing polytetramethylene glycol and ethylene glycol as main components as diol components. Terephthalates and their cationically dyeable polyester fibers, nylon 6, nylon 6
6, synthetic fibers such as polyamide, polyacrylic, polypropylene, polyvinyl chloride, polyvinyl alcohol, etc., regenerated cellulose fibers such as cuprammonium rayon, viscose rayon, purified cellulose fibers, regenerated protein fibers,
Circular knitted fabric with natural fiber materials such as semi-synthetic fibers, cotton, silk, wool, etc., as well as covering, corespun yarn, air covering, ply-twisted, cross-twisted, interlaced conjugated fibers and their respective fibers as they are It is processed into a cross-knitted / cross-woven fabric which is cross-knitted or cross-woven such as flat knitted fabric, warp knitting, and dyed, and is used for various purposes.

The fabric using the polyurethane elastic fiber of the present invention can give a polyurethane cross-knitted woven fabric which gives a good appearance of the product with excellent dyeability and dyeing fastness, and can be used for girdle, brassiere, intimate goods, and underwear. Stretch foundation, socks rubber, tights, pantyhose, waistband, bodysuit, spats, swimwear, stretch sportswear, etc.
It is suitable for applications such as stretch fabrics, stretch outers, bandages, supporters, medical wear, stretch lining, and disposable diapers.

The polyurethane composition used in the present invention may contain, if desired, other compounds usually used, for example, hindered amine, benzotriazole, triazine, benzophenone ultraviolet absorbers, hindered phenols, and organic phosphorus oxides. Inhibitor, fungicide, semicarbazide stabilizer, coloring agent, titanium oxide matting agent, zinc oxide,
It may be used in combination with a solid solution comprising two or more kinds of oxides of magnesium oxide, hydrotalcite-based inorganic, zinc and / or magnesium and / or aluminum, an inorganic filler and the like.

[0043]

The present invention will be described in more detail with reference to the following examples and comparative examples, but the present invention is not limited to these examples. Various measurement methods and various pretreatments of fibers described in the examples were performed using the methods described below.

<Number average molecular weight of polyvinylpyrrolidone,
Measurement method of molecular weight distribution> It is measured using a gel permeation chromatograph (GPC) and determined from a standard polystyrene calibration curve. An example is LC-6 manufactured by Shimadzu Corporation.
The measurement in A is performed using a separation column Polymer Labor.
Ateliers PL gel 5 μm MIXED-C: solvent, dimethylformamide (0.01 mol LiBr)
Addition): column flow rate 1.0 ml / min: column temperature 5
0 ° C .: Measured at a sample concentration of 0.2% (W / V) using an RI detector. The molecular weight distribution (MWD) was determined from the following equation. MWD = weight average molecular weight / number average molecular weight

<Measurement method of breaking strength and elongation> Measured at 20 ° C. and 65% RH using a tensile tester (UTM-3-100 manufactured by Orientec Co., Ltd.). The yarn sample length was measured at a strain rate of 1000% for 1 minute at a width of 5 cm, and the elongation at break and the load at 300% elongation were measured.

<Measurement of R / S stress ratio> An elastic yarn marked at 50 mm in a tension-free and linear state is stretched and fixed to a length of 75 mm, immersed in boiling water for 60 minutes as it is, and further immersed in that state After passing through a tenter adjusted to 120 ± 1 ° C., the passing time of the tenter box is set to 60 seconds, the elastic yarn is immediately taken out, sufficiently relaxed to a length of 50 mm or less, and left at room temperature for 16 hours. At the initial stage of the elastic yarn, the mark portion was attached at a distance of 50 mm between the chucks of a tensile tester (UTM-3-100 type manufactured by Orientec Co., Ltd.) at a distance of 50 mm at a temperature of 20 ° C., 65% RH atmosphere, and 1000% strain for 1 minute. Distance between chucks at speed 20
It is stretched to 0 mm, that is, 300% elongation, and is immediately recovered at the same speed and returned to a chuck distance of 50 mm, that is, 0% elongation.
This was repeated three times, and the stress at the third elongation (S) and the stress at the time of recovery (R) were read to calculate R / S.

<Evaluation of spinnability> Spinning was carried out for 1 hour, and it was expressed as good when there was no yarn breakage within 1 hour. When winding was impossible due to frequent yarn breakage in the winding godet roller shape, it was expressed that spinning was impossible. <Wet heat set rate measuring method> The wet heat set rate was determined by the following measurement and mathematical formula. The tension-free and linear elastic yarn length Lw0 is stretched and fixed to 1.5 times the length, then put into a steam box and sealed as it is, and filled with live steam. After 60 seconds while maintaining ± 1 ° C. from the time when the temperature in the steam box reached 120 ° C., the steam in the steam box was discharged, the elastic yarn was immediately taken out, and Lw0 was removed.
Relax well to the following lengths and leave at room temperature for 16 hours. Again, the elastic yarn was set in a non-tensioned and linear state, and when the length at that time was set to Lw1, the set ratio was defined by the following formula. Wet heat setting rate (%) = [(Lw1-Lw0) / Lw0]
× 100

<Dry heat set rate measuring method> The dry heat set rate was determined by the following measurement and mathematical formula. After stretching and fixing the length L0 of the elastic yarn in a tensionless and linear state to a length of 2.0 times, it is passed through a tenter adjusted to 180 ± 1 ° C. as it is, and the passing time of the tenter box is set to 30 seconds. Take out the yarn, relax sufficiently to a length of Ld0 or less, and leave it at room temperature for 16 hours. Again, the elastic yarn was set in a non-tensioned and linear state, and when the length at that time was set to Ld1, the set ratio was defined by the following formula. Dry heat setting rate (%) = [(Ld1-Ld0) / Ld0]
× 100

<Measurement of Dyeability of Acid Dye Raw Fiber> The dyeability of the acid dye raw yarn described in Examples and Comparative Examples was measured by the following method. The elastic fibers were knitted by a knitting machine with 300 needles to obtain an elastic fiber bare tube knitted fabric. Nylon 66 (trade name: Asahi Kasei Leona), 16 denier, 8 filaments were knitted by a 300 knitting tube knitting machine to obtain a nylon 66 bare tube knitted fabric. These bare elastic fiber knitted fabric and nylon 66 bare knitted fabric were dyed in the same bath under the following conditions.

Dyeing conditions Weight ratio Elastic fiber bare tube knitted fabric: Nylon 66 bare tube knitted fabric = 1: 4 Bath ratio 1:20 Heating rate 2 ° C./min Dyeing temperature × time 95 ° C. × 60 minutes Dye recipe NYLOSAN GOLDEN YELLOW N4R
L 0.346% owf NYLOSAN RUBIN N5BL 200% 0.0423% owf NYLOSAN BLUE NGFL 167% 0.111% owf Auxiliary ammonium sulfate 2 g / l Washed with water, washed with running water, dried for 5 minutes, dried naturally at room temperature, dyed, washed with water, dried The dyed elastic fiber bare knitted fabric was subjected to color measurement with a spectrophotometer Macbeth MS-2020 to determine the L value (brightness). The higher the L value, the lighter the color, and the lower the value, the darker the color.

<Measurement of Reactive Dye Raw Fiber Dyeability> The measurement of the reactive dye raw yarn dyeability described in Examples and Comparative Examples was performed by the following method. Elastic fibers were knitted with a needle knitting machine using a 300 needle knitting machine to obtain an elastic fiber bare cylinder knitted fabric. JIS made by Japan Standards Association
Attached white cloth rayon taffeta for dyeing fastness test (JISL
0803). The elastic fiber bare tube knitted fabric and rayon taffeta were dyed in the same bath under the following conditions.

Dyeing conditions Weight ratio Elastic fiber bare tube knitted fabric: rayon taffeta = 1: 4 Bath ratio 1:50 Heating rate 2 ° C./min Dyeing temperature × time 60 ° C. × 30 minutes Dye recipe SUMIFIX BRILLIANT BLUE R SPECIAL 1% owf assistant Glauber's salt 50 g / l Soda ash 15 g / l washing After dyeing Soaping agent (Gran-up PL, manufactured by Sanyo Chemical Co., Ltd.) 2 g / l 80 ° C. × 10 minutes Running in water 5 minutes Drying Room temperature natural drying Dyeing, water washing, drying, The dyed elastic fiber bare knitted fabric was subjected to color measurement with a spectrophotometer Macbeth MS-2020 to determine the L value (brightness). It can be said that the higher the L value is, the lighter the color is and the lower the L value is, the darker the color is.

<Dyeability of Cloth> In Examples and Comparative Examples, the dyeability of the fabric was measured by measuring the surface of the dyed pantyhose leg and the surface of the rayon-bearing sheet itself with a spectrophotometer Macbeth MS-2020. The value (lightness) was determined. It can be said that the higher the L value is, the lighter the color is and the lower the L value is, the darker the color is.

<Measurement of PS Width Setting Ratio and Length Setting Ratio of Pantyhose> Pantyhose was knitted by the methods described in Examples and Comparative Examples, and then set under the following conditions. Foot shape Maximum forefoot width 17.6cm Minimum ankle width 8.5cm Straight line distance from center point of thigh width direction to tip of toe 80.5cm Set temperature 120 ° C Set time 30 seconds

The finished pantyhose is left for 24 hours, and the maximum width of the thigh of the leg: W1 cm, and the linear distance from the center of the thigh in the width direction of the leg to the tip of the toe:
L1 cm was measured, and the PS width set rate and the length set rate were calculated by the following equations. PS width set rate (%) = (W1 / 17.6) × 100 Length set rate (%) = (L1 / 80.5) × 100

<Measurement of Width Setting Ratio of Bare Sheeting> Bare sheeting was knitted by the methods described in Examples and Comparative Examples, and after dyeing, final finishing was performed under the following conditions. Tenter setting pin inner width 185 cm Tenter setting temperature 180 ° C. Tenter passing time 30 seconds The finished bare fabric was allowed to stand for 24 hours, the length Wb1 cm inside the hole of the tenter pin was measured, and the bare fabric width setting ratio was calculated. Bear sheeting width setting rate (%) = (Wb1 / 185) × 10
0

<Shape stability of pantyhose> Ten women who randomly extracted pantyhose were worn, and normal washing for 8 hours was repeated 5 times. 5
The shape of the pantyhose after repeated washing and that of the non-wearing pantyhose were compared, and the grade was determined by visual judgment based on the following criteria and compared with the non-wearing pantyhose. Grade 5: The leg has a contraction ratio of less than 5% in the vertical direction and little change in heel roundness. Grade 4: Less than 5% of the vertical shrinkage of the leg portion, with a slight decrease in roundness of the heel. Class 3: The leg portion has a contraction ratio in the vertical direction of 5% or more and less than 10%, and has a slightly reduced roundness of the heel. Grade 2: A leg whose shrinkage in the vertical direction is 5% or more and less than 10%, and whose heel roundness is considerably reduced. Grade 1: The leg has a contraction rate of 10% or more in the vertical direction, and the heel roundness is considerably reduced.

<Washing Shrinkage of Bare Sheets> The washing shrinkage rate of bare sheets was measured by the JIS-L-1042G method. In addition,
In the following examples, parts mean parts by weight, and% means percent by weight based on the solid content of polyurethane.

[0060]

Example 1 150 parts of polytetramethylene glycol having an average molecular weight of 1,800 and 31.2 parts of 4,4'-diphenylmethane diisocyanate were placed in a stream of nitrogen gas at 95%.
The mixture was reacted with stirring at 90 ° C. for 90 minutes to obtain a prepolymer having an isocyanate group. Then, after cooling to room temperature, 270 parts of dry dimethylacetamide was added and dissolved to obtain a prepolymer solution. On the other hand, 2.34 parts of ethylenediamine and 0.37 parts of diethylamine were dissolved in 157 parts of dry dimethylacetamide, and this was added to the above prepolymer solution at room temperature to give a viscosity of 1,90 parts.
A polyurethane solution of 0 poise (30 ° C.) was obtained.

To the viscous polymer solution thus obtained, 1% by weight of a reaction product of P-cresol, dicyclopentadiene and isobutylene having a molecular weight of about 2300 as an antioxidant and titanium oxide 0 as a lubricant were added to the solid content of polyurethane. 0.5% by weight was dispersed in dimethylacetamide with a homomixer to obtain a uniform spinning solution.
This is designated as spinning dope A. The spinning dope A further comprises polyvinylpyrrolidone, a thermoplastic urethane resin, and a tertiary nitrogen-containing polyurethane added to 100 parts by weight of a polyurethane polymer solid as the addition amount and combination composition described in Table 1, respectively. After defoaming the stock solution, normal dry spinning is performed, and the hot air temperature at the head of the spindle is 320 ° C. and the speed is 60 ° C.
The polyurethane elastic fibers A to F of the present invention were obtained as 15 denier / 2 filament elastic fibers by winding at 0 m / min.

The elastic properties of the obtained elastic fibers A to F are all such that the elongation at break is 600% or more, the stress at an elongation of 300% is 0.2 to 0.8 g / denier, and the elastic fibers are 50% or less.
After immersion in boiling water for 1 hour under elongation, 300% elongation of elastic fiber after exposure for 60 seconds in an atmosphere of dry heat of 120 ° C., elongation 200% elongation after repeating three times (S) and rebound stress The polyurethane elastic fiber having a ratio (R / S) of (R) of 0.1 to 0.8 was a polyurethane elastic fiber suitable for clothing use.

The spinning performance of the obtained polyurethane elastic fiber and the measurement of various physical properties described in the present specification (spinning property
Table 1 shows the results of wet heat setting rate, dry heat setting rate, acid dye original thread dyeing property, and reactive dye original thread dyeing property. However,
Polyvinylpyrrolidone (abbreviated as PVP in the table) has a number average molecular weight of 15,000 and a molecular weight distribution (MWD = 1.42).
Was used. Thermoplastic urethane resin (in the table: TPU
Abbreviated. ) Is 1,4-butanediol, polyoxytetramethylene glycol having a number average molecular weight of 650 (molar ratio 9: 1) and methylene-bis (4-phenylisocyanate) (molar ratio 0.99: 0.11: 1. 0) having a number average molecular weight of 32,000 (urethane group concentration: 4.8 meq / g).

Tertiary nitrogen-containing polyurethane (in the table: NP
Abbreviated as U. ) Is N, N-bis (2-hydroxypropyl) -t-butylamine, N, N-bis (2-hydroxyethyl) -butylamine (molar ratio 45:55) and isophorone diisocyanate (molar ratio 0.495: 0.6
05: 1.000) in a dimethylacetamide solution in the presence of a dibutyltin dilaurate catalyst and having a reduced viscosity of 0.1.

[0065]

Comparative Example 1 Using the spinning dope A of Example 1, as a comparative example of the present invention, a spinning dope added as a combination composition and in the amount added as shown in Table 1 was spun in the same manner as in the present invention to obtain polyurethane elastic fibers. a to g were obtained and compared. However, the polyurethane elastic fiber f in Table 1 was prepared by cooling a polyurethane melt obtained according to Example 14 of JP-B-37-8972 once to 50 ° C., and converting it into a 28% dimethylacetamide solution. As a result of spinning according to Example 1,
And polyurethane elastic fiber g in Table 1 is disclosed in JP-A-51-8.
The results obtained by spinning a dimethylformamide solution of a polyurethane graft-copolymerized with N-vinylpyrrolidone and 2-dimethylaminoethyl methacrylate described in Example 1 of Japanese Patent No. 0392 in the same manner as in the present invention are shown in Table 1. Described. However, the same polyvinylpyrrolidone, thermoplastic urethane resin, and tertiary nitrogen-containing polyurethane were used as in Example 1. The results of the spinning performance and the various physical property measurements (spinning property, wet heat setting rate, dry heat setting rate, acid dye dyeing property, reactive dye dyeing property) described in the present specification of the obtained polyurethane elastic fiber are shown in the table below. It is shown in FIG.

[0066]

[Table 1]

As shown in Table 1, the polyurethane elastic fiber of the present invention to which the specific polyvinylpyrrolidone is added in an effective amount has good spinnability, and excellent setting and dyeing properties. Furthermore, a surprising synergistic effect was observed when used in combination with a specific thermoplastic urethane resin and a tertiary nitrogen-containing polyurethane. On the other hand, polyurethane elastic fibers composed of a conventionally known composition cannot be stably spun due to poor spinnability,
It was found that the polyurethane composition had an elongation at break of less than 300% and was not suitable for clothing use. The level of elastic recovery was not at a satisfactory level.

[0068]

Example 2 166.7 parts of a copolymerized polyether diol having an average number molecular weight of 2,000 and a neopentylene group copolymerization ratio of 10 mol% prepared from tetramethylene glycol and neopentyl glycol, and 4,4'-diphenylmethane diisocyanate 31.2 parts were reacted with stirring at 95 ° C. for 90 minutes in a nitrogen gas stream to obtain a prepolymer having an isocyanate group. Then, after cooling to room temperature, dry dimethylacetamide 2
70 parts were added and dissolved to obtain a prepolymer solution. On the other hand, 2.34 parts of ethylenediamine and 0.37 parts of diethylamine were dissolved in 157 parts of dry dimethylacetamide, and this was added to the prepolymer solution at room temperature to obtain a polyurethane solution having a viscosity of 2,300 poise (30 ° C.). Was.

In the thus obtained viscous polymer solution,
1% by weight of a reaction product of P-cresol, dicyclopentadiene and isobutylene having a molecular weight of about 2300 as an antioxidant and 0.5% by weight of titanium oxide as a lubricant were dispersed in a dimethylacetamide homogen mixer based on the polyurethane solid content. Then, a uniform spinning solution was obtained. This is designated as spinning dope B. The spinning dope B further comprises polyvinylpyrrolidone, a thermoplastic urethane resin, and a tertiary nitrogen-containing polyurethane added to 100 parts by weight of the solid polyurethane polymer as the addition amounts and combination compositions described in Table 2, respectively. By using the stock solution in the same manner as in Example 1, polyurethane elastic fibers G and H were obtained as the polyurethane elastic fibers of the present invention having 15 denier / 2 filaments.

However, the same polyvinylpyrrolidone, thermoplastic urethane resin and tertiary nitrogen-containing polyurethane as in Example 1 were used. Of the obtained polyurethane elastic fiber,
Spinning performance and measurement of the various physical properties described in this specification (spinning property, wet heat setting rate, dry heat setting rate, acid dye dyeing property,
Table 2 shows the results of the reaction dyeing.

[0071]

COMPARATIVE EXAMPLE 2 As a comparative example, Example 2 was performed using the spinning solution B.
The elastic fibers h and i were obtained according to the method described in (1). Table 2 shows the results.
Is shown in Comparative Example 2. As shown in Table 2, the polyurethane elastic fiber of the present invention obtained by adding an effective amount of a specific polyvinylpyrrolidone to a polyurethane polymer using a copolymerized polyether diol as a raw material has good spinnability, setability, Excellent dyeability. Furthermore, a surprising synergistic effect was observed when used in combination with a specific thermoplastic urethane resin and a tertiary nitrogen-containing polyurethane. On the other hand, the performance of polyurethane elastic fibers comprising a conventionally known composition is not at a level where the performance is sufficiently satisfactory.

[0072]

[Table 2]

[0073]

Example 3 Zocchi pantyhose was obtained under the following conditions using the covering yarns of the elastic fibers B, F and H of the examples shown in Tables 1 and 2 for all the leg portions. Covering condition Elastic fiber draft 2.79 times Number of twists 2318 turns / meter Cover yarn Nylon 66 (trade name: Leona Asahi Kasei) 8 denier / 4 filament

Knitting conditions 400 knitting needles knitting machine knitting machine 3.75 inches knitting machine rotation speed 500 rpm total number of leg sections 2540 courses Number of yarn feeder 4 pieces leg section knitting structure smooth

Dyeing conditions Bath ratio 1:20 Heating rate 2 ° C./min Dyeing temperature × time 95 ° C. × 60 minutes Dye recipe NYLOSAN GOLDEN YELLOW N4R
L 0.346% owf NYLOSAN RUBIN N5BL 200% 0.0423% owf NYLOSAN BLUE NGFL 167% 0.111% owf Auxiliary ammonium sulfate 2 g / liter Rinse and wash with running water for 5 minutes Dyeing properties and PS width of these pantyhose fabrics Table 3 shows the set rate and the length set rate. The examples had high dyeing properties, and were excellent in all of the PS width set ratio, the length set ratio, and the form stability. In addition, these pantyhose were good in appearance with brown uniform dough as a whole.

[0076]

Comparative Example 3 A pantyhose was obtained in exactly the same manner as in Example 3 except that the elastic fibers a, e, and i of Comparative Examples shown in Tables 1 and 2 were used. Table 3 shows the results of measuring the dyeability, PS width set ratio, and length set ratio of these pantyhose fabrics. The comparative example has low dyeability,
The S width set ratio, length set ratio, and form stability were all inferior to the examples. Moreover, in these pantyhose, unbleached polyurethane elastic fibers were peeled off in brown fabric, white streaky spots were visible, and the appearance was impaired and the fabric quality was reduced. .

[0077]

[Table 3]

[0078]

Embodiment 4 Elastic fibers B, F, and H shown in Tables 1 and 2
Was used to obtain rayon-bearing bare sheeting under the following conditions. Knitting conditions Knitting machine Kashio 30 inches Knitting machine gauge 40 gauge / inch Number of yarns supplied 36 Companion yarn Rayon 75 denier Knitting structure Smooth Elastic fiber knitting draft 2 times Preset conditions Tenter setting pin inner width 185 cm Tenter setting temperature 180 ° C Tenter passing time 30 seconds

Dyeing conditions Bath ratio 1:20 Heating rate 2 ° C./min. Dyeing temperature × time 60 ° C. × 30 minutes Dye recipe SUMIFIX BRILLIANT BLUE R SPECIAL 1% owf Auxiliaries Glauberite 50 g / L Soda ash 15 g / L Wash After dyeing Soaping agent (Gran Up PL, Sanyo Chemical Co., Ltd.) 2 g / l 80 ° C. × 10 minutes Rinse with running water 5 minutes

Finishing Conditions Tenter setting pin inner width 185 cm Tenter setting temperature 170 ° C. Tenter passing time 30 seconds Table 4 shows the dyeability of the bare fabric and the bare fabric width setting ratio. In the examples, the dyeability was high, and the bare sheet width setting ratio and the washing shrinkage ratio were both excellent. Further, the bare sheeting was dyed on a uniform blue fabric as a whole, and showed a good appearance.

[0081]

Comparative Example 4 a, e, i of Comparative Examples shown in Tables 1 and 2
A bare sheeting was obtained in exactly the same manner as in Example 4 except for using. Table 4 shows the results of measuring the dyeability of these bare fabrics and the width ratio of the bare fabric. In the examples, the dyeability was low, and both the bare sheet width setting ratio and the washing shrinkage ratio were inferior to the examples of the present invention. In addition, when these blue fabrics are stretched, the unbleached polyurethane elastic fibers are noticeable from the fabric when the blue fabric is stretched,
White dot-like streaks appeared and peeling occurred, impairing the appearance and deteriorating the fabric quality.

[0082]

[Table 4]

[0083]

The polyurethane elastic fiber of the present invention is excellent in dyeability, color fastness after washing, and thermoformability, and a product made of a fabric using the polyurethane elastic fiber is excellent in that it does not lose its shape even when worn and washed. It exhibited good shape retention and elastic recovery.

Claims (5)

[Claims] 1. A polyurethane polymer obtained by reacting (a) a polymer diol having hydroxyl groups at both terminal groups with a number average molecular weight of 500 to 5,000, an organic diisocyanate, and a chain extender having a polyfunctional active hydrogen atom, by 100 weight (B) a polyurethane elastic fiber to which (b) 0.1 to 15 parts by weight of polyvinylpyrrolidone having a number average molecular weight of 5,000 to 500,000 is added. 2. (a) 100% by weight of a polyurethane polymer obtained by reacting a polymer diol having hydroxyl groups at both terminal groups with a number average molecular weight of 500 to 5000, an organic diisocyanate and a chain extender having a polyfunctional active hydrogen atom. Parts by weight of (b) polyvinylpyrrolidone having a number average molecular weight of 5000 to 500,000, 0.1 to 15 parts by weight and (c) a linear or branched alkylene group having 2 to 10 carbon atoms, or a divalent The molar ratio (A) / (B) of the low molecular diol (A) having hydrogen groups at both terminals of the alicyclic hydrocarbon group and the high molecular diol (B) having a number average molecular weight of 400 to 3,000 is 1 to 1 99
And a reaction product of an organic diisocyanate and a polyurethane containing 1 to 15 parts by weight of a thermoplastic urethane resin having a number-average molecular weight of 10,000 to 40,000 and having a terminal hydrogen group and a urethane group concentration of 3 meq / g or more. Elastic fiber. 3. (a) 100% by weight of a polyurethane polymer obtained by reacting a polymer diol having a hydroxyl group at both terminal groups with a number average molecular weight of 500 to 5,000, an organic diisocyanate, and a chain extender having a polyfunctional active hydrogen atom. (B) 0.1 to 15 parts by weight of polyvinylpyrrolidone having a number average molecular weight of 5000 to 500,000 and (d) a tertiary nitrogen-containing diol represented by the following general formula (1) and an organic diisocyanate A polyurethane elastic fiber comprising 0.5 to 10 parts by weight of a tertiary nitrogen-containing polyurethane having a hydrogen group at the end and having a reduced viscosity of 0.02 to 0.7. Embedded image (In the formula, R ₁ and R ₂ each represent a linear or branched alkylene group having 1 to 5 carbon atoms, and R ₃ represents a linear or branched alkyl group having 1 to 10 carbon atoms.) 4. A polyurethane polymer obtained by reacting (a) a polymer diol having a hydroxyl group at both terminal groups with a number average molecular weight of 500 to 5,000, an organic diisocyanate and a chain extender having a polyfunctional active hydrogen atom, by 100 weight (B) 0.1 to 15 parts by weight of polyvinylpyrrolidone having a number average molecular weight of 5000 to 500,000, (c) a linear or branched alkylene group having 2 to 10 carbon atoms, or The molar ratio (A) / (B) of the low molecular diol (A) having hydrogen groups at both terminals of the alicyclic hydrocarbon group and the high molecular diol (B) having a number average molecular weight of 400 to 3,000 is 1 to 1 No. 99 and a reaction product of an organic diisocyanate (C), wherein a terminal is a hydrogen group and a urethane group concentration is 3 meq / g or more, and a thermoplastic urethane resin having a number average molecular weight of 10,000 to 40,000 is 1 To 15 parts by weight and (d) a terminal tertiary nitrogen-containing diol represented by the following general formula (1) and an organic diisocyanate having a terminal hydrogen group and a reduced viscosity of 0.02 to 0.7. A polyurethane elastic fiber to which 0.5 to 10 parts by weight of a tertiary nitrogen-containing polyurethane is added. Embedded image (In the formula, R ₁ and R ₂ each represent a linear or branched alkylene group having 1 to 5 carbon atoms, and R ₃ represents a linear or branched alkyl group having 1 to 10 carbon atoms.) 5. An elastic fabric comprising the polyurethane elastic fiber according to claim 1.