JP2001098446A - Knit or woven union cloth containing polyurethane polyurea - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a knit or woven union cloth containing a polyurethane polyurea elastic fiber and having excellent mold-fitting property and decreased tendency to expose the elastic fiber on the surface of the union cloth. SOLUTION: The knit or woven union cloth contains 0.5-35% polyurethane polyurea elastic fiber having a set ratio of 40-75%, a blue L value of 20-35 and a high-temperature strength retention of >=45%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a knitted fabric which has an excellent heat setting property and can obtain a functionally uniform color.

[0002]

2. Description of the Related Art A polyurethane polyurea elastic fiber obtained by subjecting an isocyanate-terminated prepolymer synthesized with a polyalkylene ether glycol and an excess of organic diisocyanate to chain extension with a diamine is known, and a polyamide fiber is mainly used as a mating material. It is knitted and woven with cellulosic fibers such as polyester fiber, cotton and rayon, foundation, socks, pantyhose,
It is used as a stretchable material in clothing in various fields such as swimwear, sportswear, and leotards.

[0003] Polyurethane polyurea urea elastic fibers exhibit an excellent elastic function in which hard segments comprising urea groups form strong hydrogen-bonding physical crosslinks. However, in the field where the stopping property of the product fabric is particularly required,
For example, when processing in the circular knitting field for legs such as zokki pantyhose and tights, the warp knitting field for inner sports such as brassiere, girdle and swimwear, and the textile field for outerwear such as bottoms, polyurethane polyurea elastic fiber has poor heat setting property. However, there was a problem that it was difficult to sew due to the difficulty of wearing because the finish was not large according to the mold, and the edge of the fabric was curled (a phenomenon of curling round and round). In addition, there is also a problem that the product is set many times to set a desired width or is set at a higher temperature, so that the production efficiency and the heat efficiency are deteriorated.

On the other hand, elastic fibers having no urea group, such as polyurethane elastic fibers (elastic fibers consisting only of urethane bonds) and polyetherester elastic fibers (polyester copolymerized with a polyalkylene ether glycol component), and polyurethane polyurea elastic fibers It is known as well. Elastic fibers not containing these urea groups are excellent in heat setting properties and have good mold stopping properties of product fabrics,
Since it does not have a hard segment composed of a urea group, it has a drawback in that the strength after processing is larger than that of a polyurethane polyurea elastic fiber. That is, practical clothing has a problem in durability.

[0005] Further, when the conventional elastic fiber is dyed with a polyamide fiber such as nylon 6 or nylon 66 or wool which is mixed as a mating yarn, the dyeing property of the dye is low. It lacks the same color as wool or wool or does not dye.
For this reason, there is a problem of so-called stripping in which the elastic fibers are exposed to the outside of the cross-knitted fabric, and the stripping of elastic fibers different from the polyamide fibers in the outside of the fabric due to the stripping, or peculiar to the elastic fibers. At present, the phenomenon of so-called glaring of glaring occurs, and the quality of the fabric is significantly reduced. In particular, it is known that the better the elastic fiber is in the heat setting property and the better the stopping property of the product cloth, the greater the exposure of the elastic fiber by peeling and the lower the product quality.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a polyurethane polyurea elastic fiber which has a good die closing property, a small amount of peeling and is excellent in durability. An object of the present invention is to provide a mixed knitted fabric.

[0007]

Means for Solving the Problems As a result of diligent research for providing a polyurethane polyurea elastic fiber and a polyamide fiber or a wool knitted woven fabric which have good mold stopping performance, less peeling and excellent durability. By adding a specific urea compound to the polyurethane polyurea polymer, it is possible to obtain a polyurethane polyurea elastic fiber having both heat setting property, dyeability and heat retention strength, and this improved polyurethane polyurea elastic fiber By mixing and weaving polyamide fiber or wool as a mating material to be mixed with a specific mixing ratio,
We have solved the problem.

According to the present invention, a polyurethane polyurea elastic fiber having a set ratio of 40% or more and 75% or less and a blue L value of 20 or more and 35 or less and having a heat resistance retention of 45% or more is 0.5% by weight. % Is a mixed knitted fabric containing polyurethane polyurea elastic fibers which is mixed and contained at a ratio of not less than 35% and not more than 35%. The polyurethane polyurea elastic fiber contained in the polyurethane knitted fabric containing the polyurethane polyurea elastic fiber of 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, an organic diisocyanate, and a chain extender of a diamine compound. A polyurethane polyurea polymer synthesized using an end blocking agent of a monoamine compound as a raw material is used as an elastic fiber forming polymer, and a specific urea compound to be described in detail later is 1 to
It is prepared by adding 15% by weight and spinning using a known spinning method.

The set ratio of the polyurethane polyurea elastic fibers used in the present invention is from 40% to 75%. 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 rate 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 rate, and power that are characteristic of the polyurethane polyurea elastic fiber knitted fabric will be lost. It loses its properties as a dough.

The blue L value of the polyurethane polyurea elastic fiber used in the present invention is 20 or more and 35 or less. As will be described in detail later, the blue L value is the lightness of the polyurethane polyurea elastic fiber knitted fabric when dyed with a specific blue dye. The higher the L value, the lighter the color, and the higher the L value, the deeper the color. . If the blue L value is greater than 35, the color of the polyurethane polyurea is light, and the peeling of the fabric is likely to occur.
If it is less than 20, the color will be too deep and it will look darker than the color of the polyamide fiber or wool fiber of the mating material, the color of the polyurethane polyurea elastic fiber will prevail on the surface of the fabric, breaking the color balance of the whole fabric Sometimes.

The polyurethane polyurea elastic fiber used in the present invention has a heat-resistant and strong retention of 45% or more. When the heat and strength retention is less than 45%, even if the desired fabric set size can be obtained, the durability at the time of wearing becomes low due to wear of the polyurethane polyurea elastic fibers at the time of wearing, fatigue due to repeated elongation, and the like. The mixture ratio of the polyurethane polyurea elastic fibers in the knitted fabric of the present invention is 0.5% or more and 35% or more.
It is as follows. If the mixing ratio is less than 0.5%, the stretch characteristics of the polyurethane polyurea elastic fiber are unlikely to appear as a fabric, and if the mixing ratio is larger than 35%, the dye distribution rate is lost at the time of dyeing, hindering the color development of the mating material and deteriorating the fabric quality. Or the power of the fabric is too high. The appropriate range varies depending on the structure of the dough, but 0.5% to 5% for woven fabric, 5% to 25% for circular knitted products, 15% to 35% for Russell fabric, and pantyhose. In this case, 0.5% or more and 25% or less are appropriate. Here, the mixing ratio means the content ratio of the polyurethane polyurea elastic fiber according to claim 1 contained in the finished fabric before sewing, but in the case of a pantyhose that takes the form of a product immediately after knitting, such as pantyhose, The content of the polyurethane polyurea elastic fiber in the weight including all the legs is defined as the content.

The mixed mating material other than the polyurethane polyurea elastic fiber constituting the cross-knitted fabric of the present invention is N6 or N66.
Polyester fiber such as polyethylene fiber, polyethylene terephthalate, polytrimethylene terephthalate, polytetramethylene terephthalate, cationic dyeable polyester fiber, etc., natural fiber such as acrylic fiber, wool, cotton, silk, copper ammonia re-rayon, viscose rayon , An acetate rayon or the like, or a knitted or woven fabric coated, entangled, twisted, or the like with these fibers, to obtain a fabric. The polyurethane polyurea elastic fiber used in the cross-knitted fabric of the present invention has excellent coloring properties, especially acid dyes and gold-containing dyes, so that when the mating material is not substantially dyed with the acid dye or the gold-containing dye, Dyeing with a dye suitable for the mating material, and separate spinning by so-called shading, in which only the polyurethane elastic fiber is dyed with an acid dye or a gold-containing dye with good homochromaticity, are also possible. From the viewpoint of dyeing efficiency and cost, it is generally preferable to use an acid dye, a polyamide fiber or wool that can be dyed with a gold-containing dye, or a polyamide fiber and wool, and more preferably a polyamide fiber or wool, or a polyamide fiber. The total mixing ratio of wool and wool is 8% or more of the knitted fabric.
If it is less than 8%, when dyeing with an acid dye or a gold-containing dye, the dye concentration in the dyeing bath becomes thin, so that uniformity cannot be obtained, or the balance of dye distribution between polyamide fibers, wool and polyurethane polyurea elastic fibers. And the effect of coloring the polyurethane polyurea elastic fiber is reduced. Here, the mixing ratio of each material can be determined from the weight by dissolving in a solvent that does not dissolve other materials while being a good solvent for the material, and for example, polyurethane polyurea fiber is an aqueous solution of dimethylacetamide, nylon is an aqueous solution of hydrochloric acid. The polyester fiber is a caustic soda aqueous solution, the acrylic fiber is a nitric acid aqueous solution, the cellulosic fiber is copper ammonia, and wool is left to the end because there is no suitable solvent.

The yarn form of the polyurethane polyurea elastic fibers used in the cross-knitted fabric of the present invention is substantially the same as that of a coated elastic yarn, a core spun yarn, a spun twist yarn even in a so-called bare state in which the polyurethane polyurea elastic fibers themselves are inserted during the cross-knitting. More specifically, it may be in the form of a coated yarn in which a polyurethane polyurea elastic fiber is used as a core and a mating yarn is twisted to form a sheath, and the method is not limited to the examples, for example, covering, spinning, twisting and twisting. Either case is effective, but the effect can be properly selected depending on the purpose and application of the knitted fabric. The mainstream of pantyhose and woven fabrics is used in the form of coated elastic yarn, core spun yarn, and pants-yarn yarn.Especially when the inelastic fiber to be coated is a transparent yarn or the number of twists is small, the polyurethane polyurea elastic fiber is used. When the fabric is cross-woven due to the strong influence of the color, the polyurethane elastic fiber used in the present invention has a remarkable coloring effect. In the case of inner underwear and direct knit in pantyhose, it is often used in bare state such as bare sheeting, and in recent years, even those using woven cloth have begun to appear, and when used in this state, it is more difficult to use cloth than when using in covered state Since the probability that the polyurethane polyurea elastic fiber comes out on the surface is increased, the coloring effect of the polyurethane elastic fiber used in the present invention is more remarkable than when used in a coated state.

Hereinafter, the urea compound added to the polyurethane polyurea elastic fiber used in the present invention, the polyurethane polyurea elastic fiber used in the present invention, and a method for preparing the same will be described in detail. In the present invention, the urea compound added to the polyurethane polyurea elastic fiber is a reaction product of the following compounds (a), (b) and (c).

(A) A nitrogen-containing compound containing a bifunctional amine comprising at least one of a primary amine and a secondary amine and at least one of a tertiary nitrogen and a heterocyclic nitrogen. Organic diisocyanate, (c) one selected from the group of mono- or dialkyl monoamines, alkyl mono-alcohols, and organic mono-isocyanates. This reaction is carried out in the above-mentioned (a), It is necessary to adjust the molar equivalent ratio of the compounds (b) and (c).

The urea compound thus obtained contains a tertiary nitrogen skeleton represented by the following formula (1) and a urea bond represented by the following formulas (2) and (5). However, when the alkyl monoalcohol is a urea compound participating in the reaction, a urethane bond represented by the following formula (6) is also included. The urea compound to be added to the polyurethane polyurea elastic fiber is selected from (1) to (1) according to the selection of the compound (c).
(4) It is classified into urea compounds of the formulas (5) and (6) represented by the following two structural formulas including the structure represented by the formula (n in the structure represents one or more polymerization repetitions). You.

When the compound (c) is a mono- or di-alkyl monoamine or alkyl mono-alcohol: (c)-[(b)-(a)] n- (b)-(c) (5) In the case of isocyanate: (c)-[(a)-(b)] n- (a)-(c) (6) A preferred structure of the urea compound is represented by the formula (6) in which (c) is an organic isocyanate. It is a structure that is represented. This 2
The urea compounds having different types of structures are preferably added alone, but may be used as a mixture.

In the compound (a) used for obtaining the urea compound used in the present invention, primary amine and secondary amine
Examples of the nitrogen-containing compound containing a bifunctional amine comprising at least one of tertiary amines and 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-
Piperidine derivatives such as aminoethyl) -4-methylpiperazine; pyrrolidone derivatives such as 4-aminoethylpiperidine, N-amino-4- (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 are exemplified. Preferred nitrogen-containing compounds are piperazine and piperazine derivatives, and the urea compound obtained has extremely good solubility in amide solvents. N-
(2-Aminoethyl) piperazine and N- (2-aminopropyl) piperazine are preferred. These compounds are
They can be used alone or as a mixture.

As the compound (b) used to obtain the urea compound used in the present invention, as the organic diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, Hexamethylene diisocyanate, 3-methylhexane-1,6-diisocyanate, 3,3′-dimethylpentane-1,5-diisocyanate, 1,3-
And 1,4-cyclohexylene-diisocyanate,
4,4′-dicyclohexylmethane-diisocyanate, m- and p-xylylene diisocyanate, α,
α, α ′, α′-Tetramethyl-p-xylylene diisocyanate, 4,4′-diphenylmethane-diisocyanate, isophorone diisocyanate, 2,4-tolylene diisocyanate and the like are exemplified. Preferred are alicyclic diisocyanates such as isophorone diisocyanate and 4,4'-dicyclohexylmethane-diisocyanate, and these can be used alone or as a mixture.

The compound (c) used for obtaining the urea compound used in the present invention is a mono- or dialkylmonoamine which is a monoamine having an alkyl group having 1 to 10 carbon atoms, 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 is illustratively mentioned. These can be used alone or as a mixture.

The compound (c) used to obtain the urea compound used in the present invention has 1 to 10 carbon atoms.
Alkyl monoalcohol having an alkyl group of, for example, methanol, ethanol, 2-propanol, 2-
Methyl-2-propanol, 1-butanol, 2-ethyl-1-hexanol, 3-methyl-1-butanol and the like can be mentioned. These can be used alone or as a mixture.

The mono- or dialkylamine and the alkyl alcohol can be used alone or as a mixture, but it is preferable to use them alone. In the compound (c) used to obtain the urea compound used in the present invention, examples of the organic monoisocyanate include 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, but they 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 alkyl alcohol is blocked by an organic monoisocyanate is generated, and the effective amount of the urea compound having the structure of the formula (7) or (8) is reduced. The resulting compound is
In the process of processing the polyurethane polyurea elastic fiber, it causes scum that bleeds out from the fiber and stains the knitting machine and the dyeing bath.

The compound (c) used to obtain the above-mentioned urea compound used as an additive modifier in the present invention is selected from the above three kinds as described above, and is obtained from (a) and (b). It has a function of blocking the active terminal (amino group or isocyanate group) of the urea compound, and this active terminal reduces the spinning stability and the robustness of the polyurethane polyurea elastic fiber. In the reaction for preparing the urea compound, when the reaction molar equivalent is (a)> (b), an organic monoisocyanate is selected as the compound (c) because the terminal of the urea compound is an amino group, and (a) <
In the case of (b), since the terminal of the urea compound is an isocyanate group, at least one of a mono- or dialkylamine and an alkyl monoalcohol needs to be selected as the compound of (c). Preferably, an organic monoisocyanate compound is selected as described above.

The urea compound used in the present invention is characterized in that 2 to 40 urea binding units represented by the following formulas (7) and (8) are contained 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 formula (9) (n in the structure represents one or more polymerization repetitions).

[0025] A urea compound having a desired number of urea bonding units is
It can be obtained by adjusting the molar ratio of the charged compounds of (a), (b) and (c). That is, (a):
If the 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 dialkylmonoamine, and n + 1 for alkylmonoalcohol.

When the compound (c) is an organic monoisocyanate, the structure of the urea compound is represented by the following formula (10) (n in the structure represents one or more polymerization repetitions). At this time, if the molar ratio is adjusted so that (a) :( b) :( c) = n + 1: n: 2, the number of urea bond units present in one molecule is n + 3.

Since the number of urea bond units present in one molecule of the urea compound used for the additive modification is in the range of 4 to 40, when converted into the number of polymerization repetitions n in the structure, mono- or dialkyl monoamine, organic 1-37 for monoisocyanate, 3-39 for alkyl monoalcohol
It is. When the number of urea bond units is less than 4 or more than 40,
Sufficient heat setting property cannot be obtained. On the other hand, if the number of urea bonding units is less than 4, bleed-out may occur in the processing step of the polyurethane polyurea elastic fiber, causing scum to stain the knitting machine or the dyeing bath. On the other hand, when the number of urea bonding units is 4
If it exceeds 0, the urea compound added in a predetermined amount in the dope precipitates in the polyurethane polyurea spinning solution, causing breakage of the polyurethane polyurea elastic yarn during the spinning or a decrease in the elongation of the polyurethane polyurea elastic fiber. And the elastic function is impaired. The preferred number of urea bond units is 4 per molecule of the urea compound.
~ 15.

The number of urea bonding units present in one molecule of the urea compound used in the present invention is (a), (b),
It can be adjusted by selecting the molar ratio of the charged compound (c). The reaction temperature during the synthesis of the urea compound is
20-60 ° C is preferred. This synthesis reaction is preferably performed in an amide-based polar solvent capable of dissolving the polyurethane polyurea polymer, for example, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, or the like. When using a solvent that does not dissolve the polyurethane polyurea polymer, the reaction product can be taken out as a solid after the reaction, dissolved in a solvent in which the polyurethane polyurea polymer dissolves, 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 (b), and phenyl isocyanate 2 is used as (c). 50 moles
50 ° C. so as to obtain a dimethylacetamide solution in weight%
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 the reaction method is not limited to this. Other known methods can be used.
At this time, the number of repeating polymerizations n of the urea compound obtained is 1
And the number of urea bond units existing per molecule is 4
Becomes

The most general method for preparing the polyurethane polyurea elastic fiber used in the present invention is a method of dry spinning a spinning solution obtained by adding a urea compound dissolved in an amide polar solvent to a polyurethane polyurea polymer solution. The urea compound can be added at any stage from the completion of the polymerization of the polyurethane polyurea polymer to the spinning.

The amount of the urea compound to be added to the polyurethane polyurea elastic fiber may be such that 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. The content is preferably 1 to 15% by weight based on the polyurethane polyurea polymer. When the added amount of the urea compound is less than 1% by weight, the effects of heat setting property and dyeing property are small. If it exceeds 15% by weight, not only does the heat setting effect saturate and the dyeing fastness deteriorates, but also the spinning yarn breaks and the spinning stability decreases, and the strength, elongation and elasticity are also reduced. Elastic functions such as recovery are also impaired. A more preferable addition amount is 2 to 10% by weight.
It is.

When the urea compound added to the polyurethane polyurea elastic fiber used in the present invention is added to the polyurethane elastic fiber (elastic fiber having only urethane bond), it has a heat setting effect, but when added to the polyurethane polyurea elastic fiber. Not only is the degree of effect smaller, but also the elastic function and spinning stability of the fiber are impaired.

In preparing the polyurethane polyurea fiber of the present invention, a known heat setting property improving technique can be additionally used. For example, JP-A-7-31692
In addition, 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 Japanese Unexamined Patent Publication (Kokai) No. 2 (1994) may be simultaneously contained. In this case, the total amount of the thermoplastic polymer and the urea compound of the present invention is 15% by weight or less, and the amount of the known thermoplastic polymer does not exceed the amount of the urea compound of the present invention. It is preferable to add in the range.

The reason that the polyurethane polyurea elastic fiber containing the urea compound specified in the present invention exhibits excellent heat setting property and dyeability without sacrificing elastic function and spinning stability at least is mainly due to the dyeability. And the effect of a specific urea compound containing a specific number of urea bond units. That is, the dyeability and fastness are excellent because at least one of a primary amine and a secondary amine is used.
This is an effect of a nitrogen-containing compound containing a functional amine and at least one of tertiary nitrogen and heterocyclic nitrogen that strongly adsorbs and holds an acid dye or a disperse dye. Also,
An excellent heat setting property is an 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, the urea bonds form an extremely strong hydrogen-bonding physical crosslink to form a crystalline domain. for that reason,
It is considered that while exhibiting an excellent elasticity function at normal temperature, the hydrogen bond is hardly broken even at high temperature, so that heat setting is hardly performed.

The urea compound of the present invention having a specific number of urea bond units forms a strong hydrogen bond with the urea bond in the polyurethane polyurea elastic fiber and assimilates with the crystalline domain in the polyurethane polyurea elastic fiber. It becomes a polyurethane polyurea elastic fiber exhibiting an elastic function. However, the urea compound of the present invention has an effect of lowering the glass transition temperature of the crystalline domain,
At high temperatures, hydrogen bonds are broken and the crystalline domains easily flow through the heat, resulting in polyurethane polyurea elastic fibers having excellent heat setting properties. If the amount of the urea compound of the present invention added to the polyurethane polyurea elastic fiber is too small, the heat setting effect is insufficient. Conversely, if the addition amount is too large, the heat setting effect will be sufficiently satisfactory, but not only the glass transition temperature of the crystalline domain will be too low but heat flow will occur at a high temperature during spinning and spinning stability cannot be ensured. In addition, the elastic function is impaired.

The polyurethane polyurea polymer of the polyurethane polyurea elastic fiber used in 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. 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
Copolymerized polyether glycols composed of 2-dimethylpropylene groups, copolymerized polyether glycols composed of tetramethylene groups and 3-methyltetramethylene groups, or 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, or the like. No. 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,
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.

As the polyurethane polyurea polymer, a known polyurethane polyurea formation 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 polyurea polymer.

The polyurethane polyurea elastic fiber used in the present invention can be obtained by dry spinning a spinning solution containing 1 to 15% by weight of the urea compound of the present invention based on a polyurethane polyurea polymer. The relationship between the content of the urea compound of the present invention in the polyurethane polyurea polymer and the set ratio, blue L value, and heat retention strength is as follows. As the urea compound content increases, the set rate increases, the blue L value decreases, and the heat resistance retention rate decreases. That is, when the content of the urea compound increases, the yarn moves in the direction of higher set, darker color, and lower strength. The polyurethane urea elastic fiber used in the present invention contains the urea compound for simultaneously satisfying the set ratio of 40% or more and 75% or less, the blue L value of 20 or more and 35 or less, and the heat resistance strength retention of 45% or more according to claim 1. The rate is 1 to 15% by weight, and more preferably 2 to 6% by weight in consideration of spinning easiness during practical production and various physical properties of the completed yarn.

In addition to the urea compound of the present invention, the stock solution for spinning may contain organic or inorganic compounding agents useful for known polyurethane polyurea elastic fibers, polyurethane elastic fibers, and polyurethane compositions, such as ultraviolet absorbers and antioxidants. ,
Light stabilizers, gas-coloring inhibitors, colorants, matting agents, lubricants, etc. can be added simultaneously or sequentially. The polyurethane polyurea polymer spinning dope thus obtained is
A polyurethane polyurea elastic fiber can be produced by forming into a fibrous shape by known dry spinning, wet spinning, or the like. Dry spinning, which exhibits excellent elasticity and is excellent in productivity, is preferred.

The resulting polyurethane polyurea elastic fibers having a higher denier per single yarn are more advantageous for improving the heat setting property. Preferably, 5 to 5 yarns
30 denier. 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 denier, the orientation is large, and if it exceeds 30 denier, the orientation relaxation is small, 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 can be applied to any kind of elastic fibers.

The polyurethane-polyurea elastic fibers of the present invention may be added to polydimethylsiloxane, polyester-modified silicone, polyether-modified silicone, amino-modified silicone,
Mineral oil, mineral fine particles, such as silica, colloidal alumina, talc, etc., higher fatty acid metal salt powders, such as magnesium stearate, calcium stearate, etc., higher aliphatic carboxylic acids, higher aliphatic alcohols, paraffin, polyethylene, etc. An oil agent such as a shaped wax may be applied alone or in combination as needed.

[0046]

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. In addition, the evaluation results of the examples and the comparative examples are summarized and shown in Tables 1, 2, 3, and 4 for comparison. In the examples and the like, the evaluation values of the elastic fibers and the measurement values relating to the knitted and knitted fabrics were determined by the following measurement methods. [1] Measurement of breaking strength and 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), and the breaking strength (g) and the breaking elongation (%) are measured. [2] Method of evaluating heat setting property A test yarn having an initial length of 5 cm is placed in a pressurized steam atmosphere at 120 ° C for 15 seconds under 100% elongation, and then dried in a dryer at 120 ° C for 30 seconds. Then, in an atmosphere of 50 ° C.,
Let the time shrink. Furthermore, the yarn length (Lcm) is read after standing at 20 ° C. and a 65% RH atmosphere for 16 hours. In addition, 5
Leaving at 0 ° C. is a process for accelerating the change over time.
The heat setting rate (%) is calculated by the following equation. The higher the heat setting rate, the more excellent the mold stopping property of the fabric.

Heat setting rate (%) = (L−5) / 5 × 100 [3] Blue L value measuring method Knitting 15 denier polyurethane polyurea elastic fiber with a single knitting machine having a number of 370 needles and a diameter of 3.75 inches. A vertical knitted fabric of elastic fibers was obtained. Further, nylon 6 fiber 50 denier / 17 filament (trade name: Toray Nylon) was similarly knitted to obtain a nylon 6 tubular knitted fabric.
These were dyed and fixed in the same bath under the following conditions.

Dyeing Conditions Dye Kayanol Milling Blue 2
RW (manufactured by Nippon Kayaku Co., Ltd.) 1.3% owf Nylon 6 knitted fabric weight 4g Elastic yarn fiber knitted fabric weight 1g Bath ratio 20: 1 ammonium sulfate 2g / l Temperature rising rate 2 ° C / min Temperature, time 95 ° C × 60 min Fix condition Sunlife TN-8 (Nichika Chemical) 4% owf Nylon 6 knitted fabric weight 4 g Elastic yarn fiber knitted fabric weight 1 g Bath ratio 20: 1 Ammonium sulfate 2 g / l Heating rate 2 ° C / min Temperature, Time 80 ° C. × 30 minutes For dyeing and fixing, soft water having a Ca ion concentration of 3 ppm or less passed through a softener was used consistently, and a mini-color dyeing machine (Texam Giken) was used as a dyeing machine.

The dyed elastic fiber tubular knitted fabric was dewatered, air-dried at room temperature for 12 hours, and the L value (brightness) of Hunter chromaticity was measured with a Macbeth colorimeter in a state where the tubular knitted fabric was folded in three, that is, six fabrics were piled up. . [4] Measurement of heat retention strength Tensile test yarn having an initial length of 5 cm was passed through a pin tenter set at 180 ° C for 60 seconds under 100% elongation, and further left for 16 hours in an atmosphere of 20 ° C and 65% RH. Then, relax and measure the strength S1 (g) by the method of [1]. Assuming that the yarn strength before heat setting is S0, the heat resistant strength retention rate is calculated by the following equation.

Heat retention strength = S1 / S0 × 100 (%) [5] Preparation of pantyhose Polyamide elastic fiber (Leona 10 manufactured by Asahi Kasei Corporation)
d / 5f) and covering the test yarn (draft rate 2.7,
Twisting number 1600 T / m, single cover S twist, Z twist two each), knitting machine (Nagata Simplex KT-6)
Type, 400 gauge) and leg part total course 2500
Knitted zokki pantyhose. On the other hand, the panties were adjusted to 12 g / foot including nylon and conventional polyurethane polyurea elastic fibers, and were common to all pantyhose. After the knitted fabric is preset at 50 ° C., it is dyed at 95 ° C. for 45 minutes. After the fix treatment and the softening agent treatment, the knitted fabric is covered on the stainless steel last and set with pressurized steam at 120 ° C. for 15 seconds.
Dry for 0 seconds. Pull out the knitted fabric from the last, 20
It is left for 3 days in an atmosphere of 65 ° C. and 65% RH. [6] Evaluation of heat setting property of cross-knitted fabric The length (cm) of the leg portion of the pantyhose prepared in the above [5] is measured. The longer the length, the better the heat setting property of the used polyurethane polyurea elastic fiber. Finished width (cm) for woven and knitted fabrics
Is measured. The wider one indicates that the used polyurethane polyurea elastic fiber used has excellent heat setting property. [7] Peeling Evaluation The finished cross-knitted fabric was visually judged, and the state of the peeling was judged on the 1st to 5th grades. Grade 5 is a level at which no polyurethane polyurea elastic fibers can be recognized on the surface.
Grade 4 is a level at which the appearance of polyurethane polyurea elastic fibers cannot be confirmed, but a slight glare is noticeable. Grade 3 is a level at which polyurethane polyurea elastic fibers can be recognized on the surface. At the level where you can recognize that the secondary polyurethane elastic fibers are exposed on the surface, and that 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 white. [8] Durability of pantyhose 10 female panelists wear pantyhose for 8 hours / 1 day, have them perform their daily life, have them inspected every time they are finished, and wear when the polyurethane polyurea elastic fiber is cut. The number was recorded. For example, if a cut is found after wearing three times, the wearing durability of the pantyhose is 3. The durability was determined by averaging the values for 10 persons.

[9] Evaluation of mold processing performance A hemispherical hot iron ball with a diameter of 10 cm heated to a surface temperature of 180 ° C with the fabric fixed in a relaxed state without slack between two 2 cm-thick fixtures cut into a diameter of 15 cm 6 so that the indentation depth of the dough becomes 10 cm.
Immediately after 0 second, the hot iron ball was taken out, left in a shaped bump-like shape at 20 ° C. × 65% RH for 12 hours, and the height of the bump was measured.

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 placed in a stream of nitrogen gas at 60 ° C. The mixture was reacted with stirring for 90 minutes 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% by weight 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%.
And 5% by weight of a urea compound composed of N- (2-aminoethyl) piperazine, isophorone diisocyanate and phenyl isocyanate (molar ratio 2: 1: 2) having 4 urea bonding units. And JP-A-7
5% by weight of polyurethane polymer described in JP-316922A
Was added to obtain a stock solution for spinning. The spinning solution was spun by dry spinning to obtain a polyurethane polyurea elastic fiber having 15 d / 2 filaments (hereinafter referred to as elastic fiber A) and 40 d / 4 filaments (hereinafter referred to as elastic fiber B).

Using this elastic fiber A, a pantyhose pantyhose was prepared. Here dyeing is Lanasyn
Black S-DL (Metallic acid dye made by Clariant) 4% owf, fix is HIFIX SL
(Dainippon Pharmaceutical Co., Ltd.) 6% owf, and all other conditions were performed according to the conditions except for the weight condition of the fabric described in [3] Blue L value measurement method.

(Example 2) Acryl / nylon 6 was blended at a weight ratio of 75/25 to obtain a blended yarn having a spun yarn count of 64 meters. Draft in which this yarn and elastic fiber B are knitted
In step 5, a bare sheeting was prepared. This was opened, 60 ° C x 20
After scouring, the mixture was preset at 180 ° C. for 45 seconds and dyed black with a conventional cationic dye.
Syn black S-DL 1% owf was added to dye the bare fabric. The dough was final set at 175 ° C. for 45 seconds and finished.

Example 3 The same processing was performed using wool instead of nylon 6 of Example 2. (Example 4) The elastic fiber B was drafted as acrylic 3 using acrylic /
A core spun yarn having a twist of 300 T / M and a count of 60 meters was made of nylon 6. The core-spun yarn had a nylon content of 18% and the elastic fiber B had a content of 8%, and a plain weave fabric of 60-meter acrylic spun yarn was used as the warp with this yarn as the weft. This was scoured, pre-set and dyed in the same manner as in Example 1 and, at that time, the same bath
n Black S-DL 0.4% owf was added for staining. The dough was final set at 175 ° C. for 45 seconds and finished.

(Example 5) A mold was formed using the finished cloth obtained in Example 2. (Comparative Example 1) 4% by weight of a urea compound having 4 urea bond units in the production of the polyurethane polyurea fiber of Example 1.
And the polyurethane polyurea elastic fibers 15d (hereinafter referred to as elastic fibers X) and 40d
(Hereinafter referred to as elastic fiber Y). Also, Japanese Patent Application Laid-Open No. 8-329
According to the method described in Item 69, polyurethane fiber (hereinafter referred to as elastic fiber Z) 15d was obtained by dry spinning.

Using the elastic fibers X and Z described above, pantyhose was obtained by the method of Example 1. (Comparative Example 2) A bare sheeting finished in exactly the same manner as in Example 2 except that the acrylic / nylon 6 was made of only acrylic and no addition of Lanasyn Black S-DL was obtained.

Comparative Example 3 A bare sheeting finished in exactly the same manner as in Example 2 except that the elastic fiber A was replaced with the elastic fiber Y was obtained. (Comparative Example 4) In Example 4, acryl / nylon 6 was changed to acryl only, and Lanasyn Black SD was used.
A finished fabric was obtained in exactly the same manner except that L was not added.

(Comparative Example 5) The same molding as that of Example 5 was performed using the fabric of Comparative Example 3. Here, Example 2 and Example 3 and Comparative Example 2 Bare sheeting of Comparative Example 3 was pre-set, the final set width was the same for all samples in each step, and the fabrics of Example 4 and Comparative Example 4 were pre-set. In the final set, the working width was the same for all samples in each step.

Tables 1, 2, 3, and 4 collectively show the evaluation results of the above Examples and Comparative Examples. In each of the examples, the setability was high, there was no peeling, the durability was better than that of the same setability, and the mold was excellent in moldability and even more effective in preventing peeling. Further, the bare sheeting of the example was finished with high curl without curl.

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[Table 1]

[0062]

[Table 2]

[0063]

[Table 3]

[0064]

[Table 4]

[0065]

The polyurethane urea elastic fiber-containing mixed woven fabric according to the present invention uses polyurethane urea fiber which is excellent in heat setting property and color matching property with the fiber to be mixed.
It is possible to obtain a garment made of a polyurethane urea elastic fiber-containing fabric such as pantyhose, tights, and the like, which shows good mold stopping properties and in which the peeling is not conspicuous.

Claims (8)

[Claims] 1. A polyurethane polyurea elastic fiber having a set ratio of 40% or more and 75% or less, a blue L value of 20 or more and 35 or less, and a heat resistant strength retention of 45% or more is incorporated into a fabric at 0.5%. A mixed knitted fabric containing at least 35% or less. 2. The polyurethane polyurea elastic fiber comprises (a) a bifunctional amine comprising at least one of a primary amine and a secondary amine, and at least one of a tertiary nitrogen and a heterocyclic nitrogen. A urea compound obtained by reacting a nitrogen-containing compound containing the compound with (b) an organic diisocyanate, and (c) one selected from the group consisting of mono- or dialkylmonoamines, alkylmonoalcohols, and organic monoisocyanates; The mixed knitted fabric according to claim 1, wherein the content is 1 to 15% by weight based on the polyurethane polyurea polymer. 3. The polyurethane polyurea elastic fiber according to claim 2, wherein the urea compound has 4 to 40 urea binding units per molecule represented by the following formulas (1) and (2). The mixed knitted fabric according to claim 1, comprising: 4. The method according to claim 1, wherein the nitrogen-containing compound (a) constituting the urea compound according to claim 2 is at least one selected from the group consisting of piperazine and bifunctional piperazine derivatives. Knitted fabric. 5. The mixed knitted fabric according to claim 1, wherein the mixture ratio of polyamide fibers or wool or the total amount of polyamide fibers and wool in the material constituting the mixed knitted fabric is 8% or more. 6. The cross-knitted woven fabric according to claim 5, which is a core spun yarn or a spun twist yarn covered or twisted with a coated elastic yarn covered with a non-elastic fiber on a core yarn of a polyurethane polyurea elastic fiber. 7. The knitted fabric according to claim 5, wherein the polyurethane polyurea elastic fibers are inserted in a bare state. 8. The knitted fabric according to claim 5, which is molded.