JP2001214341A - Stretchable fabric excellent in dyeability - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an elastic fabric comprising cellulose fibers polyurethane- urea elastic fibers excellent in heat setting properties without exhibiting the exposure of the polyurethane-urea elastic fibers to the surface and a glittering appearance in dyed products. SOLUTION: This stretchable fabric comprises polyurethane-urea elastic fibers modified with cellulose fibers and a urea compound and simultaneously satisfies >=40% and <=75% heat setting ratio and >=40 and <=60 blue L value The fabric contains the polyurethane-urea elastic fibers having <=10% deterioration ratio of the blue L value in an amount of >=0.5 and <=35 mass % in the fabric.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stretch fabric having excellent heat setting properties and excellent dyeability.

[0002]

2. Description of the Related Art A polyurethane polyurea elastic fiber obtained by subjecting an isocyanate-terminated prepolymer synthesized from a polyalkylene ether glycol and an excess of organic diisocyanate to a chain extension with a diamine is a polyamide fiber, a polyester fiber, cotton or rayon. In the form of a cross-knitted woven fabric mixed with a counterpart fiber material such as cellulosic fiber, it is a stretchable functional material used for clothing in various fields such as foundations, socks, pantyhose, swimwear, sportswear and leotards.

[0003] Polyurethane polyurea elastic fibers are elastic fibers in which hard segments comprising urea groups form strong hydrogen-bonding physical crosslinks and exhibit excellent elastic functions. However, polyurethane urea elastic fiber fabric products are particularly required in the fields where mold stopping properties are particularly required, for example, socks for leggings such as zokki pantyhose and tights, circular knitting and warping for inner sports such as brassiere, girdle and swimwear. When processing products in the field of outer fabrics such as knitting and bottoms, polyurethane-polyurea elastic fibers with poor heat-setting properties are not finished as large as the type, making it difficult to wear, and the edges of the fabric are curled (a phenomenon in which the fabric is curled round and round). ) And it is difficult to sew. In connection with this problem, it is necessary to set a plurality of times in order to perform a desired width on the elastic fiber fabric, and in addition, it is necessary to set at a relatively high temperature. There is also the problem of inferiority.

On the other hand, polyurethane elastic fibers (elastic fibers comprising only urethane bonds) and polyetherester elastic fibers (elastic fibers having no urea group such as polyester obtained by copolymerizing a polyalkylene ether glycol component) are polyurethane-polyurea elastic fibers. Compared with polyurethane fiber, it has excellent heat setting property and good mold stopping performance of product fabric, but has no hard segment consisting of urea group, so the strength drop after processing is larger than that of polyurethane polyurea elastic fiber. There is a problem in durability as an elastic fiber material.

[0005] Polyurethane urea elastic fibers are inferior in dyeing properties of polyurethane urea fibers when dyeing composite yarns or composite fabrics using cellulosic fibers or cotton as a mating fiber for dyeing with cellulose dye. To
Depending on the dyeing recipe, the so-called "peel-off" phenomenon, in which the elastic fibers appear to be exposed to the outside of the composite fabric after dyeing, due to the fact that the same color with the cellulosic fiber or cotton is remarkably inferior or not dyed. And there is a disadvantage that the product becomes unsightly. When the peeling phenomenon appears on the mixed fabric of the elastic fiber and the cellulose fiber, the elastic fiber of a different color from the flickering and the cellulosic fiber on the surface of the fabric makes the face look into the face, or a glaring called a glare peculiar to the elastic fiber. The gloss is conspicuous, and the appearance quality of the fabric is significantly reduced. In particular, there is a problem that the exposure of the elastic fiber becomes larger as the composite elastic fiber component is more excellent in heat setting property and the mold stopping property of the product fabric is better, and the deterioration of the quality due to peeling increases. .

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a dyed product which is excellent in heat setting property and which suppresses the appearance of peeling and glare when dyed by a general-purpose dyeing method for cellulose fibers. Another object of the present invention is to provide a composite elastic fabric obtained by mixing cellulose fibers and polyurethane urea fibers.

[0007]

Means for Solving the Problems The present applicant first added a urea compound containing at least four urea binding units represented by the following formulas (1) and (2) to a polyurethane urea elastic fiber. By doing so, the heat setting property of the polyurethane urea elastic fiber and the dyeing property for acid dyes were found to be improved, and a patent application was filed in Japanese Patent Application No. 11-75303.

[0008]

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The present inventor has found that polyurethane urea elastic fibers to which the above-mentioned urea compound is added can be fast dyed to almost any dyeing concentration by a direct dye, a reactive dye or the like generally used for dyeing cellulose fibers. As a result, the present invention was conceived. That is, the present invention comprises a cellulose fiber and a polyurethane polyurea elastic fiber, has a heat setting ratio of 40% or more and 75% or less, and has a blue L value of 40 or more and 6% or less.
It is a stretchable fabric that simultaneously satisfies the condition of 0 or less, and contains 0.5% to 35% by weight of a polyurethane polyurea elastic fiber having a blue L value deterioration rate of 10% or less.

[0010] The stretchable fabric of the present invention is a knitted or woven fabric obtained by mixing a cellulose fiber and a polyurethane urea elastic fiber and combining them to exhibit stretchability.
A knitted or woven fabric obtained by cross-weaving or cross-knitting a polyurethane urea elastic fiber in the form of a bare yarn or an elastic fiber yarn in the form of a processed yarn compounded by processing such as coating, entanglement, or twisting, or knitting of the processed yarn described above. It can be a textile.

In the present invention, the cellulose fiber is a cellulosic fiber such as natural cellulose fiber represented by cotton, cuprammonium rayon, viscose rayon, acetate rayon and the like. A mixed elastic fabric is obtained by mixing by entanglement and twisting. The stretchable fabric of the present invention contains at least 8% by mass of a cellulose fiber component, and thus can be dyed into an elastic fabric having no glare and a glare-free appearance using a dye that dyes the cellulose fiber such as a reactive dye.

The polyurethane polyurea elastic fiber used in the present invention is prepared by a known polyurethane polyurea reaction technique, that is, a reaction of an excess mole of organic diisocyanate 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 an isocyanate group at the terminal, and then add a chain extender and a terminal terminator to an amide-based polar solvent containing the intermediate polymer, and react them by a wet or wet method to give a polyurethane polyurea polymer. A known polyurethane urea elastic fiber obtained by applying dry spinning, wherein 1 to 15 mass of a urea compound containing at least 4 urea binding units represented by the above formulas (1) and (2) in the molecule. %
A modified polyurethane urea elastic fiber having a heat set rate and a blue L value and a blue L value deterioration rate due to a reactive dye as defined above. Here, the heat set rate, the blue L value and the blue L value deterioration rate are performances related to the processing performance of the polyurethane urea elastic fiber defined below. [1] Heat setting rate Heat setting rate (%) = {(L−5) / 5} × 100 (3) (However, from a polyurethaneurea elastic fiber immersed in boiling water for 30 minutes in a relaxed state, a tension-free, linear 5cm elastic fiber
Collect and use this as the initial long fiber sample. After placing the initial long fiber sample in a 100% stretched state under 120 ° C. pressurized steam for 15 seconds, it is dried at 120 ° C. in a drier for 30 seconds, and then allowed to shrink in a 50 ° C. atmosphere for 1 hour (day after day). Change acceleration treatment), and then the sample was placed in an atmosphere of 20 ° C. and 65% RH 16
The length of the sample after standing is read, and this is defined as the fiber length (L) after the heat treatment. [2] Blue L value White cloth attached to rayon for JIS color fastness test (JIS L
0803) and 1 g of a tubular knitted fabric of bare polyurethane urea elastic fiber (30 dtex / 1f) (one-necked circular knitted fabric, 370 needles, yarn feeding elongation ratio 2.8 times), and a mini color dyeing machine (Texam Giken Bath ratio using the same bath
At 50, Sumfix brilliant blue
e R Special (reactive dye: CI Reac
fiveDye Blue 19) Stain at a staining concentration of 1% omf, followed by soaping. After dehydrating the dyed sample of polyurethane urea elastic fiber, it is dried at room temperature for 12 hours to prepare a dyed tube knitted sample. Using a Macbeth color machine, measure the L value (brightness) of Hunter chromaticity by folding the dyed tube knitted sample into three pieces (equivalent to six layers of cloth) (wavelength of measurement light 360
７740 nm (every 20 nm)), and this is defined as a blue L value.

Dyeing conditions: Na ₂ SO ₄ 50 g / l Na ₂ CO ₃ (input after heating up to 60 ° C.) 15 g / l Heating rate 2 ° C./min Temperature, time (time after heating up) 60 ° C., 30 minutes Soaping conditions: Gran up PL 2 g / l (Sanyo Chemical: soaping agent) Bath ratio 1: 100 Heating rate 2 ° C / min Temperature, time (time after heating) 80 ° C, 30 minutes [3] Blue L Value deterioration rate (%) The dyed tube knitted sample prepared by measuring the blue L value is JIS-L
A washing test in accordance with -0884 was applied, and after the washing test sample was dehydrated, dried at room temperature for 12 hours. After drying, the sample was folded in three (corresponding to six dough layers) using a Macbeth color machine.
Hunter-Measure L value (brightness) of chromaticity (wavelength of measurement light 36
0 to 740 nm (every 20 nm)), and a value obtained by using the following equation is defined as a boo L value deterioration rate.

The urea compound added to the polyurethane urea elastic fiber used in the present invention includes (a) a bifunctional amine comprising at least one of a primary amine and a secondary amine, a tertiary nitrogen and A nitrogen-containing compound containing at least one heterocyclic nitrogen, and (b) an organic diisocyanate, and (c) one selected from the group consisting of mono- or dialkylmonoamines, alkylmonoalcohols, and organic monoisocyanates. It is a urea compound obtained by the reaction.

The elastic fabric of the present invention must contain the polyurethane urea elastic fiber in an amount of 0.5% to 35% by weight in the fabric. When the mixing ratio of the polyurethane urea elastic fiber is less than 0.5% by weight, it is difficult to exhibit the stretching properties of the polyurethane polyurea elastic fiber of the fabric. On the other hand, when the mixing ratio is more than 35% by weight, the fiber in the dyeing bath at the time of dyeing is used. The distribution ratio of the dye to the dye is lost, so that it is difficult to dye mixed fibers such as cellulose fibers at a desired dyeing concentration, to make post-processing of the fabric difficult, or to stretch the fabric more than necessary. The preferable mixing ratio of the polyurethane urea elastic fiber varies depending on the weaving and knitting structure of the elastic cloth, but is 0.5% by mass or more and 5% by mass or less for woven fabric, 5% by mass or more and 25% by mass or less for circular knitted product, 15 mass% or more and 35 mass% or less for Russell dough, and 5 mass% or more and 25 mass% or less for leg materials such as pantyhose. Here, the mixing ratio refers to the content ratio of polyurethane polyurea elastic fibers contained in the finished fabric before sewing, but in the case of an elastic cloth that takes the form of a secondary product immediately after knitting, such as pantyhose, the panty portion And the content of the polyurethane polyurea elastic fiber component in the weight including the entire leg portion.

Hereinafter, the present invention will be described in detail. The elastic fabric of the present invention is excellent in setting properties and is a composite fabric in which a polyurethane urea elastic fiber modified to be able to be dyed firmly with a dye capable of dyeing a cellulose fiber, for example, a direct dye or a reactive dye, is mixed with the cellulose fiber. Therefore, by using a practical dyeing method widely used for cellulose fiber fabrics, the appearance of the peeling appearance and the glare appearance is suppressed, and a dyed elastic fabric with a good appearance can be easily produced.

In the present invention, the mixing of the polyurethane urea elastic fiber and the cellulose fiber can be performed by applying any known complex processing means. Regardless of which composite processing means is applied, the polyurethane urea elastic fiber is 1 to 15% by mass, preferably 2 to 10% by mass of the polyurethane urea polymer constituting the fiber. A bifunctional amine comprising at least one of a primary amine and a secondary amine, a nitrogen-containing compound comprising at least one of a tertiary nitrogen and a heterocyclic nitrogen,
By including (b) an organic diisocyanate and (c) a urea compound obtained by reacting with a mono- or dialkyl monoamine, an alkyl mono-alcohol, and one selected from the group of organic mono-isocyanates, a composite fabric is obtained. It has been modified to satisfy the required levels of heat setting property and dyeability for reactive dyes. If both of the urea compounds exceed 15% by weight, not only does the heat setting effect saturate and the dyeing fastness deteriorates, but also the spinning stability decreases due to spun yarn breakage, and the strength and elongation are reduced. Also, the elastic function such as elastic recovery is impaired.

The set ratio of the polyurethane polyurea elastic fiber used in the present invention is 40% to 75% or less. 40
%, Sufficient dough setting property cannot be obtained, and setting at a desired dough size requires a high-temperature setting and a long setting time. Conversely, if the set ratio is too large and exceeds 75%, the set will be too effective and the fabric will not be glued, the waist will be lost, and the stretchability, elongation and power, which are the characteristics of stretchable fabrics using polyurethane polyurea elastic fibers, will be lost. And loses its properties as a dough.

The polyurethane urea elastic fiber used in the present invention is added with a urea compound so that the dyeability with respect to the reactive dye satisfies the Blue L value and the Blue L deterioration rate of 40 to 60 and 10% or less, respectively. Blue L value means Sumino Bri, a blue reactive dye
liant Blue R Special (reactive dye, CI Reactive Dye Blue 1)
9; manufactured by Sumitomo Chemical Co., Ltd.) The color density of the polyurethane polyurea elastic fiber dyed in the coexistence of cellulose fiber is represented by a colorimetric lightness value. The higher the L value, the lighter the color. Indicates darkness. If the blue L value is greater than 60, the color of the polyurethane polyurea is thin, and the peeling of the fabric is liable to occur. If the value is less than 40, the color is too dark, so it looks darker than the color of the cellulosic fiber or cotton of the mating material, In some cases, the color of the polyurethane polyurea elastic fiber prevails on the surface of the fabric, thus breaking the color balance of the entire fabric. Further, the blue L value deterioration value indicates the selection fastness of the above-mentioned dyeing.

The urea compound to be added to the polyurethane polyurea elastic fiber used in the present invention comprises: (a) a bifunctional amine comprising at least one of a primary amine and a secondary amine; Reacting a nitrogen-containing compound containing at least one of the cyclic nitrogens with (b) an organic diisocyanate, (c) a mono- or dialkyl monoamine, an alkyl mono-alcohol, or an organic mono-isocyanate; The reaction product obtained by The reaction is performed by adjusting the molar equivalent ratio of (a), (b) and (c) in the reaction so that no active terminal remains in the urea urea compound.

The urea compound contains a tertiary nitrogen skeleton represented by the following formula (3) and a urea bond represented by the following formulas (4) and (5). However, when an alkyl monoalcohol is reacted, a urethane bond represented by the following formula (6) is also included.

[0022]

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The urea compound to be added to the polyurethane polyurea elastic fiber used in the present invention has two kinds of structures (n in the formulas) satisfying the structures of the above formulas (3) to (6) depending on the selection of the starting compound (c) to be used. Is one or more polymerization repetitions).

[0024]

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A more preferred structure is a case where (c) represented by the formula (8) is an organic isocyanate. These urea compounds having two types of structures are preferably used alone, but may be used as a mixture. (A) a bifunctional amine comprising at least one of a primary amine and a secondary amine used to obtain a urea compound;
Examples of the nitrogen-containing compound containing at least one of tertiary nitrogen and heterocyclic 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 derivatives such as 2-methylpiperazine, 1- (2-aminoethyl) -4- (3-aminopropyl) piperazine,
2,5- and 2,6-dimethylpiperazine, N, N '
-Bis (2-aminoethyl) piperazine, N, N'-bis (3-aminopropyl) piperazine, N- (2-aminoethyl) piperazine, N-amino- (2-aminoethyl) -4-methylpiperazine and the like , Piperidine derivatives such as 4-aminoethylpiperidine, N-amino-4-
Pyrrolidone derivatives such as (2-aminoethyl) piperidine, N-bis (2-aminoethyl) amine-piperidine,
For example, 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 may be used alone or as a mixture.

(B) used to obtain a urea compound
Examples of the organic diisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 3-methylhexane-1,6-diisocyanate, and 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, alicyclic diisocyanates such as isophorone diisocyanate and 4,4'-dicyclohexylmethane-diisocyanate are preferred. These may be used alone or as a mixture.

(C) used to obtain a urea compound
As the mono or dialkyl monoamine of the formula,
A monoamine having 10 alkyl groups, for example,
Isopropylamine, n-butylamine, t-butylamine, diethylamine, 2-ethylhexylamine, diisopropylamine, di-n-butylamine, di-t-
Butylamine, di-isobutylamine, di-2-ethylhexylamine and the like. Further, the alkyl chain may contain a tertiary nitrogen atom or an oxygen atom. For example, 3-dibutylamino-propylamine, 3-diethylamino-propylamine, 3-ethoxypropylamine, 3- (2-ethylhexyl) Oxy) propylamine. These may be used alone or as a mixture.

Further, the alkyl monoalcohol (c) used for obtaining the urea compound may have 1 carbon atom.
A monoalcohol having an alkyl group of 10 to 10, for example, methanol, ethanol, 2-propanol,
-Methyl-2-propanol, 1-butanol, 2-ethyl-1-hexanol, 3-methyl-1-butanol and the like. 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. Further, the organic monoisocyanate (c) used to obtain the urea compound includes n-butyl isocyanate, phenyl isocyanate, 1-naphthyl isocyanate, p-chlorophenyl isocyanate, cyclohexyl isocyanate, and m- Tolyl isocyanate, benzyl isocyanate, m-nitrophenyl isocyanate and the like can be mentioned. These isocyanate compounds can be used alone or as a mixture. However,
It cannot be mixed with the above-mentioned mono- or dialkylamines and alkyl alcohols. A compound in which the active hydrogen of a mono- or dialkylamine or an alkyl alcohol is blocked by an organic monoisocyanate not only reduces the effective amount of the urea compound having the structure of the formula (7) or (8), but also decreases the fiber content. In the processing step, the blocking compound bleeds out of the polyurethane polyurea elastic fiber and causes scum which stains the knitting machine and the dyeing bath.

The compound (c) used to obtain the urea compound used in the present invention is selected from the above three kinds as described above, and the active terminal (amino) of the urea compound obtained from the compound (a) and the compound (b) is used. Group or isocyanate group). This active terminal deteriorates the spinning stability of the polyurethane polyurea elastic fiber and decreases the fastness. When the reaction molar equivalent is (a)> (b), the terminal of the urea compound is an amino group, so that (c) selects an organic monoisocyanate, and when (a) <(b), the terminal of the urea compound is Is an isocyanate group (c)
Needs to select at least one of a mono- or dialkylamine and an alkyl monoalcohol. Preferably,
As described above, this is a choice of the organic monoisocyanate.

The urea compound used in the present invention is characterized in that the number of urea binding units represented by the following formulas (1) and (2) is 4 to 40 in one molecule.
When the compound (c) is a mono- or dialkylmonoamine or an alkylmonoalcohol, the structure of the urea compound is represented by the above formula (7) (n in the structure represents one or more polymerization repetitions). The urea compound having a number can be obtained by adjusting the molar ratio of the charged compounds (a), (b) and (c). That is, (a) :( b) :( c) =
When adjusted so that n: n + 1: 2, the average number of urea bond units present in one molecule is n + 3 for mono or dialkyl monoamine, and n + for alkyl mono alcohol.
It becomes 1.

When the compound (c) is an organic monoisocyanate, the structure of the urea compound is represented by the above formula (8) (n in the structure represents one or more polymerization repetitions). At this time, (a) :( b) :( c) = (n + 1): n: 2
By adjusting so that the average urea bond unit number existing in one molecule is n + 3. Urea compound to be added to the polyurethane polyurea elastic fiber used in the present invention,
The number of urea bonding units present in one molecule is in the range of 4 to 40. When converted to the average number of repeating polymerizations n in the structure,
1 to 37 for mono- or dialkyl monoamines and organic monoisocyanates, 3 to 3 for alkyl monoalcohols
39. If the average number of urea bond units is less than 4 or more than 40, sufficient heat setting properties cannot be obtained. On the other hand, when the average number of urea bonding units is less than 4, bleeding out of the polyurethane polyurea elastic fibers in the fabric processing step may cause scum that stains the knitting machine or the dyeing bath. further,
If the average number of urea bonding units exceeds 40, the urea compound precipitates in the polyurethane polyurea spinning solution to cause breakage of the spun yarn, or the elongation of the polyurethane polyurea elastic fiber is reduced, whereby the elastic function is impaired. The preferred average number of urea bonding units is 4 to 4 per molecule of the urea compound.
Fifteen.

The average number of urea bonding units present in one molecule of the urea compound to be added to the polyurethane polyurea elastic fiber used in the present invention can be adjusted by the reaction charge molar ratio of the compounds (a), (b) and (c). . Reaction temperature is 2
0-60 ° C is preferred. The reaction is preferably carried out in an amide-based polar solvent in which the polyurethane polyurea polymer dissolves, for example, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, or the like. When a solvent that does not dissolve the polyurethane polyurea polymer is used, a solid content is taken out after the reaction, dissolved in a solvent in which the polyurethane polyurea polymer is dissolved, and added to the polyurethane polyurea polymer.

As an example of the reaction method, 2 mol of N- (2-methylamino) piperazine is used as the compound (a), 1 mol of isophorone diisocyanate is used as the compound (b), and phenyl isocyanate is used as the compound (c). The reaction is carried out at 50 ° C. for 2 hours so that the mole becomes a 50 mass% dimethylacetamide solution. The reaction is carried out by dropping isophorone diisocyanate and phenyl isocyanate dropwise into N- (2-methylamino) piperazine dissolved in dimethylacetamide, but the reaction method is not limited to this. Other known methods can be used. The average number of repeated polymerizations n of the urea compound obtained at this time is 1, and the average number of urea bond units existing per molecule is 4.

The urea compound prepared as described above is dissolved in an amide-based polar solvent, added to a polyurethane polyurea polymer solution, and used as a spinning solution by dry spinning or wet spinning. Modified polyurethane urea elastic fibers can be obtained. The addition can be performed at any stage from the completion of the polymerization of the polyurethane polyurea polymer to the spinning.

The heat setting property of the polyurethane urea elastic fiber can be given a higher level of heat setting property by adding another improvement technique. For example, JP-A-7-
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 316922 may be simultaneously contained. In this case, the total amount of the thermoplastic polymer and the urea compound of the present invention is preferably 15% by mass or less, 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 polyurea elastic fiber containing a urea compound used in the present invention exhibits excellent heat setting property and dyeing property without sacrificing elastic function and spinning stability at least is mainly due to the dyeing property. It is presumed to be due to the action of a specific nitrogen-containing compound having excellent fastness, and secondly to the action of a urea compound containing a specific number of urea bond units.
That is, the dyeing property and the fastness are excellent because a bifunctional amine comprising at least one of primary amine and secondary amine and a nitrogen-containing amine containing at least one of tertiary nitrogen and heterocyclic nitrogen are used. This is the effect of the compound adsorbing and holding the dye. Also, the excellent heat setting property is
This is the effect of a urea compound having 4 to 40 urea binding units in one molecule.

The polyurethane polyurea elastic fiber is a segmented polymer having a urethane bond and a urea bond. Among them, urea bonds form extremely strong hydrogen bonding physical cross-links to form crystalline domains, and are excellent at room temperature. While exhibiting an elastic function, even at a high temperature, the hydrogen bond is hardly broken, so that heat setting is hardly performed.
The urea compound of the present invention having the number of urea bond units specified and specified, generates a strong hydrogen bond and a urea bond in the polyurethane polyurea elastic fiber, assimilate with the crystalline domain in the polyurethane polyurea elastic fiber, At room temperature, it becomes a polyurethane polyurea elastic fiber exhibiting an excellent elastic function. However, the urea compound of the present invention 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 is easily heated, so that the polyurethane polyurea elastic fiber excellent in heat setting property is obtained. Becomes If the addition amount of the urea compound of the present invention to the polyurethane polyurea elastic fiber is too small, the heat setting effect becomes insufficient. Conversely, if the addition amount is too large, the heat setting effect will be sufficiently satisfactory,
The glass transition temperature of the crystalline domain is too low, causing a heat flow at a high temperature during spinning to not only ensure spinning stability, but also impair the elastic function.

The polyurethane polyurea polymer of the polyurethane polyurea elastic fiber used in the present invention has a hydroxyl group 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. Manufactured from compound endblockers. As the polymer glycol, various diols composed of substantially linear homo- or copolymer, for example, polyester diol, polyether diol,
Polyester amide diol, polyacryl diol,
Examples thereof include 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, tetramethylene group and 2,2
Examples thereof include copolymerized polyether glycols composed of 2-dimethylpropylene groups, copolymerized polyether glycols composed of tetramethylene groups and 3-methyltetramethylene groups, and mixtures thereof. Among them, showing excellent elastic function,
Polytetramethylene ether glycol and copolymerized polyether glycol comprising a tetramethylene group and a 2,2-dimethylpropylene group are preferred.

The organic diisocyanate used in the polyurethane polyurea polymer of the polyurethane polyurea elastic fiber used in the present invention is, for example, an aliphatic, alicyclic or aromatic diisocyanate in an amide polar solvent under the reaction conditions. Any of those which are soluble or liquid can be applied. For example, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate,
2,4- and 2,6-tolylene diisocyanate, m-
And p-xylylene diisocyanate, α, α, α ′,
α'-tetramethyl-xylylene diisocyanate,
4,4′-diphenyl ether diisocyanate, 4,
4'-dicyclohexyl diisocyanate, 1,3- and 1,4-cyclohexylene diisocyanate, 3-
(Α-isocyanatoethyl) phenyl isocyanate, 1,6-hexamethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, a mixture thereof, or a copolymer thereof, and the like. Can be Preferably,
4,4'-diphenylmethane diisocyanate.

The diamine compound of the chain extender used in the polyurethane polyurea polymer of the polyurethane polyurea elastic fiber used in the present invention includes, for example, ethylenediamine, 1,2-propylenediamine, 1,3-diaminocyclohexane, 2-methyl-1 , 5-pentadiamine,
Hexamethylenediamine, triethylenediamine, m-
Xylylenediamine, piperazine, o-, m- and p-
Examples thereof include phenylenediamine, diamines having a urea group described in JP-A-5-155841, and 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 polyurea polymer of the polyurethane polyurea elastic fiber used in the present invention include, for example, isopropylamine, n-butylamine, t-butylamine and 2-amine.
Monoalkylamines such as ethylhexylamine, or dialkylamines such as diethylamine, diisopropylamine, di-n-butylamine, di-t-butylamine, di-isobutylamine, and di-2-ethylhexylamine are used alone or in combination. Can be used. Also, 1,1-dimethylhydrazine can be used as a mixture with the monoamine compound.

For the polyurethane polyurea polymer, a known polyurethane polyurea 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, a polyurethane polyurea polymer is obtained by adding and reacting a chain extender and a terminal terminator to the amide-based polar solvent containing the intermediate polymer.

The polyurethane polyurea 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 a polyurethane polyurea polymer. In the spinning dope, in addition to the urea compound of the present invention, a known polyurethane polyurea elastic fiber,
Polyurethane elastic fibers, organic or inorganic compounding agents useful in polyurethane compositions, such as UV absorbers, antioxidants, light stabilizers, gas-coloring inhibitors, coloring agents, matting agents, lubricants, etc. simultaneously or It can be added sequentially.

The polyurethane polyurea polymer spinning solution thus obtained can be formed into a fibrous shape by known dry spinning, wet spinning, or the like to produce polyurethane polyurea elastic fibers. Dry spinning, which exhibits excellent elasticity and is excellent in productivity, is preferred. In the polyurethane polyurea elastic fiber thus obtained, the larger the decitex per single yarn, the better 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. This is because the orientation is large at less than 5.6 dtex and the orientation relaxation is small at more than 33 dtex, but the crystal size becomes large and the crystal flow during heat setting becomes difficult to occur. This is not limited to polyurethane polyurea elastic fibers, but is applicable to all types of elastic fibers.

After spinning, the polyurethane polyurea elastic fiber is coated with polydimethylsiloxane, polyester-modified silicon, polyether-modified silicon, amino-modified silicon, mineral oil, mineral fine particles such as silica, colloidal alumina, talc, etc. For example, magnesium stearate, calcium stearate and the like,
An oil agent such as a solid wax at room temperature such as a higher aliphatic carboxylic acid, a higher aliphatic alcohol, paraffin, or polyethylene may be applied alone or in an optional combination as needed.

The elastic fabric of the present invention can be a composite fabric including all mixed forms of cellulose fibers and polyurethane urea elastic fibers. The elastic fabric is a knit or a woven fabric, and its knitting structure or woven structure is arbitrarily selected according to the use of the fabric. The form in which the polyurethane urea fiber is compounded in the fabric structure includes a form of bare yarn and a form of composite processed yarn such as a covering yarn. A typical example of processing into a fabric in the form of bare yarn is a woven fabric using a knitted fabric obtained by plating or the like and a weft using bare yarn. Covering method, spinning method, ply twist method, spun twist method, etc., in which a bare polyurethane elastic fiber yarn such as a coated elastic yarn or a core spun yarn is used as a core fiber and formed into a sheath coating layer in a twisted state of cellulose fiber (yarn). The elastic fabric of the present invention also includes a knitted fabric obtained by knitting or weaving the composite processed yarn alone or by cross-knitting with another cellulose fiber yarn. Processing of elastic fabrics. Depending on whether the embodiment is a knitted or knitted fabric using bare yarn or a knitted or woven fabric using coated yarn.

Examples of knitted materials diversified into elastic fabrics include:
Examples include a plain weave of bare bears, warp knitting such as circular knitting, Russell, and two-way tricot, and examples of woven fabrics include woven fabrics of any knitting and woven structures such as plain weave, twill weave, and satin weave. Naturally, these stretch knitted fabrics are used in various types of stretch foundations, such as swimwear, girdle, brassiere, intimate products, and underwear.
Applying processing means such as sewing to various products such as sock mouth rubber, tights, pantyhose, waistband, body suit, pats, stretch sportswear, bandages, supporters, medical wear, stretch lining, disposable diapers, etc. The next product. Elastic fabrics are sometimes prepared in the form of secondary products on a knitting machine, such as pantyhose, swimwear and the like.

In any case, the stretchable fabric of the present invention
Depending on the form of the fabric, it can be widened, rope-shaped, or 2
In the form of the next product, it can be processed by a Wins dyeing machine or the like which is a dyeing method widely used for cellulose fiber fabrics. Then, after dyeing, it is finished through a setting step for molding into a widened state or a secondary product state. The processing of the stretchable fabric of the present invention can be performed by applying a refining-presetting-dyeing-final setting step commonly used in a method of processing a cellulose fiber product.

The dyed product of the elastic fabric of the present invention can firmly dye the polyurethane urea fiber component in the fabric to an appropriate color density, so that when the dyed fabric is stretched or deformed, it is exposed to the surface of the fabric. Due to the polyurethane urea elastic fiber component, peeling and glare are hardly noticeable. In the fabric structure, if the coated inelastic fiber is a transparent fiber or a processed yarn having a small number of twists, the effect of the color of the polyurethane polyurea elastic fiber is strong, so that a cross-knitted fabric, such as inner underwear or direct underwear, is used. In the knit in pantyhose, the deterioration of the aesthetic appearance of the product, which is often caused in the bare state by the exposure of the polyurethane urea elastic fiber component in the bare state, is significantly suppressed by using the fabric prepared according to the present invention.

[0051]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. Prior to the description of Examples, the performance of polyurethane elastic elastic fibers and the method of evaluating elastic cloth will be described. [1] Evaluation method of heat setting property The polyurethane polyurea elastic fiber extracted from the stretchable fabric is immersed in boiling water in a relaxed state and treated for 30 minutes. After that, the polyurethane polyurea elastic fiber was used as a sample having an initial length of 5 cm in a tension-free and linear state.
After 15 seconds in a pressurized steam atmosphere at 120 ° C. under 0% elongation, it is dried in a dryer at 120 ° C. for 30 seconds. Then, it is shrunk in an atmosphere at 50 ° C. for 1 hour. In addition, 2
After standing at 0 ° C and 65% RH for 16 hours, the yarn length (L
cm). The leaving at 50 ° C. is a process for accelerating the change over time. The heat setting rate (%) is calculated by the following equation (13).

Heat setting rate (%) = (L−5) / 5 × 100 (13) The higher the heat setting rate, the more excellent the mold stopping property of the fabric. [2] Blue L value measurement method 1 g of a tubular knitted fabric of a polyurethane elastic fiber (33 dtex / 1 f) (a single-neck knitting machine manufactured by Koike, number of needles: 370, yarn feeding extension ratio: 2.8 times) was produced.

Further, for JIS color fastness test (JIS
L 0803) 4 g of rayon-attached white cloth was collected.
These were dyed and soaped in the same bath under the following conditions. -Dyeing conditions: Dye Sumfix Brilliant Blue R. Special (Sumitomo Chemical CI Reactive Dye Blue 19) 1.0% omf Rayon attached white cloth weight 4g Elastic yarn fiber tube knitted fabric weight 1g Bath ratio 50: 1 Na2SO4 50g / L Na2CO3 15g / L Heating rate 2 ° C / Min Temperature, time 60 ° C x 30 minutes * Na2CO3 is charged after heating up to 60 ° C ・ Soaping conditions: Granup PL (Sanyo Chemical) 2g / L Rayon attached white cloth weight 4g Elastic yarn fiber tube knitted fabric weight 1g Bath ratio 100: 1 Heating rate 2 ° C / min Temperature, time 80 ° C × 10 minutes For dyeing and fixing, use soft water with a Ca ion concentration of 3 ppm or less through a softener, and use a mini color dyeing machine (Texam Giken) It was used.

The dyed elastic fiber knitted fabric was dewatered, air-dried at room temperature for 12 hours, and the Hunter chromaticity L value (brightness) was measured with a Macbeth colorimeter in a state where the knitted fabric was folded in three, that is, six fabrics were stacked. , Blue L value. [3] Measurement of Blue L Value Deterioration Rate The blue L value deterioration rate is defined as L0 by measuring the blue L value measured after drying the dyed elastic yarn fiber knitted fabric at room temperature for 12 hours after dehydration, and JIS-L-0844. The blue L value measured after dewatering the elastic yarn fiber tubular knitted fabric washed according to the above and air-drying at room temperature for 12 hours is represented by L1 and is represented by the following equation (14). Blue L value deterioration rate (%) = (L1−L0) / L0 × 100 (14) [4] Evaluation of heat setting property of fabric The finished width of fabric or knitted fabric (cm) was measured without tension and without wrinkles. The wider one indicates that the polyurethane polyurea elastic fiber used has better heat setting property.

[5] Evaluation of peeling The finished stretched fabric was visually evaluated in a state where the fabric was stretched by applying a load of 1 kg weight in the width direction, and the state of the peeling was determined by class 1 to 5. Grade 5 is a level at which no polyurethane polyurea elastic fibers can be recognized on the surface. Grade 4 cannot confirm that polyurethane polyurea elastic fibers are exposed on the surface, but is a level at which a little glare is recognized. Grade 3 is a level at which polyurethane polyurea elastic fibers can be recognized on the surface. Grade 2 is a level at which polyurethane elastic fibers can be recognized on the surface and the color is different from the color of the mating yarn. Grade 1 is a level at which polyurethane polyurea fibers are clearly visible and visible on the surface, and are not stained or recognized as white. Example 1 1,500 g (parts by weight, the same applies hereinafter) of polytetramethylene ether glycol having a number average molecular weight of 1,800 and 312 g of 4,4′-diphenylmethane diisocyanate were stirred at 60 ° C. for 90 minutes in a nitrogen gas stream. The reaction was continued to obtain a polyurethane prepolymer having an isocyanate group. Next, after cooling to room temperature, 2,600 g of dry dimethylformamide was added and dissolved to obtain a polyurethane prepolymer solution.
On the other hand, 23.4 g of ethylenediamine and 3.7 g of diethylamine were dissolved in 1,400 g of dry dimethylformamide, and the prepolymer solution was added thereto at room temperature to obtain a polyurethane polyurea polymer solution having a viscosity of 3,200 poise (30 ° C.). I got

To the polymer solution thus obtained, 1.5 mass% of an isobutylene adduct of a polyadduct of p-cresol and dicyclopentadiene, and N, N-bis (2-hydroxyethyl) -t-butylamine 5%, 2- (2'-hydroxy-3 ', 5-dibenzyl-phenyl) -benzotriazole 0.3%, magnesium stearate 0.1%.
5% by weight and 4% by weight of a urea compound having 4 urea bond units consisting of N- (2-aminoethyl) piperazine, isophorone diisocyanate and phenyl isocyanate (molar ratio 2: 1: 2). JP-A-7-31
No. 6922, a polyurethane polymer (1,4-butanediol, polytetramethylene ether glycol having a number average molecular weight of 650 <molar ratio 9: 1> and 4,4′-diphenylmethane diisocyanate <molar ratio 0.99:
0.11: 1> (polyurethane polymer having a number average molecular weight of 30,000) to give a stock solution for spinning. The spinning solution was spun by dry spinning to obtain a polyurethane polyurea elastic fiber having 33 dtex / 2 filaments (hereinafter referred to as elastic fiber A).

The bare textile was knitted (24GG, knitting width: 180 cm) by plating with elastic fiber A and cotton spun yarn of 15 tex by braiding draft 3.0. After refining the plate, it was refined at 60 ° C. for 20 minutes, and then pre-set at 190 ° C. for 45 seconds (a setting machine manufactured by Tsujii Dyeing Machine Co., 185 cm wide).
This was treated under the following dyeing conditions (width of fabric at the time of dyeing: 150 cm,
The bare fabric was dyed without tension. 180 ° C
× 45 seconds final set (Tsujii Dyeing Machine set machine,
(Finish width: 157 cm).

Dyeing conditions: Dye Sumifix Black EX conc. gran (manufactured by Sumitomo Chemical Co., Ltd., reactive dye CI Reactive Dye Black 5) 6.0% omf Bath ratio 50: 1 Na2SO4 50 g / liter Na2CO3 20 g / liter (input after heating) Temperature rising rate 2 ° C./minute Temperature , Time 60 ° C. × 30 minutes ・ Soaping condition: Gran-up PL (Sanyo Kasei) 2 g / liter Bath ratio 100: 1 Heating rate 2 ° C./min Temperature, time 80 ° C. × 10 minutes Evaluation result of dyed finished fabric Shown in

The elastic fiber of Example 1 had a small blue L value and a small blue L value deterioration rate. Further, the bare sheeting of Example 1 had a high setting property, had no peeling, had no curl, and had a high quality. [Comparative Example 1] 4% by mass of a urea compound having 4 urea bond units in the production of the polyurethane polyurea fiber of Example 1.
Without adding the polyurethane polymer described in JP-A-7-316922 (the polyurethane polymer described in JP-A-7-316922 (1,4-butanediol, polytetramethylene ether glycol having a number average molecular weight of 650) <
The same except that 1% by weight of a polyurethane polymer having a number average molecular weight of 30,000 comprising a molar ratio of 9: 1> and 4,4′-diphenylmethane diisocyanate (a molar ratio of 0.99: 0.11: 1>) was added. Under the conditions, a polyurethane polyurea elastic fiber 33dtex (hereinafter referred to as elastic fiber X) was spun. )
Polyurethane-polyurea elastic fiber 33dtex (hereinafter referred to as elastic fiber X) was spun under the same conditions except that 1% by weight was added.

Under the same conditions as described in Example 1, bare cotton was knitted by plating the elastic fiber X and a cotton spun yarn of 15 tex. This was opened and subjected to the same dyeing processing as in Example 1 to obtain a finished bare sheeting cloth. Show evaluation results
Figure 1 shows. Comparative Example 2 The production of the polyurethane polyurea fiber of Example 1 was carried out according to the method described in JP-A-8-32969 (JP-A-8-3969).
No. 2969 (PTMG having a molecular weight of 2000)
2000 g and 503 g of MDI were put into a stirring vessel sealed with nitrogen and reacted at 85 ° C. to obtain an MDI-terminated prepolymer. Next, 2000 g of this prepolymer was added to D
MAC 3840 g, and further added 68.7 g of a chain extender EG so as to have a hard ratio of 1.0, reacted, and further added butanol as an end-capping agent)). Elastic fiber Y) 40
dtex was obtained. Elastic fiber Y and a cotton spun yarn of 15 tex were plated by braiding draft 3.0 according to the method of Example 1 to obtain a bare sheeting. Rebelling this,
The same dyeing process as in Example 1 was performed to finish bare sheeting fabric. Table 1 shows the evaluation results of the finished knitted fabric. Example 2 The same procedure as in Example 1 was carried out except that the dyeing conditions were as follows.

Dyeing conditions: Dye Sumix Brillid Red G (reactive dye CI Reactive Dye Red 112 manufactured by Sumitomo Chemical Co., Ltd.) 3% omf Bath ratio 30: 1 Na2SO4 80 g / l Na2CO3 20 g / l (after heating) (Charging) Temperature rising rate 2 ° C./l Temperature, time 80 ° C. × 30 minutes The evaluation results of the dyed finished fabric are shown in Table 1.

The elastic fiber had a small blue L value as in Example 1 of Example 2, and the degradation rate of the blue L value was also small as in Example 1. In addition, the bare sheeting of Example 2 had high setability, had no peeling, had no curl, and had a high quality. [Example 3] The staining was carried out under the same conditions as in Example 1 except that the staining was carried out under the following conditions.

Dyeing Conditions: Dye Sumifix Brillie Blue R. Special (reactive dye CI Reactive Dye Blue 19 manufactured by Sumitomo Chemical Co., Ltd.) 1% omf bath ratio 50: 1 Na2SO4 50 g / l Na2CO3 20 g / l (input after heating) Heating rate 2 ° C./l Temperature Table 1 shows the evaluation results of the dyed finished fabric.

The elastic fiber had a small blue L value as in Example 1 of Example 3, and the degradation rate of the blue L value was also small as in Example 1. Further, the bare sheeting of Example 3 had a high setting property, had no peeling, had no curl, and had a high quality.

[0065]

[Table 1]

[0066]

The composite stretch fabric of the cellulose fibers and the polyurethane urea elastic fibers according to the present invention is excellent in the setting property at the time of heat setting, the dyeing property at the time of dyeing, the fastness by washing and the like, and the elastic function. The stretchable fabric of the present invention can provide a dyed elastic fabric which has good settability in the finishing after dyeing and the shaping finish, does not cause curl in the fabric, and hardly causes peeling.

Claims (4)

[Claims] 1. A heat setting rate of 40% or more comprising cellulose fiber or cotton and polyurethane polyurea elastic fiber.
0.5% by mass of a polyurethane polyurea elastic fiber satisfying 5% or less and a Blue L value of 40 or more and 60 or less and having a Blue L value deterioration rate of 10% or less
Stretch fabric containing at least 35% by mass. 2. The polyurethane polyurea elastic fiber is selected from (a) a bifunctional amine group comprising at least one of primary amine and secondary amine and at least one of tertiary nitrogen and heterocyclic nitrogen. Obtained by reacting a nitrogen-containing compound containing a nitrogen-containing group with (b) an organic diisocyanate and (c) one selected from the group consisting of mono- or dialkylmonoamines, alkylmonoalcohols, and organic monoisocyanates. The stretchable fabric having excellent dyeability according to claim 1, wherein the urea compound is contained in an amount of 1 to 15% by weight based on the polyurethane polyurea polymer. 3. The stretchable fabric according to claim 2, wherein the urea compound contains 4 to 40 urea binding units represented by the following formulas (1) and (2) in one molecule on average. . Embedded image 4. The stretchable fabric according to claim 2, wherein the nitrogen-containing compound is at least one selected from the group consisting of piperazine and bifunctional piperazine derivatives.