METHOD FOR THERMAL MOLDING OF FILAMENT PRODUCT

Abstract

Provided is a thermal molding method for producing a thermally molded article having excellent abrasion resistance at its melt-fused part. Polyamide 6 and a copolyester are prepared separately. The copolyester contains terephthalic acid, ethylene glycol, and 1,4-butanediol as copolymerization units. The copolyester may further contain ε-caprolactone and/or diethylene glycol as a copolymerization unit. A multifilament yarn in which core-sheath type composite filaments each containing a core component and a sheath component at a ratio of 1 to 4:1 by mass are bundled is produced by a composite melt-spinning method using the polyamide 6 as the core component and the copolyester as the sheath component. Using the multifilament yarn, a product of filaments is produced by weaving, knitting, knitting and braiding, or braiding. The product of filaments is heated to melt the copolyester and fuse the core-sheath type composite filaments to each other while retaining the initial filament form of the polyamide 6, thus thermally molding the product of filaments.

Claims

1. A method for thermal molding a product of filaments, the method comprising: a step of producing multifilament yarns by bundling core-sheath type composite filaments, wherein the core-sheath type composite filaments are obtained by a composite melt-spinning method, using a copolyester containing terephthalic acid, ethylene glycol, and 1,4-butanediol as copolymerization units for a sheath component, and using polyamide 6 for a core component, and the core-sheath type composite filaments have a mass ratio of core component : sheath component being 1 to 4:1; a step of producing a product of filaments using the multifilament yarns; and a step of heating the product of filaments to melt the copolyester and fuse the core-sheath type composite filaments to each other while retaining initial filament form of the core component of polyamide 6.

2. The method for thermal molding a product of filaments according to claim 1, wherein the copolyester further contains ε-caprolactone and/or diethylene glycol as the copolymerization unit.

3. The method for thermal molding a product of filaments according to claim 1, wherein the product of filaments is produced by using a yarn thread including a plurality of the multifilament yarns arranged in parallel.

4. The method for thermal molding of a product of filaments according to claim 1, wherein the product of filaments is selected from the group consisting of a knitted or woven fabric, net, and cord.

5. The method for thermal molding of a product of filaments according to claim 1, wherein the net is a knotless net, and the core-sheath type composite filaments are fused to each other entirely including strands and intersections.

Description

EXAMPLES

Example 1

[Preparation of Multifilament Yarn]

[0016] As a sheath component, a copolyester having a melting point of 160° C. was prepared. This copolyester included 86.8 mol of terephthalic acid, 36.8 mol of ethylene glycol, 49.2 mol of 1,4-butanediol, 13.2 mol of ε-caprolactone, and 0.8 mol of diethylene glycol in terms of the molar ratio of copolymerization units. On the other hand, polyamide 6 having a melting point of 225° C. was prepared as a core component. The above-mentioned copolyester and polyamide 6 were supplied to a composite melt-spinning apparatus equipped with a core-sheath type composite spinneret having a hole diameter of 0.6 mm and 192 holes, and composite melt-spinning was performed with the spinneret temperature being set to 270° C. and the ratio of the copolyester and polyamide 6 being 1:2.7 by mass. A yarn thread in which the produced 192 core-sheath type composite filaments were bundled was subjected to cooling, stretching, and relaxation treatments by a conventional means to produce a multifilament yarn with 1670 dtex/ 192 filaments.

[Preparation of Product of Filaments and Thermal Molding)]

[0017] A yarn thread having two of the produced multifilament yarns arranged in parallel were wound on a bobbin for braiding, and then introduced into an 8-carrier square braiding machine to produce an 8-strand braid. In the 8-strand braid, the sheath components of the core-sheath type composite filaments in the braid were fused to each other under the conditions of a temperature of 180° C. and a time of 1 minute to produce a thermally molded cord in which the whole was integrated.

Example 2

[0018] A thermally molded cord was produced by the same method as Example 1 except that the ratio of the copolyester and polyamide 6 was changed to 1:1.5 (by mass).

Example 3

[0019] A yarn thread was produced, in which 16 of the multifilament yarns produced in Example 1 were arranged in parallel. By hanging four of the yarn threads on a braid netting machine and braiding the yarn threads, a knotless net having strands and intersections was produced. This knotless net was introduced into a pin tenter type heat treatment apparatus and heat-treated for 3 minutes in an atmosphere of 180° C. while applying tension in the width direction. Subsequently, it was left at room temperature and cooled to produce a thermally molded net. In this thermally molded net, the sheath components were melted, and the core-sheath type composite filaments were fused to each other at both the strand parts and the intersections. In addition, the diameter of the strand was about 4 mm and the area of the intersections part was about 40 mm.sup.2, and the mesh had a square shape and had an area of about 6 cm.sup.2. Using the net, a tubular and rectangular parallelepiped aquaculture net was produced.

Comparative Example 1

[0020] Except that polyethylene (manufactured by Japan Polyethylene Corporation, product number UJ580) with a melt flow rate of 59.8 g/ 10 minutes (the melt flow rate value under the conditions of a temperature of 280° C., a load of 2.16 kgf) at a melting point of 123° C. was used as the sheath component, a multifilament yarn with 1670 dtex/ 192 filaments was produced in the same method as Example 1. Using the multifilament yarn, a thermally molded cord was produced by the same method as Example 1 except that the temperature was set to 150° C.

Comparative Example 2

[0021] Except that polyethylene terephthalate (the melting point 256° C., the limiting viscosity [η] 0.75) was used instead of the polyamide 6 as the core component, 8-strand braid was produced by the same method as Example 1. Then, in the 8-strand braid, the sheath components of the core-sheath type composite filaments in the braid were fused to each other under the conditions of a temperature of 180° C. and a time of 1 minute to produce a thermally molded cord in which the whole was integrated. The limiting viscosity [n] was measured at a concentration of 0.5 g/dl and a liquid temperature of 20° C. using an equal-weight mixture of phenol and ethane tetrachloride as a solvent.

[0022] The thermally molded cords produced in Examples 1 and 2 and Comparative Example 1 were evaluated for abrasion resistance using an abrasion resistance tester manufactured by Yonekura Mfg. Co., Ltd. Specifically, a 1 kg weight was hung on one end of a thermally molded cord, and the other end was gripped with a chuck so as to be made contact with a hexagonal rod at a right angle. Then, the other end was reciprocated. The reciprocation was performed for about 20 minutes with the number of reciprocating motions of 30±1 time/minute and a stroke width of 230 mm±30 mm. As a result, the thermally molded cords according to Examples 1 and 2 kept the initial fused state to some extent, though waste was generated. On the other hand, in the thermally molded cord according to Comparative Example 1, the fusion came undone and the multifilament yarns were exposed to become fibrous. From the above, it is shown that the thermally molded cords according to Examples 1 and 2 have excellent abrasion resistance. Further, it is shown that the thermally molded net according to Example 3, in which the strands are braided, has excellent abrasion resistance as with the thermally molded cords according to Examples 1 and 2.

[Test for Bending Fatigue]

[0023] Using the thermally molded cords produced in Examples 1 and 2 and Comparative Examples 1 and 2 as samples, a bending fatigue test was performed by the following method.

[0024] First, in accordance with JIS L-1013 (2000) 8.5.1 tensile strength test for standard condition, the tensile strength (N) of each sample before bending was measured using Autograph AG-1 manufactured by Shimadzu Corporation at a grip interval of 250 mm and a tensile speed of 300 mm/min. Each sample was subjected to a MIT type folding endurance tester manufactured by MYS-TESTER Company Limited and bent at an angle of ±120° and a test speed of 175 times/minute. The number of bendings was 500, 2000 and 5000. The tensile strength (N) was measured for each sample after the bendings by the same method as mentioned above, and the results are shown in Table 1. Then, the strength retention (%) was calculated by the following formula and the results are shown in Table 2. Strength retention (%)=[(Tensile strength of a sample after bendings (N))/(Tensile strength of a sample before bendings (N))]×100.

TABLE-US-00001 TABLE 1 [Tensile strength (N)] Before After 500 After 2000 After 5000 bendings bendings bendings bendings Example 1 543 542 551 520 Example 2 452 476 463 432 Comparative 459 459 421 414 Example 1 Comparative 482 421 307 225 Example 2

TABLE-US-00002 TABLE 2 [Strength retention (%)] Before After 500 After 2000 After 5000 bendings bendings bendings bendings Example 1 100 99.8 101.5 95.8 Example 2 100 105.5 102.5 95.6 Comparative 100 100 91.8 90.2 Example 1 Comparative 100 87.4 63.6 46.7 Example 2

[Durability Test Against Alkalinity]

[0025] Using the 8-strand braids and the thermally molded cords produced in Examples 1 and 2 and Comparative Example 2 as samples, durability tests against alkalinity were performed by the following two methods.

(1) Test for Strength Retention (%)

[0026] A 3N sodium hydroxide aqueous solution was prepared using sodium hydroxide (99%, manufactured by Maruzen Co., Ltd.). Next, the samples (8-strand braids and thermally molded cords) were immersed in the sodium hydroxide aqueous solution having a weight 10 times or more the weight of the samples and left to stand for 960 hours. Subsequently, the samples were pulled out of the sodium hydroxide aqueous solution, rinsed in pure water for 10 seconds×2 times, and then washed with running water for 1 minute. Next, the dried samples from which water contained in the samples was removed by air-drying for 2 days were measured for tensile strength (N1) under the same conditions as in the above-mentioned bending fatigue test. Then, the tensile strength (N0) of the 8-strand braids and the thermally molded cords before immersion in sodium hydroxide aqueous solution was also measured under the same conditions, and the strength retention (%)=(N1/N0)×100 was calculated.

(2) Test for Weight Loss Rate (%)

[0027] The samples (8-strand braids and thermally molded cords) before immersion in the sodium hydroxide aqueous solution was placed in a dryer at 50° C. for 24 hours, and then placed in a desiccator containing a desiccant for 1 hour or more. Subsequently, the weight (W0) of each sample was measured at room temperature. On the other hand, the dried samples of the above-mentioned (1) were placed in a dryer at 50° C. for 24 hours, and then placed in a desiccator containing a desiccant for 1 hour or more. Subsequently, the weight (W1) of each sample was measured at room temperature. Then, the weight loss rate (%)=[(W0−W1)/W0]×100 was calculated.

[0028] The test results of the strength retention (%) of the above-mentioned (1) and the test results of the weight loss rate (%) of the above-mentioned (2) are shown in Table 3.

TABLE-US-00003 TABLE 3 Strength Weight retention loss rate N0 N1 (%) (%) Example 1 (8-strand braid) 564 500 88.7 26.8 Example 1 (thermally 533 453 85.0 26.8 molded cord) Example 2 (8-strand braid) 513 423 82.5 39.9 Example 2 (thermally 477 413 86.4 36.9 molded cord) Comparative (8-strand braid) 475 174 36.6 70.0 Example 2 Comparative (thermally 480 403 83.9 6.0 Example 2 molded cord)

[Durability Test Against Acidity]

[0029] The strength retention (%) and the weight loss rate (%) were tested by the same method as [Durability test against alkalinity] except that sulfuric acid (98%, guaranteed reagent, manufactured by Kanto Chemical Co., Inc.) was used instead of the 3N sodium hydroxide aqueous solution to make a 5N acidic aqueous solution. The results are shown in Table 4.

TABLE-US-00004 TABLE 4 Strength Weight retention loss rate N0 N1 (%) (%) Example 1 (8-strand braid) 564 133 23.6 1.7 Example 1 (thermally 533 156 29.2 −5.3 molded cord) Example 2 (8-strand braid) 513 232 45.3 7.8 Example 2 (thermally 477 368 77.2 −0.1 molded cord) Comparative (8-strand braid) 475 471 99.3 0.2 Example 2 Comparative (thermally 480 474 98.6 0.0 Example 2 molded cord)

[0030] For reference, a yarn thread in which two nylon multifilament yarns (manufactured by Unitika Ltd., product number “N742”, 940 dtex/96 filaments) were arranged in parallel was wound around a bobbin for braiding, and then introduced into an 8-carrier square braiding machine and an 8-strand braid was produced. This 8-strand braid was subjected to the durability test against acidity mentioned above and the strength retention (%) was measured. As a result, the initial tensile strength (N0) was 838N, but the tensile strength (N1) after the immersion treatment was 123N, and the strength retention (%) was 14.7%. Polyamide resins tend to be inferior in durability to acids, but the multifilament yarns used in the Examples has a core-sheath type composite filament with the sheath of the copolyester and the core of the polyamide 6, in which the polyamide 6 is covered with the copolyester, so that the strength retention (%) against acidity is improved as compared with the case where a nylon multifilament yarn is used.