JPH07145316A - Polyamide composition with excellent light resistance - Google Patents

Abstract

PURPOSE:To obtain the composition which has satisfactory heat resistance and does not develop coarse particles during melting. CONSTITUTION:This polyamide composition contains a copper complex in an amount of 10-1,000ppm by weight, in terms of copper amount, based on the polyamide, the complex consisting of cuprous bromide and a compound having a thiol group in a molar ratio of 1:1.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyamide composition, and more specifically, to a molded article such as a polyamide fiber or a film which can be advantageously applied to applications requiring high light resistance and heat resistance such as automobile interior materials. Provided is a polyamide composition.

[0002]

2. Description of the Related Art Polyamide is widely used in the form of fibers, films, etc. for clothing, interiors and industrial materials because it has excellent strength, abrasion resistance, impact resistance and dyeability. . However, polyamide has a drawback that it is susceptible to oxidative deterioration, and especially when it is heated to a high temperature, the oxidative deterioration is remarkable. As a remedy for this, a method of adding a copper compound and 2-mercaptobenzimidazoles as antioxidants (light resistance and heat resistance improver) is known (Japanese Patent Publication No. 38-22720, Japanese Patent Publication No. 48-7858). JP-B-48-7859, JP-B-48-7860, JP-B-60-1
7309, Japanese Patent Publication No. 61-45662).

[0003]

In the conventional method, when the polyamide is melted, the lightproofing agent undergoes thermal decomposition to produce an insoluble chemical compound, and during melt spinning, an operation such as an increase in back pressure of the spinning nozzle or yarn breakage occurs. The above problems may occur, and the dyeing product is not satisfactory in high-temperature light resistance.

The present invention has been made in view of the above circumstances, and an object thereof is not to produce an insoluble matter at the time of performing melt spinning and the like, and to obtain excellent light resistance and dyeability. It is intended to provide a polyamide composition capable of exhibiting heat resistance and a molded product thereof.

[0005]

That is, the present invention contains a complex consisting of cuprous bromide and a compound containing a thiol group in a molar ratio of 1: 1 in an amount of 10 to 1000 ppm in terms of copper weight based on the weight of polyamide. It is a polyamide composition having excellent light resistance.

The compound containing a thiol group is not particularly limited, but 2-mercaptobenzazoimidazole,
2-mercapto-1-methylimidazole, 2-mercaptobenzothiazole, 6-amino-2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 5-mercapto-1-methyltetrazole, 2-mercaptothiazoline, 2
-Mercaptopyridine, 2-mercapto-4-pyrimidone, and their derivatives.

The method of incorporating a complex of cuprous bromide and a compound containing a thiol group can be carried out by premixing cuprous bromide and a compound containing a thiol group as a complex, or without forming each complex. Any method of blending may be used, but it is added to the polyamide pellets during polymerization of the polyamide or before spinning. Generally, a method of coating the polyamide pellets before spinning is adopted.

The polyamide to which the present invention is applicable includes
Nylon 6, Nylon 12, Nylon 6-6, Nylon 6-1
0, aliphatic polyamides such as polyxylene adipamide, aromatic polyamides, alicyclic polyamides, and copolyamides and mixed polyamides of these polyamides.

[0009]

EXAMPLES The present invention will be described below with reference to examples. Example 1 25 g of cuprous bromide and 2-mercaptobenzimidazole 26.2
g in 200 ml of N, N-dimethylformamide,
After slowly pouring liter to form a precipitate, 70 ℃
It was stirred for 1 hour. After cooling, the precipitate was filtered off, washed with distilled water repeatedly, and vacuum dried to form cuprous bromide.
49 g (yield 96%) of a complex consisting of 2-mercaptobenzimidazole in a molar ratio of 1: 1 was obtained. The infrared absorption spectrum of this copper complex is shown in FIG. The melting point of this copper complex is about 275.
The temperature is 0 ° C, and the nylon melts at the time of spinning at high temperature and is well mixed.

While blending dried nylon 6 resin chips (water content: 0.05 to 0.20%) in a nitrogen atmosphere, 50
After heating to -80 ℃, add 0.05 wt% of polymeric nonionic surfactant to the resin, and apply the synthesized fine particle copper complex so that the amount of copper becomes 100ppm and blend for 1 hour or more. did. The resin is heated and melted, and the extruder (temperature:
260 to 280 ℃, pressure: 100 to 200 kg / cm ² ), a beam branched for multiple weights (temperature: 250 to 280 ℃), a metering pump, and then spun into filament form from a spinning nozzle, 200 to 200
It was wound at 800 m / min, further stretched 2 to 5 times, buckled by heating, and wound on cheese as crimped processed yarn.
The initial nozzle back pressure during spinning was 142 kg / cm ² , and the nozzle filter back pressure hardly increased even after continuous spinning for 2 weeks. FIG. 2 shows how the nozzle filter back pressure increases together with the comparative example.

Further, 3 g of nylon thread was dissolved in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP), and coarse particles in nylon were filtered off with a Teflon filter having an average pore size of 5 μm. After that, a fluorescent X-ray analyzer (RIGAKU X-RAY S
As a result of copper analysis by PECTROMETER 3270), a fluorescent X-ray intensity of 0.19 kilocounts / second (kcps) per 1 g of nylon was shown. The magnitude of this value corresponds to the relative amount of coarse copper particles in nylon.

As the light resistance test sample, first, 1000 denier, 64 filaments (triangular cross-section yarn) and crimp amount CC = 20
%, Crimp stability CD = 15% of BCF nylon was set by 2 plies by a conventional method, and then tufted to prepare a saxony type carpet (unit weight: 1300 g / m ² ). Next, with the following 1: 2 type gold-containing complex salt dye prescription, after boiling for 60 minutes with a Wins dyeing machine, washing with hot water, washing with water and drying, after fusion bonding a polyethylene film on the back surface of the carpet by a conventional method,
A 10 mm thick miscellaneous felt was used as a sample. [Dyeing recipe] Irgalan Yellow GRL 0.04% owf Irgalan Red Brown RL 0.06% owf Irgalan Gray GL 0.34% owf Albegal SW (Ciba Geigy Co., Ltd. auxiliary agent) 1.0% owf Albegal FFD (Ciba Geigy Co., Ltd. auxiliary agent) 0.1 g / l Maysan PC (Meisei) Chemical industry pH adjuster) 0.5 g / l Soda ash 0.3 g / l

The light resistance was evaluated by using a UV long life fade meter (JIS B7 manufactured by Suga Test Instruments Co., Ltd.) as a tester.
751 compliant, model: FAL-5HB · BR, vertical test piece holder used). As the irradiation conditions, accelerated light resistance test W
AL-2H (JIS D0205-1987) was applied correspondingly, and irradiation was performed at a black panel temperature of 83 ± 3 ° C. for a total irradiation time of 200 hours.
The test product was changed up and down every 20 hours. The shape of the irradiated sample was assumed to be used in a house car, and a low-density polyethylene film was fused on the back surface of the irradiated sample, and a house car felt with a thickness of 10 mm was also used as the irradiated sample. The degree of discoloration is
Use gray scale (JIS L0804) for discoloration and
The grade was evaluated in 9 steps between No. 1 and No. 1. The determination result of the light fastness was 3 to 4 grade. The results are shown in Table 1 together with the comparative examples.

Example 2 The complex consisting of cuprous bromide and 2-mercaptobenzimidazole of Example 1 in a molar ratio of 1: 1 was applied to a resin tip of nylon 6 so that the amount of copper was 25 ppm. Spun The initial nozzle back pressure during spinning was 140 kg / cm ² , and the nozzle filter back pressure hardly increased even after continuous spinning for 2 weeks. FIG. 2 shows how the nozzle filter back pressure increases together with the comparative example. The evaluation results of coarse particles in the nylon yarn also showed a value of 0.15 kcps, which was about the same as in Example 1.
Further, after the nylon thread was dyed with a metal-containing dye, the light fastness was judged to be grade 3, which was a good result. Table 1 shows the evaluation results of the coarse copper particles in the nylon yarn and the judgment results of the light fastness.

Example 3 Nylon 6 resin chips were coated and spun so that 2-mercaptobenzimidazole content was 192 ppm and cuprous bromide content was 80 ppm. Cuprous / 2-mercaptobenzimidazole = 1
/ 1 molar ratio). The initial nozzle back pressure during spinning was 145 kg / cm ² , and the nozzle filter back pressure hardly increased even after continuous spinning for 2 weeks. Fig. 2 shows how the nozzle filter back pressure increases. The evaluation results of coarse particles in the nylon yarn also showed a value of 0.24 kcps, which was about the same as in Example 1. Further, after the nylon thread was dyed with a metal-containing dye, the light fastness was judged to be grade 3, which was a good result. Table 1 shows the determination results of light fastness. Although the light resistance is slightly inferior to the copper complex of Example 1, almost the same copper complex is formed during spinning.

Comparative Example 1 Cuprous bromide was applied to a resin tip of nylon 6 so that the amount of copper was 100 ppm, and in the same manner as in Example 1, evaluation of coarse copper particles during spinning and light fastness of carpet were carried out. The degree was evaluated. The results are shown in Table 1 and FIG.

Comparative Example 2 Cuprous iodide was applied to a resin tip of nylon 6 so that the amount of copper was 100 ppm, and evaluation of coarse copper particles during spinning and light fastness of carpet were carried out in the same manner as in Example 1. The degree was evaluated. The results are shown in Table 1 and FIG.

Comparative Example 3 A resin tip of nylon 6 was coated so that the amount of 2-mercaptobenzimidazole was 240 ppm and the amount of cuprous iodide was 100 ppm. In addition, the evaluation of coarse copper particles during spinning and the lightfastness of carpet were performed. The results are shown in Table 1 and FIG.

[0019]

[Table 1]

[0020]

EFFECTS OF THE INVENTION According to the present invention, it is possible to provide a polyamide composition which has good heat resistance, does not generate coarse particles during melting such as melt spinning, and has excellent light resistance.

[Brief description of drawings]

FIG. 1 is a diagram showing an infrared absorption spectrum of a copper complex used in Examples.

FIG. 2 is a graph showing an increase in back pressure during melt spinning in Examples and Comparative Examples.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Etsukazu Sekida 1-1 Kureha-cho, Tsuruga-shi, Fukui Prefecture Toyobo Co., Ltd. Tsuruga nylon factory (72) Inventor Toshio Matsushima 1-1 Kureha-cho, Tsuruga-shi, Fukui Prefecture Toyobo Co., Ltd. Tsuruga Nylon factory (72) Inventor Hideo Sekiya 2-8 Dojimahama, Kita-ku, Osaka Toyobo Co., Ltd.

Claims (1)

[Claims] 1. A light resistance characterized by containing 10 to 1000 ppm as a weight of copper with respect to a polyamide, a complex having a molar ratio of 1: 1 of cuprous bromide and a compound containing a thiol group. With a polyamide composition.