JP2002339189A - Stretchable cloth and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a stretchable cloth having excellent dyeability, giving a final product having high quality, suppressed Memuki defect (exposure of urethane fiber on the surface), soft texture and excellent durability and composed of an elastic fiber and a polyamide synthetic fiber. SOLUTION: The stretchable cloth is composed of a polyurethane elastic fiber and a polyamide synthetic fiber. The thermal welding force of the polyurethane elastic fiber in the cloth before dyeing is >=0.100 cN/dtex.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stretchable fabric comprising a polyurethane-based elastic fiber and a polyamide-based synthetic fiber, which is excellent in dyeing processability and gives a finished finished product of good quality.

[0002]

2. Description of the Related Art Stretchable fabrics composed of polyurethane-based elastic fibers and polyamide-based synthetic fibers are mainly used in foundations, socks, swimwear, sportswear, leotards, and the like.
It is used as a stretchable material in clothing in many fields. Polyurethane elastic fibers exhibit an excellent elastic function. However, in the field where the stopping property of the product fabric is particularly required,
For example, in the field of circular knitting such as shorts, the field of warp knitting for inner sports such as brassiere, girdle, and swimwear, and the field of textiles for outerwear such as bottoms, polyurethane-based elastic fibers are used in the form-fixing property and heat-melting during dyeing. Due to poor wearability, it is not finished as expected, resulting in difficulties in wearing and causing a so-called laughing defect (a defect that does not recover as soon as it is released after the fabric is stretched and released). That included the problem.

[0003] Further, since polyurethane-based elastic fibers are fused only at a relatively high temperature, when the processing temperature is increased,
For example, polyamide fibers, which are the main knitting / weaving materials, are yellowed, and the quality of the product is poor due to warp and the like, and it is difficult to obtain a good finished product. Therefore, in order to reduce defects such as warps, strict production control is required in the knitting and inspection processes, and the yield has been significantly reduced. In addition, in the dyeing process, avoid the color tone and solid color
It was necessary to carry out print dyeing in which defects were not noticeable.

[0004] When dyeing a cross-knitted fabric with a polyamide fiber typified by nylon 6 or nylon 66 fiber, the polyurethane-based elastic fiber has the same color as the polyamide fiber depending on the dyeing recipe because of its low dyeing property with an acid dye. The poor elasticity or the non-dyeing of the polyurethane-based elastic fiber causes a problem that the elastic fiber is exposed to the outside of the stretchable fabric, that is, so-called peeling. Elastic fibers of a different color from the polyamide fibers glare to the outside of the fabric due to peeling, or the glaring characteristic of elastic fibers, so-called glaring, occurs, which significantly lowers the grade of the fabric. Is the current situation.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art, to provide excellent dyeing workability (production efficiency and thermal efficiency) and to achieve a finished product quality (warping, laughter defect). It is an object of the present invention to provide a stretchable fabric comprising an elastic fiber and a polyamide-based synthetic fiber, which is excellent in durability, has less peeling, has a soft texture, and has excellent durability.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, a polyurethane elastic fiber obtained by adding a specific urea compound to polyurethane urea and a polyamide-based synthetic fiber. Finding that the object of the present invention is achieved by cross-weaving with fibers,
The present invention has been completed.

That is, the present invention relates to (1) a stretchable fabric composed of a polyurethane-based elastic fiber and a polyamide-based synthetic fiber, wherein the polyurethane-based elastic fiber in the cloth before dyeing has a heat-sealing force of 0.1%. (2) (a) at least one kind of bifunctional amine selected from primary amine and secondary amine, and tertiary nitrogen and complex A nitrogen-containing compound containing at least one nitrogen selected from cyclic nitrogen, (b) an organic diisocyanate, and (c) the aforementioned (a)
And at least one selected from mono- or di-alkyl monoamines having 1 to 10 carbon atoms, alkyl mono-alcohols having 1 to 10 carbon atoms, and organic monoisocyanates for blocking the active terminal of the urea compound obtained from (b). The elastic fabric consisting of polyurethane urea containing 1 to 15% by mass of the urea compound obtained by the reaction with the polyurethane urea, and a stretchable fabric composed of a polyamide synthetic fiber are subjected to 150 to 195 before dyeing. A process of producing a stretchable fabric, wherein the fabric is passed through a presetting process at a temperature of ℃.

[0008] The stretchable fabric of the present invention comprises polyurethane-based elastic fibers and polyamide-based fibers. As the structure of the stretchable fabric of the present invention, for example, bare sheeting, other circular knitting, warp knitting such as Russell, 2-way tricot, plain weave,
There are woven structures such as twill weave and satin weave, and all those having a knitting or weaving structure are included. The heat fusibility of the polyurethane elastic fiber used in the present invention in the fabric before dyeing needs to be 0.100 cN / dtex or more, and preferably 0.120 cN / dtex or more.
If the heat fusion force before dyeing is less than 0.100 cN / dtex, sufficient fusibility of the fabric cannot be obtained at the time of dyeing.
As in the present invention, the fusion force of the polyurethane-based elastic fiber is 0.100 cN / dtex or more, preferably 0.120 cN / dtex.
By setting it to cN / dtex or more, it is possible to reduce defects such as warp lines generated in the finished stretchable fabric.

[0009] The drawbacks of the stretchable fabric, such as warping, are consistently caused in the dyeing process, such as tentering by heat setting in the presetting process, shrinkage by dyeing, and heat setting in the finishing process. It is considered that, when the fabric is repeatedly stretched and shrunk in the process of heat history due to tentering or the like, loops forming the stretchable fabric do not become uniform, which is likely to occur. However, the stretchable fabric of the present invention has a heat-sealing force of 0.100 cN / dtex or more after pre-setting before dyeing, and preferably 0.10 cN / dtex or more.
By using a polyurethane-based elastic fiber of 120 cN / dtex or more, the loop is heat-sealed and fixed at a low temperature, and the loop of the stretchable fabric is hardly deformed. As a result, it is possible to reduce the fluctuation of the width of the fabric due to the elongation and shrinkage of the fabric in the subsequent dyeing and finishing processes, and to reduce warp and laughter (after stretching the fabric while wearing it, release the fabric immediately, A uniform stretchable fabric without defects such as non-recovery defects is formed, and excellent in durability (shrinkage and shape loss due to washing).

[0010] Further, since the loop is heat-sealed and fixed at a low temperature, the temperature of the pre-setting step before dyeing can be reduced, and the dyeing processability (production efficiency, thermal efficiency) can be reduced.
Is improved, and the heat deterioration of the polyamide fiber can be suppressed, so that a stretchable fabric having a soft texture can be finished. In order to prevent improper mold stopping during fabric processing, curling of the end of the fabric, and to prevent shrinkage and shape collapse due to washing in the product, the setting rate of the polyurethane-based elastic fiber used in the present invention is 30% or more. Is preferable, and 50% or more is more preferable. At the time of processing the fabric, the polyurethane elastic fiber is fully stretched by heat, that is, 100% or less is preferable in order to prevent so-called settling and to prevent a reduction in power and elongation recovery function of the product.

The set ratio is obtained by the following measuring method. 1/30 g / dtex (d
tex is nominally decitex), a test yarn having a length of 5 cm is passed under a 100% elongation with a pin tenter set at 160 ° C under a 100% elongation for a passage time of 60 seconds.
After standing for 16 hours in an atmosphere of 0 ° C. and 65% RH, the yarn length L (cm) when an initial load of 1/30 g / dtex (dtex is a nominal decitex) is applied to the polyurethane elastic fiber is read. The set rate (%) is calculated from the following equation. Set rate (%) = [(L-5) / 5] × 100

The blue L value of the polyurethane elastic fiber used in the present invention is preferably from 20 to 35. Although the details will be described later, the blue L value is the lightness of a polyurethane-based elastic fiber bare fabric (a fabric using bare polyurethane elastic fibers) when dyed with a specific blue dye. The lighter the color, the smaller the color. If the blue L value exceeds 35, the color of the polyurethane-based elastic fiber when it is dyed is light, and the fabric is likely to be peeled off. If the blue L value is less than 20, the color develops too deeply, so that it looks darker than the color of the polyamide synthetic fiber that is the mating material, and the color of the polyurethane elastic fiber prevails on the surface of the cloth, and the color of the entire cloth There is a risk of breaking the balance.

The heat-resistant and strong retention of the polyurethane elastic fiber used in the present invention is preferably at least 30%, more preferably at least 50%, from the viewpoint of preventing a decrease in durability when worn. In the stretchable fabric of the present invention, the mixing ratio of the polyurethane-based elastic fiber can take a very wide range depending on the structure of the fabric and the thickness of the yarn used, but the stretchability of the polyurethane-based elastic fiber is sufficiently exhibited. Is preferably 0.5% by mass or more, and the dye distribution ratio at the time of dyeing is appropriately maintained, the color development of the polyamide-based synthetic fiber is prevented from lowering, and the power of the fabric is prevented from being excessively increased by 35% by mass. The following is preferred.

The yarn form of the polyurethane-based elastic fiber used in the present invention is such that, even in the state of a bare yarn, a polyurethane-based elastic fiber such as a coated elastic yarn, a core spun yarn, and a trouser twist yarn is substantially used as a core and a polyamide-based synthetic fiber is used. It may be in the state of a coated yarn that is twisted to form a sheath. The coated yarn is produced by, for example, covering, spinning, twisting, or the like. The mainstream of woven fabrics is used in the form of coated elastic yarn, core spun yarn, and spun twist yarn, especially when the inelastic fiber to be coated is a transparent yarn or the number of twists is small.
Since the effect of the color of the polyurethane-based elastic fiber appears strongly, the color-developing effect of the polyurethane-based elastic fiber used in the present invention is remarkably exhibited when cross-knitting is performed. In the case of inner underwear and direct knit in-pantyhose, polyurethane-based elastic fibers are often used in a bare state such as bare sheeting. In recent years, some woven fabrics have also started to be used in a bare state, and when used in this state, the probability of polyurethane-based elastic fibers coming out on the fabric surface becomes higher than when used in a coated state. The coloring effect of the urethane-based elastic fibers used in (1) is remarkably exhibited.

The polyurethane elastic fiber used in the present invention is produced by presetting a polyurethane elastic fiber containing the following urea compound at 150 to 195 ° C. before dyeing. The urea compound contained in the polyurethane elastic fiber comprises (a) at least one selected from a primary amine and a secondary amine, and at least one selected from a tertiary nitrogen and a heterocyclic nitrogen. A nitrogen-containing compound containing one kind of nitrogen, (b) an organic diisocyanate, and (c) a block for blocking the active terminal of the urea compound obtained from (a) and (b).
It can be produced by reacting at least one selected from mono- or dialkyl monoamines having 1 to 10 carbon atoms, alkyl monoalcohols having 1 to 10 carbon atoms and organic monoisocyanates.

It is necessary to adjust the molar equivalent ratio of the above (a), (b) and (c) so that no active terminal remains in the obtained urea compound, and then to carry out the reaction. The urea compound contains a tertiary nitrogen skeleton represented by the chemical formula (4) and a urea bond represented by the chemical formula (1) or (2) or a urethane bond represented by the chemical formula (3) in a molecule.

[0017]

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[0018]

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[0019]

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[0020]

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The urea compound is classified into two types of structures satisfying the above formulas (1) to (4) by selecting the above (c). That is, when (c) is a mono- or dialkylmonoamine or an alkylmonoalcohol, the chemical formula (5):

[0022]

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Wherein a is a bifunctional amine comprising at least one selected from primary amines and secondary amines, and at least one nitrogen selected from tertiary nitrogen and heterocyclic nitrogen. A nitrogen-containing compound, b is an organic diisocyanate, c is a mono- or di-alkyl monoamine having 1 to 10 carbon atoms or an alkyl mono-alcohol having 1 to 10 carbon atoms, n is 1 or more) (c) is an organic mono-isocyanate Is the chemical formula (6)

[0024]

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Wherein a is a bifunctional amine comprising at least one selected from primary amines and secondary amines, and at least one nitrogen selected from tertiary nitrogen and heterocyclic nitrogen. Nitrogen-containing compound, b is an organic diisocyanate, c is an organic monomonoisocyanate, n is 1
As described above, a more preferable structure is a case where (c) is an organic isocyanate represented by the chemical formula (6).

The urea compounds having these two structures are:
It is preferable to use them alone, but they can also be used as a mixture. (A) a bifunctional amine comprising at least one selected from a primary amine and a secondary amine and at least one selected from a tertiary nitrogen and a heterocyclic nitrogen used for producing a urea compound Examples of the nitrogen-containing compound containing nitrogen include N-butyl-bis (2-aminoethyl) amine, N-butyl-bis (2-aminopropyl) amine, N-butyl-bis (2-aminobutyl) amine, N, N-bis (2-aminoethyl) -isobutylamine, N, N-bis (2-aminopropyl)-
Isobutylamine, N, N-bis (2-aminoethyl)
-T-butylamine, N, N-bis (2-aminoethyl) -1,1-dimethylpropylamine, N, N-bis (2-aminopropyl) -1,1-dimethylpropylamine, N, N-bis (2-aminobutyl) -1,1-dimethylpropylamine, N- (N, N-diethyl-3-
Aminopropyl) -bis (2-aminoethyl) amine,
N- (N, N-dibutyl-3-aminopropyl) -bis (2-aminopropyl) amine, piperazine, piperazine derivative such as 2-methylpiperazine, 1- (2-aminoethyl) -4- (3-amino Propyl) piperazine, 2,5- and 2,6-dimethylpiperazine, N,
N'-bis (2-aminoethyl) piperazine, N, N '
-Bis (3-aminopropyl) piperazine, N- (2-
Piperidine derivatives such as aminoethyl) piperazine, N-amino- (2-aminoethyl) -4-methylpiperazine, for example, 4-aminoethylpiperidine, N-amino-
4- (2-aminoethyl) piperidine, N-bis (2-
Aminoethyl) amine-piperidine and other pyrrolidone derivatives such as N-amino-4- (2-aminoethyl) -2
-Pyrrolidone, N- (3-aminopropyl) -4- (3
-Aminopropyl) -2-pyrrolidone, N-bis (2-
(Aminoethyl) amine-2-pyrrolidone and the like. Preferred nitrogen-containing compounds are piperazine and piperazine derivatives. In particular, N- (2-aminoethyl) piperazine and N- (2-aminopropyl) piperazine, which have extremely good solubility of the obtained urea compound in amide solvents, are preferred. These can be used alone or as a mixture.

The (b) organic diisocyanate used for producing the urea compound includes trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, and 3-methyldiisocyanate. Hexane-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, it is an alicyclic diisocyanate such as isophorone diisocyanate or 4,4'-dicyclohexylmethane-diisocyanate. These can be used alone or as a mixture.

Examples of the monoamine having an alkyl group having 1 to 10 carbon atoms (c) used for producing the urea compound include isopropylamine, n-butylamine, t-butylamine, diethylamine and 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.

Examples of the (c) mono-alcohol having an alkyl group having 1 to 10 carbon atoms used for producing the urea compound include methanol, ethanol, 2-
Examples thereof include propanol, 2-methyl-2-propanol, 1-butanol, 2-ethyl-1-hexanol, and 3-methyl-1-butanol. These can be used alone or as a mixture. The above mono- or dialkylamines and alkyl alcohols can be used alone or in combination. Preferably, it is used alone.

The organic monoisocyanate (c) used for producing the urea compound includes n-butyl isocyanate, phenyl isocyanate, 1-naphthyl isocyanate, p-chlorophenyl isocyanate,
Examples include cyclohexyl isocyanate, m-tolyl isocyanate, benzyl isocyanate, and m-nitrophenyl isocyanate. These can be used alone or as a mixture. However, it cannot be mixed with the above-mentioned mono- or dialkylamine and alkyl alcohol. When these are mixed, a compound in which the active hydrogen of a mono- or dialkylamine or an alkyl alcohol is blocked by an organic monoisocyanate is generated, and the effective amount of the urea compound having the structure of the chemical formula (5) or (6) is reduced. In addition, it bleeds out in the processing step of the polyurethane elastic fiber and causes scum that stains the knitting machine and the dyeing bath.

(C) used for obtaining a urea compound to be added to the polyurethane-based elastic fiber includes (a) and (b)
Used for blocking the active terminal (amino group or isocyanate group) of the urea compound obtained from the above. As a result, it is possible to prevent the spinning stability and the robustness of the polyurethane elastic fiber from being deteriorated due to the active terminal of the urea compound.
When the reaction molar equivalent is (a)> (b), since the terminal of the urea compound is an amino group, an organic monoisocyanate is selected as (c), and when (a) <(b), urea is used. Since the terminal of the compound is an isocyanate group, a mono- or dialkylamine or an alkyl monoalcohol is selected as (c). In the present invention, it is preferable to select an organic monoisocyanate.

The urea compound to be added to the polyurethane-based elastic fiber used in the present invention has the chemical formula (1) or (2)
And 2 to 40 urethane bonds represented by the chemical formula (3) in one molecule.

[0033]

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[0034]

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[0035]

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When (c) is a mono- or di-alkyl monoamine having 1 to 10 carbon atoms or an alkyl mono-alcohol having 1 to 10 carbon atoms, the structure of the urea compound is represented by the chemical formula (5) (where n in the structure is 1 that's all).

[0037]

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A urea compound having a desired number of urea bonding units can be obtained by adjusting the molar ratio of the charged components (a), (b) and (c). That is, (a):
If adjustment is made so that (b) :( c) = n: n + 1: 2, the number of urea bond units present in one molecule is n + 3 for mono or dialkyl monoamine, and n + 1 for alkyl mono alcohol. When (c) is an organic monoisocyanate, the structure of the urea compound is represented by the chemical formula (6) (n in the structure is 1 or more).

[0039]

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At this time, (a) :( b) :( c) = n +
If adjusted so as to be 1: n: 2, the number of urea bond units present in one molecule is n + 3.

From the viewpoint of imparting a good heat setting property to the polyurethane elastic fiber and a good heat fusion property by presetting before dyeing, the urea compound is contained in one molecule in the number of the urea bonding units or the urethane bonding units described above. The number is preferably 2
40, more preferably 4 to 15. In terms of the number of polymerization repetitions n in the structure, it is 1-37 for mono- or dialkylmonoamines and organic monoisocyanates, and 3-39 for alkylmonoalcohols. By setting the number of urea bond units or the number of urethane bond units in this range, bleed out of the urea compound can be reduced,
The generation of scum that stains a knitting machine or a dyeing bath can be suppressed, and yarn breakage or the like during production of polyurethane elastic fibers can be prevented.

The stretchable fabric of the present invention is obtained by pre-setting at 150 to 195 ° C. before dyeing a fabric obtained by knitting or weaving a polyurethane-based elastic fiber containing the urea compound and a polyamide-based synthetic fiber. It is manufactured by passing through a process. If the temperature of the presetting step is lower than 150 ° C., a heat fusion force of 0.100 cN / dtex or more cannot be obtained after passing through the presetting, and a long time presetting is required to increase the heat fusion force. When the temperature of the presetting step exceeds 195 ° C., the stretchability and power, which are the characteristics of the elastic fabric, are lost due to the high-temperature treatment, and the characteristics of the elastic fabric are lost. The quality of the obtained product is not stable due to the occurrence of warping and the like. A similar phenomenon occurs with a long preset.

The urea compound to be added to the polyurethane urea is produced by the following method. The number of urea bond units present in one molecule of the urea compound is adjusted by the molar ratio of the charged reactants (a), (b) and (c). Reaction temperature is 2
0-60 ° C is preferred. The reaction is preferably performed in an amide-based polar solvent in which polyurethaneurea is dissolved, for example, in dimethylformamide, dimethylacetamide, or N-methylpyrrolidone. When a solvent that does not dissolve polyurethaneurea is used, a solid content is taken out after the reaction, dissolved in a solvent in which polyurethaneurea is dissolved, and added to the polyurethaneurea.

As an example of the reaction method, (a)
2 mol of N- (2-methylamino) piperazine, (b)
1 mol of isophorone diisocyanate, (c)
2 mol of phenyl isocyanate was dissolved to form a 50% by mass dimethylacetamide solution,
C. and react for 2 hours. The reaction is carried out by dropping isophorone diisocyanate and phenyl isocyanate dropwise into N- (2-methylamino) piperazine dissolved in dimethylacetamide, but is not limited thereto. Can be used. At this time, the number of repeated polymerizations n of the urea compound obtained is 1, and the number of urea bond units existing per molecule is 4.

The polyurethane-based elastic fiber used in the present invention can be obtained by dry spinning a spinning solution obtained by adding a urea compound dissolved in an amide-based polar solvent to a polyurethane urea solution. The addition can be carried out at any stage from the completion of the polymerization of the polyurethane urea to the spinning. The addition amount of the urea compound to be added to the polyurethane elastic fiber may be any amount as long as the setting property and the dyeing property required for the product fabric can be sufficiently satisfied and the excellent elastic function and spinning stability are not impaired. 1 to 15% by mass
Is more preferable, and more preferably 2 to 10% by mass. When the added amount of the urea compound is less than 1% by mass, the effects of heat setting property, heat fusing property and dyeing property are small. On the other hand, if it exceeds 15% by mass, the heat setting effect and the heat fusing effect are saturated and the dyeing fastness is liable to be lowered, the spinning stability is lowered due to yarn breakage during spinning, and the strength, elongation and elasticity are reduced. Elastic functions such as recovery are easily damaged.

In addition, a known heat setting property improving agent can be added. For example, at least one kind of a 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 amount of the thermoplastic polymer and the urea compound of the present invention is not more than 15% by mass, and the amount of the thermoplastic polymer preferably does not exceed the amount of the urea compound of the present invention. .

The reason why the polyurethane elastic fiber containing a urea compound exhibits excellent heat-sealing property and dyeing property without sacrificing at least the elastic function and spinning stability is not clear, but is considered as follows. Can be The first is the effect of a specific nitrogen-containing compound having excellent dyeing properties and fastness, and the second is the effect of a urea compound containing a specific number of urea bond units. In other words, the dyeability and fastness are excellent,
A nitrogen-containing compound containing at least one bifunctional amine selected from a primary amine and a secondary amine and at least one selected from a tertiary nitrogen and a heterocyclic nitrogen is used as an acid dye or a disperse dye; This is considered to be the effect of strongly adsorbing and holding. It is considered that the excellent heat setting property and heat fusing property are due to the effect of the urea compound having 2 to 40 urea bonding units in one molecule.

The polyurethane-based elastic fiber is composed of a segmented polymer having a urethane bond and a urea bond. In particular, the urea bond forms an extremely strong hydrogen-bonding physical crosslink to 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 is difficult to perform thermal fusion.

The urea compound contained in the polyurethane-based elastic fiber forms a urea bond and a strong hydrogen bond in the polyurethane-based elastic fiber, and assimilates with the crystalline domain in the polyurethane-based elastic fiber. Is expressed. However, this urea compound has an effect of lowering the glass transition temperature of the crystalline domain, and at high temperatures, the hydrogen bond is broken, and the crystalline domain easily flows through the heat. Polyurethane-based elastic fiber having excellent If the amount of the urea compound added to the polyurethane-based elastic fiber is too small, the heat setting effect is insufficient. Conversely, if the addition amount is too large, the heat fusion effect will be sufficiently satisfactory, but the glass transition temperature of the crystalline domain will be too low, and a heat flow will occur at a high temperature during spinning, making it impossible to secure spinning stability. Not only that, but also the elastic function is impaired.

Polyurethane urea, which is a raw material of the polyurethane elastic fiber of the present invention, has hydroxyl groups at both ends and has a number average molecular weight of 600 to 5,000, a polymer glycol having a number average molecular weight, an organic diisocyanate, a chain extender of a diamine compound, and a monoamine compound. Manufactured from an endblocker.

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 used for the polyurethane urea, for example, all of the aliphatic, alicyclic and aromatic diisocyanates 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-
Examples thereof include hexamethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, a mixture thereof, and a copolymer thereof. Preferably, it is 4,4'-diphenylmethane diisocyanate.

The diamine compound of the chain extender used for the polyurethane urea includes, for example, ethylenediamine,
1,2-propylenediamine, 1,3-diaminocyclohexane, 2-methyl-1,5-pentadiamine, hexamethylenediamine, triethylenediamine, m-xylylenediamine, piperazine, o-, m- and p-phenylenediamine And diamines having a urea group described in JP-A-5-155841 or mixtures thereof. Preferably, ethylenediamine alone or an ethylenediamine mixture containing 5 to 40 mol% of at least one selected from the group consisting of 1,2-propylenediamine, 1,3-diaminocyclohexane, and 2-methyl-1,5-pentadiamine is there.

Examples of the terminal amine terminator monoamine compound used in the polyurethane urea include monoalkylamines such as isopropylamine, n-butylamine, t-butylamine and 2-ethylhexylamine, or diethylamine, diisopropylamine and di-n-butylamine. And dialkylamines such as di-t-butylamine, 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 a monoamine compound.

As the polyurethane urea, a known polyurethane urea-forming reaction technique can be used. For example, an excess molar amount of organic diisocyanate is reacted with a polyalkylene ether glycol having a number average molecular weight of 600 to 5000 in an amide polar solvent to prepare an intermediate polymer having a terminal isocyanate group. 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.

The polyurethane-based elastic fiber used in the present invention is obtained by spinning a spinning solution containing 1 to 15% by mass of the urea compound of the present invention with respect to polyurethane urea. In addition to the urea compound of the present invention, the spinning dope contains known polyurethane urea elastic fibers, polyurethane elastic fibers, and organic or inorganic compounding agents useful for polyurethane compositions, such as ultraviolet absorbers, antioxidants, and light stabilizers. Agent,
Gas-resistant anti-coloring agents, coloring agents, matting agents, lubricants and the like can be added simultaneously or sequentially.

The polyurethane urea spinning solution thus obtained is formed into a fibrous shape by a known dry spinning method, wet spinning method, or the like, and a polyurethane elastic fiber can be produced. As the spinning method, dry spinning which exhibits an excellent elastic function and is excellent in productivity is preferable. The obtained polyurethane-based elastic fiber has a larger decitex per single yarn, which is advantageous for improving the heat setting property. Preferably, it is 5.6 to 33 decitex per single yarn. This is considered to be due to the large relaxation of the orientation of the crystal part in the fiber. If it is less than 5.6 dtex, the orientation becomes large, and if it exceeds 33 dtex, the orientation relaxation is small, but the crystal size becomes large, and the crystal flow during heat setting becomes difficult to occur.

The resulting polyurethane-based elastic fibers were treated with polydimethylsiloxane, polyester-modified silicone, polyether-modified silicone, amino-modified silicone, mineral oil,
Mineral fine particles, for example, silica, colloidal alumina, talc, etc., higher fatty acid metal salt powders, for example, magnesium stearate, calcium stearate, etc., higher aliphatic carboxylic acids, higher aliphatic alcohols, paraffin, solid wax at room temperature such as polyethylene, etc. May be used alone or in combination as needed.

The polyurethane-based elastic fiber-containing stretchable fabric of the present invention can be used for swimwear, girdle, bra, 2.54 cm.
Mate products, various stretch foundations such as underwear, socks mouth rubber, tights, waistband, bodysuits, spats, stretch sportswear, stretch outerwear, bandages, supporters, medical wear, stretch lining, disposable diapers and other materials Can be used.

[0060]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described by way of examples. Various measurement methods used in the present invention are as follows. (1) Breaking strength, breaking elongation Tensile tester (UTM-III 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 -100 type (trademark), and the breaking strength (g) and the breaking elongation (%) are measured.

(2) Heat Fusing Force A polyurethane-based elastic fiber is knitted by a draft knitting machine with a number of needles of 370 and a diameter of 3 / 42.54 cm with a draft of 2.5 times to obtain a tubular knitted fabric of elastic fiber. . The obtained elastic fiber tubular knitted fabric is passed under a preset temperature at a preset temperature of 100% with a pin tenter for a passing time of 60 seconds, and then a tensile tester (UTM-III- manufactured by Orientec Co., Ltd.).
100 (trademark)), the distance (sample length) between the upper chuck and the lower chuck was adjusted to 10 cm, the tubular knitted fabric was set on the upper chuck, and the yarn was removed from the end of the tubular knitted fabric by the sample length of 1 cm.
Pull out to 0cm and set it on the lower chuck, 50c
The yarn is pulled at a speed of m / min, and the pull-out stress P1 (cN) when the yarn is pulled out from one end of the tubular knitted fabric is measured.

The method for measuring the decitex of the polyurethane elastic fiber is as follows. 1/30 g / dtex for polyurethane elastic fiber (dtex is nominal decitex)
And cut to a length of 100.0 cm. 1
The mass of 10 elastic fibers cut to a length of 00.0 cm, that is, the mass for a length of 1000.0 cm was measured with an electronic balance of 4 digits g after the decimal point.
Zero times, that is, the number of grams converted to a mass of 10,000 m is defined as decitex. The heat fusing force is determined by the following equation. Thermal fusion force (cN / dtex) = extraction stress P1 / decitex

(3) Blue L value 1 g of a tubular knitted fabric of elastic fibers under the same conditions as in the method for measuring the thermal fusion force.
Get. Furthermore, for JIS dyeing fastness test (JIS L
0803) 4 g of nylon-attached white cloth is collected and dyed and fixed in the same bath under the following conditions. Dyeing conditions Dye KayanolMillingBlue2RW
(Nippon Kayaku Co., Ltd.) 1.3% owf Nylon attached white cloth weight 4 g Elastic yarn fiber bare yarn knitted fabric weight 1 g Bath ratio 20: 1 Ammonium sulfate 2 g / L Temperature rising rate 2 ° C./min Temperature, Time 95 ℃ × 60min

[0064]

For dyeing and fixing, soft water having a Ca ion concentration of 3 ppm or less through a softener was used consistently.
The dyeing machine is a mini color dyeing machine (trademark, Texam Giken Co., Ltd.)
Company). After dewatering the dyed elastic fiber knitted fabric and air-drying at room temperature for 12 hours, the knitted fabric is folded in three, that is, the L value (brightness) is measured with a Macbeth colorimeter in a state where six knitted fabrics are stacked.

(4) Heat-resistant strength retention rate 1/30 g / dtex (dte)
x is the nominal length of 5c when the initial load of decitex is applied
m is passed through a pin tenter for 60 seconds at a preset temperature under 100% elongation,
Furthermore, after leaving for 16 hours in an atmosphere of 20 ° C. and 65% RH, relax, and measure the strength S1 (g) by the method (1). Assuming that the yarn strength before heat setting is S0, the heat resistant strength retention rate is represented by the following equation. Heat resistant strength retention = [S1 / S0] × 100 (%)

(5) Reinforcing The sample was tilted at 45 degrees, and the stretchable fabric was compared with a standard sample of five stages by a counter having a light source on the back and a partly polished glass judgment plate. The intensity of the streaks and plaques is determined by the transmitted light by comparing with the standard sample of the following five stages. Grade 5: No warping, no spots. Grade 4: Transmuscular, spots are thin and slightly generated. Grade 3: Transmuscular, spotted and thin. Grade 2: Transmuscular, slightly spotty. Grade 1: Transmuscular, spotted, and frequent.

(6) Laughter defect The stretchable fabric is cut to a length of 100 mm in the warp direction × 90 mm in the weft direction, and sewn in the weft direction with a two-needle overlock having a seam allowance of 7 mm. The sewing thread is Woolly nylon 210d,
A test piece is prepared with the number of needles being moved to 13 needles / 2.54 cm. Next, the test piece was washed with a weak alkaline synthetic detergent 0.13.
After immersion sufficiently in a 10% aqueous solution, the sample is subjected to an expansion / contraction fatigue tester with a chuck interval of 70 mm around the seam, and is repeatedly subjected to expansion and contraction 10,000 times at a predetermined expansion and contraction amount (described later). Grade 5: The test piece has almost no change from before being subjected to the stretching fatigue tester. Grade 4: The test piece is slightly wide and the appearance is slightly rough. Grade 3: The test piece is slightly wide and the appearance is slightly rough. Grade 2: The test piece has a large width, and the appearance is rough and the structure is displaced. Grade 1: The test piece has a wide appearance, has a rough appearance such as misalignment or broken elastic fiber, and is unsuitable as a commercial product.

The amount of elongation of the test piece when applied to the stretching fatigue tester is determined as follows. 20 through stretch fabric
0mm, cut into a size of 25.4mm weft, stretched by a Tensilon tensile tester at an initial load of 5g on the test piece, a chuck interval of 100mm, and a pulling speed of 300mm / min.
The elongation rate under a load of 9.8 N and the elongation rate under a load of 14.7 N are determined, and the amount of elongation is determined by the following equation. Elongation amount (%) = [(elongation rate under load of 9.8 N) + (elongation rate under load of 14.7)] / 2

(7) Laddering The stretchable fabric is stretched in the longitudinal direction 17
After cutting to a length of 0 mm x 90 mm in the weft direction, using a longitudinal direction as an elongation direction, and using a stretching fatigue tester with a chuck interval of 70 mm, repeating the expansion and contraction 10,000 times at an amount of expansion and contraction of 100%, the test piece was removed, and the following standard was used. evaluate. Grade 5: The test piece has almost no change from before being subjected to the stretching fatigue tester. Grade 4: The test piece is slightly wide and the appearance is slightly rough. Grade 3: The test piece is slightly wide and the appearance is slightly rough. Grade 2: The test piece has a large width, and the appearance is rough and the structure is displaced. Grade 1: The test piece is wide and the appearance is considerably rough due to misalignment or breakage of elastic fibers, which is unsuitable as a commercial product.

(8) Curl The stretchable fabric is cut into a length of 10 mm in the warp direction × 100 mm in the weft direction and a length of 100 mm in the warp direction × 10 mm in the weft direction, left for 4 hours, and visually evaluated according to the following criteria. Level 5: Flat and the whole surface reaches the floor. Grade 4: Slightly loose ends. Class 3: Both ends are raised (10 mm or less). Grade 2: Twist only part of the center or both ends reach the floor. Grade 1: The twist is remarkable, and it becomes spiral.

(9) Texture The handling is determined based on the following criteria. Grade 5: The texture is soft and very smooth. Grade 4: Soft texture and smooth texture. Grade 3: Soft texture, comparable to the same tissue product using nylon fiber. Grade 2: The texture is slightly hard. Grade 1: Hard texture, unsuitable as a commercial product.

(10) Stripping The finished stretchable fabric is visually judged to determine the stripped state as 1
From the 5th grade. Grade 5: Polyurethane-based elastic fibers can not be recognized at all on the surface. Grade 4: Polyurethane-based elastic fibers cannot be confirmed at the surface but glare can be slightly recognized. Recognizable on the surface. Second grade: Recognizable that polyurethane-based elastic fiber is on the surface. Further, it can be recognized that the color is different from the color of the mating yarn. It can be confirmed that the polyurethane fiber is exposed, and it can be recognized that it is not dyed or white

(11) Molding performance A stretchable cloth was fixed in a relaxed state without any slack between two fixtures having a thickness of 2 cm and hollowed to a diameter of 15 cm. A hemispherical hot iron ball is pushed into the fabric and pressed so that the depth becomes 10 cm. Immediately after 60 seconds, the hot iron ball is extracted. After standing for 12 hours at 20 ° C. × 65% RH in the shape of a shaped bump, the height of the bump to the apex is measured, and the appearance before and after processing is evaluated according to the following criteria. Grade 5: Almost no change in appearance. Grade 4: The appearance is slightly rough. Grade 3: The appearance is slightly rough. Grade 2: Roughness in appearance and organizational deviation occurred. Grade 1: Appearance is considerably rough due to misalignment or breakage of elastic fiber, which is unsuitable as a commercial product.

[0075]

Example 1 1,500 g of polytetramethylene ether glycol having a number average molecular weight of 1,800 and 312 g of 4,4′-diphenylmethane diisocyanate were reacted while stirring at 60 ° C. for 90 minutes in a stream of nitrogen gas.
A polyurethane prepolymer having an isocyanate group was obtained. Then, 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 to obtain a polyurethaneurea solution having a viscosity of 3,200 poise (30 ° C.). Was.

To the polymer solution thus obtained, 1.5 mass% of an isobutylene adduct of a polyadduct of p-cresol and dicyclopentadiene, N, N-bis (2-hydroxyethyl) -t-butylamine 5%, 2- (2'-hydroxy-3 ', 5-dibenzyl-phenyl) -benzotriazole 0.3%, magnesium stearate 0.1%.
5% by mass and 4% by mass of a urea compound composed of N- (2-aminoethyl) piperazine, isophorone diisocyanate and phenyl isocyanate (molar ratio 2: 1: 2) and having 4 urea bond units. And JP-A-7
5% by mass of a polyurethane polymer described in JP-A-316922 was added to prepare a spinning stock solution. The spinning solution was spun by a dry spinning method to obtain a polyurethane urea elastic fiber of 44 dtex (hereinafter referred to as elastic fiber A).

This elastic fiber A was drafted 2.5 times lower,
Nylon 66 (registered trademark, Leona manufactured by Asahi Kasei Corporation) 4
4dtex / 34f is covered with a twist of 300 T / M to form a weft, and the warp is nylon 66 (registered trademark, Leona manufactured by Asahi Kasei Corporation) 44 dtex / 34f (twist 120
0T / M) and the density (warp × weft) is 130 lines / 2.
A plain fabric of 54 cm × 110 / 2.54 cm was woven. This was refined at 60 ° C. for 20 minutes, then preset at 160 ° C. for 30 seconds and dyed. Staining is LanasynBla
ckS-DL (trademark, manufactured by Clariant Co., Ltd.) 4% o
The wf and the fix were 6% owf of HiFix SL (trademark, manufactured by Dainippon Pharmaceutical Co., Ltd.), and all other conditions were in accordance with the conditions except for the fabric mass condition described in (3) Blue L value measurement method. went. This fabric was final set at 150 ° C. for 30 seconds and finished.

[0078]

Embodiment 2 In the embodiment 1, the preset temperature is set to 160.
The same processing was performed except that the temperature was set to 30 ° C. × 30 seconds.

[0079]

Embodiment 3 In Embodiment 1, the preset temperature was set to 180.
The same processing was performed except that the temperature was set to 30 ° C. × 30 seconds.

[0080]

Embodiment 4 In Embodiment 1, the preset temperature was set to 195.
The same processing was performed except that the temperature was set to 30 ° C. × 30 seconds.

[0081]

Example 5 1,590 g of polytetramethylene ether glycol having a number average molecular weight of 2,500 and 318 g of 4,4′-diphenylmethane diisocyanate were reacted at 85 ° C. in a nitrogen gas stream to obtain 4,4′-diphenylmethane. A polyurethane prepolymer having a diisocyanate group terminal was obtained. Next, 3,050 g of dimethylacetamide was added and dissolved therein, and 39 g of ethylene glycol was added as a chain extender, followed by reaction at 90 ° C. for 6 hours. Further, as a terminal blocking agent, butanol 20
g was added to obtain a polyurethane solution. Next, 0.8% silicone as an additive and NH-15
0 (trademark, manufactured by Nippon Hydrazine Co., Ltd.) at 0.65%
0.33% of Sumiiza-GA-80 (trademark, manufactured by Sumitomo Chemical Co., Ltd.) and 0.12% of Sumithorp 300 # 622 (trademark, manufactured by Sumitomo Chemical Co., Ltd.) were applied, and the spinning solution was used. Spinning was performed by a dry spinning method to obtain a polyurethane elastic fiber (hereinafter, referred to as elastic fiber B) of 44 dtex. In Example 4, the above-mentioned elastic fiber B was used instead of the elastic fiber A.
Processing was carried out in the same manner as in Example 4 except that No. was used.

[0082]

Example 6 Nylon 66 (Leona (registered trademark) manufactured by Asahi Kasei Corporation) 44 dtex / 34f was used as a front,
The elastic fiber A was warped at a draft rate of 80% on the back, and a half structure was knitted under the following conditions. The knitted fabric obtained under these knitting conditions was refined at 90 ° C. for 1 minute, and was preset and dyed in the same manner as in Example 4 to obtain a two-way warp knitted fabric. The finished two-way warp knitted fabric had a basis weight of 170 g / m ² and a thickness of 0.6 mm.

[0083]

Example 7 Processing was performed in the same manner as in Example 6 except that elastic fiber B was used instead of elastic fiber A in Example 6, and processing was finished.

[0084]

Example 8 Nylon 66 (Leona (registered trademark) manufactured by Asahi Kasei Corporation) at 44 dtex / 34f front, polyurethane polyurea elastic fiber (Loica (registered trademark) HS manufactured by Asahi Kasei Corporation) 280 dtex at middle, elastic fiber A was placed on the back and the knitted fabric was knitted under the following conditions. The polyurethane polyurea elastic fiber was stretched by 80% and warped.

<Knitting conditions> Knitting machine: 28 gauge / 2.54 cm Russell knitting machine Organization: Front 20/02/20/24/42/24 Middle 00/44/22/66/22/44 Back 00 / 22/00/22/00/22 ・ Runner length: Front 114cm / 480 course Middle 14cm / 480 course Back 10cm / 480 course ・ On-board course: 70 courses / 2.54cm After refining for a minute, pre-setting, dyeing and final setting were performed in the same manner as in Example 4 to obtain a Russell knitted fabric.

[0086]

Ninth Embodiment A processing was performed in the same manner as in the eighth embodiment except that the elastic fiber B was used instead of the elastic fiber A in the eighth embodiment.

[0087]

Example 10 The finished knitted fabric obtained in Example 6 was
Molding was performed at 0 ° C. to finish.

[0088]

Embodiment 11 Processing was completed in the same manner as in Embodiment 8 except that elastic fiber B was used instead of elastic fiber A in Example 10.

[0089]

Comparative Example 1 In Example 1, the preset temperature was set to 140
The same processing was performed except that the temperature was set to 30 ° C. × 30 seconds.

[0090]

Comparative Example 2 In Example 1, the preset temperature was set to 210
The same processing was performed except that the temperature was set to 30 ° C. × 30 seconds.

[0091]

Comparative Example 3 In the production of the polyurethane urea elastic fiber of Example 4, the urea compound 4 having 4 urea bond units was used.
Polyurethane urea elastic fiber 44dtex (hereinafter referred to as elastic fiber C) was spun under the same conditions except that no% was added. Processing was performed in the same manner as in Example 4 except that the above-mentioned elastic fiber C was used instead of the elastic fiber A in Example 4, and finished.

[0092]

Comparative Example 4 Processing was performed in the same manner as in Example 6 except that elastic fiber C was used in place of elastic fiber A in Example 6, and finishing was performed.

[0093]

Comparative Example 5 Processing was carried out in the same manner as in Example 8 except that elastic fiber C was used instead of elastic fiber A in Example 8, and finished.

[0094]

Comparative Example 6 Processing was performed in the same manner as in Example 10 except that elastic fiber C was used instead of elastic fiber A in Example 10, and finishing was performed. Tables 1, 2, 3, 4, and 5 show the evaluation results of the above examples and comparative examples. As is clear from the table, the stretchable fabric of the present invention had no warp, had good setting properties, and was of high quality. Furthermore, there was no laughter, no peeling, and the texture was soft. The moldability was good, and the effect of preventing peeling was further improved.

[0095]

[Table 1]

[0096]

[Table 2]

[0097]

[Table 3]

[0098]

[Table 4]

[0099]

[Table 5]

[0100]

The stretchable fabric of the present invention has excellent workability, good finished product quality, little peeling, soft texture, and excellent durability. In particular, the stretchable fabric of the present invention is excellent in moldability for molding by heat, and is excellent in the effect of preventing peeling because polyurethane fibers jump out from the stitches that have widened when molding is performed to the surface.

 ──────────────────────────────────────────────────続 き Continued from the front page F term (reference)

Claims (3)

[Claims] 1. A stretchable fabric comprising polyurethane-based elastic fibers and polyamide-based synthetic fibers, wherein the polyurethane-based elastic fibers in the fabric before dyeing have a heat-sealing force of 0.10.
Stretchable fabric characterized by being at least 0 cN / dtex. 2. A nitrogen containing at least one bifunctional amine selected from a primary amine and a secondary amine and at least one nitrogen selected from a tertiary nitrogen and a heterocyclic nitrogen. (B) an organic diisocyanate; and (c) a mono- or di-alkyl monoamine having 1 to 10 carbon atoms for blocking the active terminal of the urea compound obtained from (a) and (b). An elastic fiber made of polyurethane urea containing 1 to 15% by mass based on polyurethane urea of a urea compound obtained by reacting at least one selected from alkyl monoalcohols and organic monoisocyanates of formulas 1 to 10, Stretchable fabric made of polyamide-based synthetic fiber is passed through a presetting process at 150 to 195 ° C. before dyeing to produce a stretchable fabric. Construction method. 3. The elasticity of the urea compound, wherein the urea compound contains 2 to 40 urethane bonds represented by the chemical formula (1) or (2) or urethane bonds represented by the chemical formula (3) in a molecule. Fabric manufacturing method. Embedded image Embedded image Embedded image