JP3407247B2 - Elastic knitted fabric - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an elastic knitted fabric which is knitted by a polyurethane elastic fiber (A) and a polyester fiber (B), and more particularly. The present invention relates to a stretchable knitted fabric obtained by cross-knitting a polyurethane-based elastic fiber having a deterioration preventing property under various chlorine water environments and a highly stretchable polyester fiber. 2. Description of the Related Art Conventionally, stretch knitted fabrics of ether-based polyurethane elastic fibers and polyamide fibers have been provided mainly for various sports fields. However, since the knitted fabric is dyed with an acid dye, for example, the wet fastness required for swimwear is inferior, the dye is transferred to other clothes, and the discoloration due to chlorine water is liable to occur. Had. In order to improve such fastness, metal-containing dyes or fixing agents have been used.However, the quality of the knitted fabric is deteriorated, and radical deterioration such as light or chlorine occurs. It was difficult to solve. [0003] In addition, a fabric made of a cross-knitted fabric of a polyester-based urethane elastic fiber and a polyester fiber has been produced.
The knitted fabric requires high-pressure dyeing at 130 ° C. to obtain good color development, resulting in deterioration of polyurethane fibers,
Due to drawbacks such as a decrease in the tension of the fabric and poor durability, sufficient practicality has been lacking. As a measure for avoiding such disadvantages, a method of improving the durability of polyurethane-based elastic fibers to chlorine (Japanese Patent Publication No. 60-44444, Japanese Patent Publication No. 61-35).
No. 283) and a method not using high-temperature and high-pressure dyeing conditions (Japanese Patent Publication No. 34-10497). [0005] However, products such as knitted knitted fabrics using polyurethane-based elastic fibers containing the above-mentioned chlorine-deterioration inhibitor have inadequate durability or copolymerized polyester-based products. Fibers have the drawback that denier of single fibers cannot be reduced due to insufficient fiber strength. The present invention provides a knitted fabric which does not have these conventional drawbacks, is excellent in coloring properties without discoloration and deterioration due to chlorine water even in products such as swimwear, and has excellent durability without reduction in tension. [0006] Means for Solving the Problems That is, the present invention is 20 to 1
00 denier polyurethane elastic fiber (A) and 30-
A cross-knitted fabric with 70 denier hollow polyester fiber (B) having a hollow ratio of 20 to 40% , wherein the fiber (A) is 0.5 to 4.5% by weight in the following compound group: A fiber containing one or more kinds, wherein the fiber (B) is a fiber mainly composed of polypropylene terephthalate, and has a stretch recovery rate of 80% or more at 30% elongation. It is a knitted fabric. * Compound group: magnesium oxide, zinc oxide, aluminum oxide, magnesium hydroxide, zinc hydroxide, aluminum hydroxide, hydrotalcite compound Polyurethane-based elastic fiber in the present invention
(A) is an elastic fiber obtained by spinning the following polymer composition mainly composed of polyurethane. As the polyurethane in the present invention, a polymer diol having a number average molecular weight of 600 or more, preferably 1,000 to 5,000 and a melting point of 60 ° C. or less, an isocyanate mainly composed of an organic diisocyanate, and a polyfunctional active hydrogen compound having a molecular weight of 400 or less And a polymer obtained by reacting Examples of the polymer diol include polyether glycols such as polytetramethylene glycol and polyethylene propylene ether glycol, and glycols such as ethylene glycol, 1.6-hexanediol, 1.4-butanediol and neopentyl glycol. Polyester glycols, polycaprolactone glycol, polyhexayl glycol obtained by reacting at least one of the above with at least one of organic dicarboxylic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid, β-methyladipic acid and isophthalic acid. One type of polymer diol such as methylene dicarbonate glycol, or a mixture or copolymer of two or more types thereof can be exemplified. As organic diisocyanates, 4 ·
4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 4,4'-dicyclohexyl methane diisocyanate, isophorone diisocyanate Or a mixture of two or more organic diisocyanates. Further, a small amount of triisocyanate may be used in combination. The polyfunctional active hydrogen compounds include ethylenediamine, 1.2-propylenediamine, hexamethylenediamine, xylylenediamine, 4.4'-diphenylmethanediamine, hydrazine, 1.4-diaminopiperazine, ethylene glycol, One type such as 4'butanediol, 1.6-hexanediol, water and the like or a mixture of two or more types thereof can be exemplified. If desired, a small amount of a terminator such as a monoamine or monoalcohol may be used in combination with these compounds. However, preferred are diamines alone and those mainly composed of diamines. The method of spinning the polyurethane-based composition into elastic fibers is not particularly limited, but it is preferable to dissolve the polyurethane-based composition in a solvent and dry spin. Examples of the solvent include N-N-dimethylacetamide, N-N-dimethylformamide, tettamethylurea, hexamethylphosphonamide, and the like.
It is not limited to these. Other than the polyurethane constituting the polyurethane-based composition, there are chlorine water deterioration inhibitors such as metal oxides and metal hydroxides.
Examples include zinc oxide, aluminum oxide, magnesium hydroxide, zinc hydroxide, aluminum hydroxide, and hydrotalcite compounds, which may be used alone or as a mixture of two or more. Particularly preferred is magnesium oxide or zinc oxide. The addition to these polyurethane solutions is not particularly limited, but the average particle diameter is 0.05 to 3 μm.
It is preferably added as m particles. The addition amount of the chlorine water deterioration inhibitor such as these metal oxides is preferably
It is 1.0 to 3.0% by weight. The denier of the polyurethane elastic fiber used in the present invention is suitably in the range of 20 to 100 denier, preferably 40 to 70. These elastic fibers are used as a draw-up yarn, a covering yarn, or a core yarn, mixed with other materials, or used as a bare yarn with other materials. The polyester fiber (B) mixed and knitted with the polyurethane elastic fiber of the present invention is obtained by spinning a polymer composition obtained by using terephthalic acid as a main carboxylic acid component and trimethylene glycol as a main glycol component. The obtained polyester fiber is targeted. Further, a polyester in which a part of the terephthalic acid component is replaced by another bifunctional carboxylic acid component may be used, or a polyester in which a part of the glycol component is replaced by the above-mentioned glycol or other diol component other than the main component. There may be. Examples of the bifunctional carboxylic acid other than terephthalic acid used herein include, for example, isophthalic acid, naphthalenedicarboxylic acid, diphenylcarboxylic acid, diphenoxydicarboxylic acid, β-hydroxyethoxy acid, p-oxybenzoic acid,
Aromatic, aliphatic and alicyclic bifunctional carboxylic acids such as adipic acid, sebacic acid, and 1,4-cyclohexanehexanecarboxylic acid can be mentioned. Examples of the diol component other than the glycol include ethylene glycol, tetramethylene glycol, and cyclohexane.
Examples thereof include aliphatic, alicyclic, and aromatic diol compounds such as 1.4-dimethanol, neopentyl glycol, bisphenol A, and bisphenol S. Further, as long as the polyester is substantially linear, polycarboxylic acids such as trimellitic acid and pyromellitic acid, polyols such as glycerin, trimethylolpropane and pentaerythritol, 5-hydroxyisophthalic acid, A monomer having a trifunctional or higher ester forming group such as 5-dihydroxybenzoic acid can be used. Further, a blend of these polymers or copolymers may be used. These polyesters contain small amounts of optional polymers, antioxidants, antistatic agents, dye improvers, dyes, pigments, matting agents, optical brighteners, inert fine particles, and other additives. Is also good. In particular, when adding inert fine particles, either the external precipitation method or the internal precipitation method can be employed. [0016] The polyester fiber may be a filament yarn or a spun yarn.
In view of the appearance of the knitted fabric, the filament yarn is preferred.
Although the denier of the filament yarn is not specified, the total denier is 30 in consideration of the thickness and texture of the fabric.
~ 70 denier is preferred. The polyester fiber can be dyed at a temperature of 100 ° C. or less and has excellent dyeability, while it is necessary to have a high elongation recovery rate. 80% elongation recovery rate at 30% elongation of polyester fiber in knitted fabric
If it is less than the above, the elongation and recovery are inferior as in the case of using conventional polyester fibers, and at the same time, the texture becomes hard, which is not preferable. The polyester fiber of the present invention exhibits excellent dyeing properties and elongation-recovery properties, but also has a low elastic modulus and a softness as a texture. It is more preferable to use hollow fibers for the purpose of increasing rigidity. The hollow ratio in the case of a hollow fiber is preferably 20 to 40%,
If it is less than 20%, the effect of rigidity is hardly obtained, and if it is more than 40%, preferable characteristics can be obtained, but when industrial production is performed, operability is deteriorated, which is not preferable. The hollow shape may be a round shape, a rectangular shape, or a porous shape. The knitted fabric is knitted by cross-knitting the polyurethane elastic fiber (A) and the polyester fiber (B). The knitted fabric may be a horizontal knitted fabric or a warp knitted fabric, but a warp knitted fabric is more preferable for applications such as swimwear. Further, the knitting may be performed by a tricot knitting machine or a Russell knitting machine. Further, the knitting structure may be any knitting structure such as half knitting, reverse half knitting, double atlas knitting, and double denby knitting, but the elongation of the knitted fabric is 50% or more, preferably 80% or more. Is preferred. It is preferable that the surface of the knitted fabric is made of polyester fiber from the viewpoint of the texture. Further, the polyester fiber may be only the polyester fiber containing the above-mentioned polypropylene terephthalate as a main component, or a part of ordinary polyethylene terephthalate fiber. The knitted fabric is scoured and relaxed under ordinary conditions,
Drying is performed. Heat set temperature is 150-190 ° C
Is suitable, and preferably 160 to 180 ° C. The dyeing is carried out in a dyeing bath at 80 to 100 ° C. for 20 to 120 minutes, preferably 40 to 60 minutes. If it is lower than 80 ° C., the dyeing effect is greatly reduced. In the case of printing, a dye which develops color with saturated steam at normal pressure may be used in order to prevent embrittlement of the polyurethane elastic fiber. The dyeing machine may be a conventional one such as a wins dyeing machine or a liquid jet dyeing machine, and may be a normal pressure machine or a high pressure machine. The dye may be one selected by the dye maker for the dispersible dyeable polyester. Since the stretchable knitted fabric described above uses urethane-based elastic fibers having improved chlorine resistance, when used for swimwear, for example, it is less likely to deteriorate due to chlorine water in pools and the like, and has a high durability. Is improved, and the texture of the knitted fabric can be improved because the polyester fiber mainly composed of polypropylene terephthalate is used, and a more suitable texture can be obtained by using the hollow fiber, and the conventional polyamide fiber The effect of being superior in wet fastness as compared with the used fabric can be exhibited. Hereinafter, the present invention will be described in detail with reference to examples. The measuring method used in practicing the present invention is as follows. (1) relative viscosity consisting of p-chlorophenol and tetrachloroethane,
It measured at 30 degreeC using the mixed solvent of 3: 1 by weight. The solution viscosity is 0.4 g / dl. (2) Elongation recovery rate Constant speed elongation tensile tester (Orientec RTM-
250 type) with a sample length of 20 cm, an initial load of 1/30 g per denier, and fixed at both ends, and stretched to 30% at a pulling rate of 10% / min.
After standing for a minute, remove the weight at the same speed and return to the initial state. Leave it for 3 minutes as it is, apply the tensile strain again at 10% / min, and extend it by 30% to finish the test.
It is calculated from the 30% elongation (E) and the residual strain (ΔE) according to the following equation. Elongation recovery rate (%) = ((E−ΔE) / E) × 100 (3) From the cross-sectional photograph of the hollow fiber, the cross-sectional area of the hollow portion and the area in the outer periphery of the fiber including the hollow portion are shown. Is calculated by the following equation. Hollow ratio = (area of hollow portion / cross-sectional area in outer periphery of fiber) × 10
(4) Seawater fastness JIS L 0847 '75 (5) Tensile force during fabric elongation Using a tensile tester similar to the elongation recovery rate, draw an SS curve at 80% elongation. (6) Deterioration of elastic fiber due to chlorine water Comparison of strength after immersion in 10,000 ppm chlorine water for 2000 hours [Example] ( Example) 1. Comparative Examples 1 to 3 ) A prepolymer was prepared by reacting polytetramethylene glycol having a hydroxyl group at both terminals and having a number average molecular weight of 2,000 with 4.4'-diphenylmethane diisocyanate in a molar ratio of 1: 2. Then, the chain is extended with 1.2 propylene diamine, and a polyurethane solution having a polymer concentration of 30% (solvent is dimethylformamide) and a viscosity of 2000 poise (30 ° C.) is used. A liquid was obtained. Magnesium oxide dispersed in dimethylformamide (having an average particle size of 0.
1 to 2 μm) was added to polyurethane, and an antioxidant, an ultraviolet absorber, and a gas yellowing inhibitor were further added, followed by mixing and stirring to obtain a spinning dope. After defoaming the spinning stock solution, the spinning solution was discharged from a spinneret having a hole diameter of 0.2 mm and 5 holes, and the solvent was removed in a spinning tube through which heated air at 180 ° C. was flown. The yarn was wound and wound at a speed of 500 m / min while applying an oil agent to the yarn at a rate of 6% to obtain a polyurethane elastic fiber (a1) having 40 denier and 5 filaments. A polypropylene terephthalate having a relative viscosity of 1.40 is melted at 260 ° C., extruded from a spinneret having 24 holes having a diameter of 0.3 mmφ, wound up once at a winding speed of 1000 m / min, and subsequently rolled up at a speed of 2 m2. .
Stretched 6 times and heat-set to 50 denier 24
A filament drawn yarn (b1) was obtained. Further, two C-shaped slit holes are used as a spinneret.
A 50-denier 24-filament hollow fiber (b2) was obtained by the same spinning and drawing method as in the above (b1) , except that the four-hole die was used. A 50 denier 24-filament polyester fiber (b3) was obtained by the same spinning and drawing method as in Example 1 except that the spinning temperature was set to 280 ° C. using polyethylene terephthalate. A polyurethane elastic fiber (a2) was obtained in the same manner as in Example 1, except that magnesium oxide was not added at all. Using the obtained fibers, a warp knitted fabric was prepared using a 28 gauge tricot knitting machine manufactured by KARL MAYER. The warping draft of the fibers (a1) and (a2) is 100%, the knitting length during knitting is (a) 70 cm / 480 course, and (b)
1), (b2) and (b3) are 160cm / course
The onboard course was 55 courses. The four types of greige fabrics thus obtained are scoured, relaxed, dried and heat-set, and each knitted fabric is dyed and soaped with a commercially available disperse dye using a normal pressure loco-type jet dyeing machine. Dry setting was performed to obtain an elastic knitted fabric.
Table 1 shows the results of the obtained knitted fabric. [Table 1] The color of the knitted fabric of Example 1 was clear, the polyurethane elastic fiber had high chlorinated water deterioration and high seawater fastness, and the knitted fabric had excellent tension. Furthermore, the knitted fabric of Example 1 in which the polyester fiber was hollow had a moderate stiffness as compared with that of Comparative Example 1 . On the other hand, in the knitted fabric of Comparative Example 3 , a decrease in seawater fastness and deterioration of the polyurethane fiber were recognized, and an appropriate knitting force of the knitted fabric could not be obtained. According to the present invention, it is possible to obtain a stretchable knitted fabric having excellent chlorine resistance and dyeing properties, and having stretch recovery properties and texture, which is suitable for sports use.

Claims (1)

(57) [Claims 1] A polyurethane elastic fiber (A) of 20 to 100 denier and a hollow ratio of 20 to 4 of 30 to 70 denier.
It met mixed knitting knitted fabric of 0% of the hollow polyester fiber (B)
The fiber (A) is a fiber containing 0.5 to 4.5% by weight of one or more of the following compound groups in the fiber, and the fiber (B) is mainly composed of polypropylene terephthalate. An elastic knitted fabric comprising a component, and a fiber having an elongation recovery rate of 80% or more at 30% elongation. * Compound group: magnesium oxide, zinc oxide, aluminum oxide, magnesium hydroxide, zinc hydroxide, aluminum hydroxide, hydrotalcite compound