JP3398476B2 - Extra fine nylon 66 multifilament yarn - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improved ultrafine nylon 66 multifilament yarn for clothing, which has less yellowing and embrittlement. [0002] Nylon 66 fiber has been used in various garment applications because of its excellent strength, durability and elasticity, high melting point and good heat resistance among nylon. In recent years, in the textile industry, the trend of fashion has progressed, and fabrics are required to have functions such as high bulkiness and elegant texture. Using mixed products with different types of fibers,
Wrinkle processing to add wrinkles to the fabric at the dyeing process stage,
It has been used as an effective means for providing the above functions. [0003] In the post-processing step of a fabric such as a mixed product of a nylon fiber with a polyester fiber or a wrinkled product, high-temperature moist heat processing conditions of 120 to 130 ° C which are not usually used for nylon fibers are required. However, the nylon 66 fiber has a disadvantage that the strength retention rate is greatly reduced when such high-temperature wet heat processing conditions are employed. [0004] This drawback is a significant problem in the use of fine denier single yarns required in the production of delicate mixed fabrics.
On the other hand, the nylon 66 multifilament yarn as a multifilament raw yarn for clothing has an unfortunate disadvantage that a fabric product is easily yellowed by heat or light. This yellowing
Also occurs in the heat setting process in the fabric dyeing process,
The dullness and yellowing of the light-colored light cloth are elegant outerwear,
The use of ultra-fine single yarn nylon 66 multifilament yarn for the inner garment has been markedly hindered. SUMMARY OF THE INVENTION The present invention solves such a disadvantage of a nylon 66 multifilament yarn using a fine denier single yarn, and has a strength embrittlement even under high temperature wet heat processing conditions. It is intended to provide a nylon 66 multifilament yarn which is less likely to yellow due to heat or the like. SUMMARY OF THE INVENTION The present invention relates to a method for manufacturing a liquid crystal display device comprising:
A nylon 66 multifilament composed of 1 denier single yarn, wherein the birefringence of the fiber is 50 × 10 ^−3.
６０60 × 10 ⁻³ , peak temperature (T _max ) of mechanical loss tangent (tan δ) is 105 to 140 ° C., 20 ° C., 60% R
A nylon 66 multifilament yarn for clothing characterized by having an initial modulus in H of 45 to 55 g / d and having 55 to 100 meq of amino end groups per kg of fiber. [0007] The nylon 66 multifilament yarn to which the present invention is applied is used for knitted fabrics for clothing, especially for thin yarns for thin fabrics, and is a single yarn of 0.3 to 1.1, preferably about 0.8 denier or less. With a total denier of 100
It is a multifilament yarn having a denier of not more than 50 deniers. In the present invention, the nylon 66 multifilament yarn has mechanical properties suitable for cross-knitting, weaving or blending with a general-purpose polyester multifilament yarn, and has an initial modulus in the range of 45 to 55 g / d. The fiber structure has a birefringence of 50 × 1
0 ^{-3 to} 60 × 10 ^-3 , and a peak temperature (T _max ) of a mechanical loss tangent (tan δ) of 105 to 140 ° C. In the present invention, the content of amino groups in the fiber must be in the range of 55 to 100 meq / kg, preferably 60 to 90 meq / kg of fiber. This region is a region in which suppression of embrittlement of fibers by high-temperature and high-temperature heat treatment at 120 to 130 ° C is recognized. 55 amino terminal groups
When the equivalent weight is less than the milliequivalent / kg, the fibers are remarkably embrittled by the above-mentioned wet heat treatment, and the strength of the fibers is reduced by 20% or more. When a polymer having an amino terminal group content of more than 100 meq / kg is used, a fiber having poor practical performance such as strength, for example, is required. On the other hand, in the above-mentioned region, yellowing during the heat treatment of the fiber is remarkably suppressed particularly when the amount of amino terminal groups is 60 meq / kg or more. Normally, synthetic fibers are knitted and woven, and then subjected to refining and dyeing. Due to this yellowing suppressing effect, the temperature is set at about 180 ° C. in a preset and finishing set made in this process. Since the yellowing of the resulting fabric is suppressed, it is possible to keep the appearance of the fabric product beautiful. The single yarn denier of the ultrafine nylon 66 multifilament yarn of the present invention is from 0.3 to 1.1 denier. When the single yarn denier is in the above range, the fabric obtained by using the single yarn denier can be imparted with excellent feel and drape, and the fabric can be made lighter and thinner.
If the single yarn denier exceeds 1.1 denier, an elegant feel and drape cannot be achieved due to high bending stress of the filament. On the other hand, if the single yarn denier is less than 0.3, a satisfactory multifilament yarn cannot be obtained due to yarn breakage during yarn production. Further, the ultrafine multifilament yarn of the present invention has a peak temperature T _max of a mechanical loss tangent (tan δ).
Is 105 ° C. or more and 140 ° C. or less. T _max is 10
Those having a temperature of less than 5 ° C. are obtained by a high-speed spinning method and have low breaking strength and high breaking elongation in mechanical properties. For this reason, when the fabric is formed using the ultra-fine multifilament yarn, fluff and yarn breakage are likely to occur, and in particular, a lightweight and thin fabric cannot be obtained. Further, in a normal nylon 66 multifilament yarn, T
_{The max} can only be obtained at 140 ° C. or less. Above, T
_The fiber properties of ultra-fine nylon 66 multifilament yarn having a _max of 105 ° C. or more and 140 ° C. or less are 20 ° C., 60% R
The initial modulus at H is 45-55 g / d,
The birefringence is 50 × 10 ⁻³ to 60 × 10 ⁻³ . The nylon 66 multifilament yarn of the present invention can be produced by melt-spinning polyhexamethylene adipamide in which the amount of amino terminal groups is adjusted substantially within the above range. The polyhexamethylene adipamide polymer used in the present invention is produced by ordinary melt polycondensation, and the polymerization system may be a batch polymerization system or a continuous polymerization system. For example, as a batch polymerization method, hexamethylene diammonium adipate (AH salt), which is a salt of hexamethylene diamine and adipic acid, is used.
A 0% by weight aqueous solution is mixed with an additive such as a polymerization degree regulator and charged into a concentration tank, and heated to about 150 ° C. to obtain about 80% by weight.
Concentrate to a concentration of. This concentrated liquid is supplied to the polymerization tank,
Continue heating. At this time, the condensed water is removed while controlling the pressure in the polymerization tank to about 18 kg / cm ² by a pressure control valve, and the internal temperature is raised to 250 ° C. Next, the pressure of the polymerization tank was gradually released to normal pressure while continuing heating,
The internal temperature is raised to 280 ° C. and maintained for several tens minutes to complete the polycondensation. The produced polymer melt can be pressed with an inert gas, extruded from a discharge mouthpiece, cooled, and pelletized. As the continuous polymerization method, Brit.
P. 674, 954 (1949) and Adv. Poly.
Tech. , 6, (3), 267 (1986) and the like. Further, the polymer chip obtained by the above polymerization method, at a temperature 20 to 80 ° C. lower than the melting point, by heating under reduced pressure vacuum or an inert gas to perform solid-phase polymerization, further increasing the degree of polymerization good. In these general polymerization methods, in order to adjust the concentration of amino terminal groups to a predetermined amount, for example, it is most preferable to add an excess of hexamethylenediamine, which is one component of the raw material, at the time of charging the raw material. Simple and effective. It can also be achieved by adding hexamethylene diamine during the course of the polymerization. Furthermore, other diamine compounds can be used, and it is also possible to increase the concentration of amino terminal groups by adding them during the preparation of raw materials or during the polymerization. The VR (formic acid relative viscosity) of the present invention may be appropriately set according to the intended use.
30 to 60. Also, a small amount of a copolymer component within a range that does not deteriorate the physical properties of the nylon 66 multifilament yarn may be contained. The nylon 66 used in the present invention may contain a small amount of commonly used additives, for example, a matting agent represented by titanium oxide, an antistatic agent such as polyethylene glycol, a heat stabilizer such as hindered phenol, an alkylenediamine. And a polymerization degree regulator such as an alkylamine. The nylon 66 multifilament yarn of the present invention is produced by applying a melt spinning drawing method to the above polymer. A known spinning method such as a spin draw method as illustrated in FIG. 1 can be employed. EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but it goes without saying that the present invention is not limited to these Examples. The method for measuring the structural characteristics and other characteristics of the filament yarn used in the present invention is as follows. (1) Dynamic loss tangent (tan δ)) For measurement of the mechanical loss tangent (tan δ), VIBRONDDV-II manufactured by Orientec Co., Ltd. is used. Measurement frequency 110Hz, heating rate 10 ° C / min, in dry air,
The tan δ-temperature (T) characteristic is measured. A tan δ peak temperature T _max (° C.) is obtained from the tan δ-temperature curve. FIG. 2 schematically shows a tan δ-T curve of the filament yarn of the present invention. (2) Birefringence (Δn) For the measurement of birefringence, a transmission interference microscope manufactured by Carl Zeiss Jena Co., Ltd. is used. Wavelength 549mμ, temperature 25
At ° C., the refractive index n ₁₁ for light vibrating parallel to the filament axis and the value of the refractive index n 垂直 for light vibrating perpendicular to the filament axis are given by: ## EQU1 ## Note that the center of the filament defines the center of gravity when the filament cross section is considered to be one plane for both the circular cross section and the irregular cross section filament. (3) Strong elongation, initial modulus Orientec Co., Ltd. TENSIRON UTM-II
It was measured by a conventional method using a -20 type tensile tester. The measurement atmosphere is 20 ° C. and RH 60%. (4) The sample length under a load of 0.1 g / d of shrinkage of boiling water is Lo, and the sample is treated in boiling water with no load for 30 minutes, and the length L is again measured under a load of 0.1 g / d. Is measured. The boiling water shrinkage BWS (%) is represented by BWS (%) = (Lo−L) / _LO × 100. (5) VR (Relative Viscosity of Formic Acid) 8.4% by weight of nylon 66 is dissolved in a 90% formic acid solution and measured at 25 ° C. by a conventional method. (6) After scouring the amino-end group-concentrated yarn at 60 ° C. for 30 minutes with a nonionic surfactant aqueous solution having a concentration of 2 g / liter at 100 times the weight to remove the finishing agent, Polymer Analysis Handbook ”edited by The Japan Society for Analytical Chemistry (Asakura Shoten Publishing) 32
Analyzed by the method of three pages. (7) The carboxyl end group concentration yarn was analyzed after the scouring treatment according to the method described in “Polymer Analysis Handbook”, edited by The Japan Society for Analytical Chemistry, Asakura Shoten, p. (8) Strength Retention by High-Temperature and High-Temperature Heat Treatment A yarn is formed into a tubular knitted fabric. After the treatment, the knitted fabric was unwound and the strength was measured, and the strength retention was determined by the following equation. (9) A heated yellowed one-piece knitted fabric is prepared, scoured, and left to dry. Next, it was placed in a hot-air oven and heat-treated at 190 ° C. for 5 minutes in an air atmosphere. The knitted fabric subjected to this treatment was subjected to color measurement using a spectrophotometer SZ-Z90 manufactured by Nippon Denshoku Industries Co., Ltd., to determine the yellowness YI. (10) Tear strength of woven fabric Tear strength (g) according to JIS-L-1096 (1990) General Fabric Test Method 6.15.5 (Pendulum method)
Was measured in the meridional and weft directions. The warp direction tear strength was the direction in which the warp was cut, and the weft direction tear strength was the direction in which the weft was cut. Example 1 Raw materials were charged at the following ratios into an autoclave having a capacity of 400 liters, and batch polymerization was carried out. 270 liters of a 50% by weight aqueous solution of AH salt, 4.2 liters of a 14% by weight aqueous solution of hexamethylenediamine, and 0.4 liters of an 8% by weight aqueous solution of titanium oxide were charged. Concentration was carried out to weight%. Next, the mixture was fed to a polymerization tank, heating was continued, the condensed water was removed while the internal pressure was controlled at 17.5 kg / cm ² , the temperature was raised to 250 ° C., and polymerization was advanced for 1.5 hours. Next, the internal temperature was raised to 280 ° C., gradually returned to normal pressure over 1 hour, and maintained for 30 minutes to complete the polymerization. The polymer obtained had a VR of 45 and an amino terminal group concentration of 80 meq / kg polymer. The obtained polymer was dried, the water content was set to 1200 ppm, and melt spinning was performed using a spinning apparatus as shown in FIG. That is, the polymer melted at an extrusion temperature of 295 ° C. was guided to a spinneret having a 96 mm spinning nozzle having a diameter of 0.2 mm and discharged. The cooling of the yarn is performed at a temperature of 18 ° C. and a speed of 0.5 using a 1.8 m long cooling air device along the running direction of the yarn.
The test was carried out under the conditions of cold air blowing sideways at m / sec. After cooling the yarn, a finishing agent is applied, and the yarn is stretched 2.0 times using two pairs of godet rolls (the temperature of the first pair of godet rolls is 65 ° C. and the temperature of the final pair of godet rolls is 160 ° C.).
Table 1 shows the fiber properties of the multifilament yarn obtained at a speed of 70d / 96f per minute. Using the above-mentioned nylon 66 multifilament as the warp and the weft, a plain woven fabric (warp density: 120 / inch, weft density: 90 / inch) was obtained. 8
After continuous scouring at 0 ° C., dyeing was performed using a jet dyeing machine. The staining conditions were as follows. Kayanol Millinq Ultra Sky SE (Nippon Kayaku) 3% owf New Bonn TS-66 (Nika Chemical) 1 g / l Bath ratio 1:20, 120 ° C × 60 minutes By the above-mentioned dyeing process, it flows in the longitudinal direction of the fabric. A wrinkled product with wrinkles was obtained. After spreading and drying this, a finishing set at 180 ° C. for 30 seconds was performed, and the characteristics of the obtained fabric were evaluated. Table 1 shows the results. Examples 2-3 and Comparative Example 1 In the polymerization of the polymer, the amount of hexamethylenediamine added as a raw material was changed, and adipic acid was added instead of hexamethylenediamine. In the same manner as in Example 1, nylon 66 polymers having different amino terminal group concentrations were obtained. Table 1 shows the VR, amino terminal group concentration and carboxyl terminal group concentration of the obtained polymer. These polymers were spun and stretched in the same manner as in Example 1 to obtain 70 d /
A 96f nylon 66 multifilament was obtained. Table 1 shows the fiber properties of the obtained multifilament yarn. These fibers were made into a fabric in the same manner as in Example 1 and subjected to a dyeing process to obtain a wrinkled product. Table 1 shows the properties of the obtained fabric. Example 4 The same procedure as in Example 1 was carried out except that the polymer obtained in Example 1 was used and the discharge amount was changed.
Thus, a nylon 66 multifilament of f was obtained. Table 1 shows the properties of the fibers of the obtained multifilament yarn. The multifilament yarn was used as a warp and a weft to form a plain fabric, and then dyed and finished in the same manner as in Example 1. (Warp density: 170 yarns / inch, weft yarn density: 90 yarns / inch) The characteristics of the obtained fabric are shown in Table 1. The obtained wrinkled product had a good feel and good appearance. Example 5 and Comparative Example 2 The nylon 66 multifilament yarn of Example 1 and Comparative Example 1 was used for the warp, and a 75d / 36f polyester plain yarn was used for the weft, and the warp density was 114 yarns / inch. A plain weave having a weft density of 84 yarns / inch was obtained. After the scouring treatment, this was subjected to presetting at 180 ° C. for 30 seconds, and two-bath dyeing was performed using a jet dyeing machine. The staining conditions are as follows. (1st bath) Kayanol Polyester Blue 3R-SF (Nippon Kayaku) 0.96% owf Bath ratio 1:30, 30 minutes at 130 ° C, PH = 5.0 Dispersant: Nikka San Salt 7000 (Nichika Chemical) 1 g / l (second bath) Kayanol Milling Blue 2RW (Nippon Kayaku) 0.48% owf Bath ratio 1:30, 100 ° C for 30 minutes, PH = 5.0 Leveling agent: Newbon TS-66 (Nichika) Chemical) 1g / l After dyeing, New Sanlex (Nichika Chemical)
Soaping was performed at 60 ° C. for 20 minutes with a 2 g / l aqueous solution. Finish setting was performed at 180 ° C. for 30 seconds to obtain a product fabric. Table 1 shows the properties of the obtained fabric. [Table 1] The nylon 66 multifilament yarn for clothing of the present invention does not cause strength embrittlement under high-temperature moist heat treatment. The mechanical performance can be maintained almost at the same level as the original yarn even in the high-temperature wet-heat processing of the wrinkled product. Further, the nylon 66 multifilament yarn of the present invention suppresses yellowing generated under various heat setting in processing, so that the elegance and appearance of the secondary product of fine denier single yarn are enhanced. Can be

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view of a spinning device used in an embodiment of the present invention. [Description of Signs] 1 Extruder 2 Spinning head 3 Cooling air device 4 Yarn 5 Finishing agent applying device 6 Godet roll 7 Winding device 8 Winding yarn

──────────────────────────────────────────────────続 き Continued on the front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) D01F 6/60 D01F 6/90

Claims (1)

(57) Claims 1. The initial modulus at 20 ° C. and 60% RH is 45 to 55 g / d, and the mechanical loss tangent (ta)
nδ), the peak temperature T _max is 105 ° C. or more and 140 ° C. or less, the birefringence is 50 × 10 ^{−3 to} 60 × 10 ⁻³ , and the single-filament denier of the constituting filament is 0.3 to 1.1 denier. And ultrafine nylon 66 multifilament yarns having 55 to 100 milliequivalents of amino end groups per kg of fiber.