JPH07216221A - Polyamide composition, fiber and molding excellent in light and heat resistances - Google Patents

Abstract

PURPOSE:To obtain a polyamide composition, remarkably improved in operating efficiency without forming infusible materials in melt spinning, etc., and excellent in light and heat resistances by blending a complex of a monovalent copper compound with a compound containing thiol group with a polyamide. CONSTITUTION:This composition is obtained by blending (A) a polyamide (e.g. nylon 6) with (B) a complex composed of a monovalent copper compound (e.g. cuprous iodide) with a compound containing thiol group (e.g. 2- mercaptobenzimidazole) at 1:3 molar ratio in an amount of 10-1000ppm expressed in terms of the weight of copper. Furthermore, the components (B) and (A) are blended by usually applying the component (B) to pellets of the component (A) before spinning or molding thereof.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyamide composition, which can be advantageously applied to applications requiring high light resistance and heat resistance such as automobile interiors, and a molded article obtained by extrusion molding or injection molding.

[0002]

2. Description of the Related Art Polyamide fiber has excellent strength, abrasion resistance, impact resistance, and good dyeability. Therefore, it is widely used in the form of fibers and films for clothing, interiors, and industrial materials. There is. However, polyamide is
It has a drawback that it is susceptible to oxidative deterioration, and particularly 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 improving agents) has been conventionally adopted (Japanese Patent Publication No. 38-22720 and Japanese Patent Publication No. 48-7).
858, Japanese Patent Publication No. 48-7859, Japanese Patent Publication No. 48-7860, Japanese Patent Publication No. 59-50769, Japanese Patent Publication No. 60-17309,
Japanese Patent Publication No. 61-45662, Japanese Patent Publication No. 5-48783).

[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 moreover, excellent light resistance and heat resistance as a dyed article. The present invention intends to provide a fiber molded product composed of a polyamide composition and a functional composition capable of exhibiting the above-mentioned properties.

[0005]

That is, the present invention is as follows.
A complex consisting of a divalent copper compound and a compound containing a thiol group in a molar ratio of 1: 3 as copper weight to polyamide
A polyamide composition excellent in light resistance and heat resistance, containing 10 ppm to 1000 ppm, a polyamide fiber and a polyamide molded product comprising the composition.

The monovalent copper compound in the present invention is not particularly limited, but copper halides such as cuprous iodide, cuprous bromide and cuprous chloride, copper thiocyanate, copper cyanide, and oxides. Copper etc. are mentioned.

The compound containing a thiol group is not particularly limited, but 2-mercaptobenzimidazole,
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 for incorporating a complex of a monovalent copper compound and a compound containing a thiol group into a polyamide fiber or a polyamide molded article is as follows: a monovalent copper compound and a compound containing a thiol group are previously mixed as a complex. , Or each of them may be compounded without forming a complex, but they are added to the polyamide pellets during polymerization of the polyamide or before spinning or molding. Generally, a method of coating the polyamide pellets before spinning or molding is used.

Polyamides to which the present invention is applicable include
Nylon 6, Nylon 12, Nylon 6-6, Nylon 6-1
Examples thereof include, but are not limited to, aliphatic polyamides such as polyxylene adipamide, aromatic polyamides, alicyclic polyamides, copolyamides of these polyamides, mixed polyamides, and the like.

[0010]

EXAMPLES Examples will be shown below, but the present invention is not limited to the following examples, and it is needless to say that appropriate modifications can be made within a range that is compatible with the gist of the preceding and following description. Yes, all of them are included in the technical scope of the present invention.

Example 1 Cuprous bromide: 25 g and 2-mercaptobenzimidazole: 78.
Dissolve 5 g in 300 ml of N, N-dimethylformamide and remove the solvent with a rotary evaporator. The residue was vacuum dried to obtain a complex consisting of cuprous bromide and 2-mercaptobenzimidazole in a molar ratio of 1: 3. The infrared absorption spectrum of this copper complex is shown in FIG. The melting point of this copper complex is about 275 ° C., and when the polyamide is melted, it is dissolved in the polyamide and mixed well.

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 is 100ppm and blend for 1 hour or more. did. The resin is heated and melted, and the extruder (temperature: 26
The filament was discharged from the spinning nozzle through a spinning nozzle at 0 to 280 ° C., pressure: 100 to 200 kg / cm ² ), a beam branched for multiple weights (temperature: 250 to 280 ° C.), and a metering pump. Later, 20
It was wound at 0 to 800 m / min, further stretched 2 to 5 times, buckled by heating, and wound on cheese as crimped processed yarn. The rise in back pressure of the nozzle filter during the melt spinning was measured, and when the back pressure reached 180 kg / cm ² , it was determined that the nozzle filter was clogged, and the number of days elapsed until that time was determined. The number of days to replace the nozzle filter was 40 days or more.

As the light resistance test sample, first, 1000 denier, 64 filaments (triangular cross-section yarn) and crimp amount CC = 20
%, Crimp stability CD = 15% BCF nylon was set by 2 plies by a conventional method, and then tufted to prepare a saxony type carpet (1300 g / m ^{2 in} basis weight). 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 prescription] Irgalan Yellow GRL 0.04% owf Irgalan Red Brown RL 0.06% owf Irgalan Gray GL 0.34% owf Albegal SW (Ciba-Geigy auxiliary) 1.0% owf Albegal FFD (Ciba-Geigy auxiliary) 0.1 g / l Meisan 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 carried out at a black panel temperature of 83 ± 3 ° C. for a total irradiation time of 200 hours. still,
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. Regarding the degree of discoloration and fading, a gray scale for discoloration and fading (JIS L0804) was used, and the grade was evaluated in 9 steps from No. 5 to No. 1. As a result of the determination of light fastness, a grade 4 to 5 was obtained. The results are shown in Table 1 together with the comparative examples.

Example 2 A complex of a cuprous bromide and a 2-mercaptobenzimidazole of Example 1 in a molar ratio of 1: 3 was applied to a resin tip of nylon 6 so that the amount of copper was 25 ppm. Then, spinning and dyeing were carried out in the same manner as in Example 1. The number of days to replace the spinning nozzle filter was 40 days or more, which was good, and the light fastness was judged to be grade 4, which was a good result. The results are shown in Table 1 together with the comparative examples.

Example 3 2-Mercaptobenzimidazole was adjusted to 710 ppm and cuprous bromide was adjusted to 100 ppm as the amount of copper (cuprous bromide / 2-mercaptobenzimidazole = 1 /
(3 mol ratio), and applied to a resin chip of nylon 6 and spun and dyed in the same manner as in Example 1. The number of days to replace the spinning nozzle filter was 40 days or more, which was good, and the light fastness was judged to be grade 4, which was a good result. The results are shown in Table 1 together with the comparative examples. Although the light resistance is slightly inferior to the copper complex of Example 1, almost the same copper complex is formed during spinning.

Example 4 2-Mercaptobenzimidazole was adjusted to 945 ppm, and cuprous bromide was adjusted to 100 ppm as the amount of copper (cuprous bromide / 2-mercaptobenzimidazole = 1 /
(4 mol ratio), and applied to a resin tip of nylon 6 and spun and dyed in the same manner as in Example 1. The number of days for replacing the spinning nozzle filter was 40 days or more, which was good, and the light fastness was 4 to 5th grade. The results are shown in Table 1 together with the comparative examples. Compared to Example 1, a complex consisting of cuprous bromide and 2-mercaptobenzimidazole in a molar ratio of 1: 3 was used, although an excess of 2-mercaptobenzimidazole remained. Have generated enough.

Example 5 Cuprous chloride: 20 g and 2-mercaptobenzimidazole: 91 g
Is dissolved in 300 ml of N, N-dimethylformamide, and the solvent is removed by a rotary evaporator. The residue was vacuum dried to obtain a complex consisting of cuprous chloride and 2-mercaptobenzimidazole in a molar ratio of 1: 3. The infrared absorption spectrum of this copper complex is shown in FIG. The melting point of this copper complex is about 265 ° C., and when the polyamide is melted, it is dissolved in the polyamide and mixed well.

A complex consisting of cuprous chloride and 2-mercaptobenzimidazole in a molar ratio of 1: 3 is 100 ppm as the amount of copper.
Nylon 6 resin chips were coated so as to become, and spun and dyed in the same manner as in Example 1. The number of days for replacing the spinning nozzle filter was 40 days or more, which was good, and the light fastness was 4 to 5th grade. The results are shown in Table 1 together with the comparative examples.

Comparative Example 1 Cuprous bromide: 25 g and 2-mercaptobenzimidazole: 26.
Dissolve 2 g in 300 ml of N, N-dimethylformamide and remove the solvent with a rotary evaporator. The residue was vacuum dried to obtain a complex consisting of cuprous bromide and 2-mercaptobenzimidazole in a molar ratio of 1: 1. The melting point of this copper complex is about 310 ° C.

100 ppm of the amount of copper was a complex consisting of cuprous bromide and 2-mercaptobenzimidazole in a molar ratio of 1: 1.
Nylon 6 resin chips were coated so as to be, and spun and dyed in the same manner as in Examples. Table 1 shows the evaluation results of the clogging of the spinning nozzle filter and the judgment results of the light fastness.

Comparative Example 2 Cuprous bromide: 25 g and 2-mercaptobenzimidazole: 52.
Dissolve 4 g in 300 ml of N, N-dimethylformamide and remove the solvent with a rotary evaporator. The residue was vacuum dried to obtain a complex consisting of cuprous bromide and 2-mercaptobenzimidazole in a molar ratio of 1: 2. The melting point of this copper complex is about 305 ° C.

100 ppm of copper was used as a complex consisting of cuprous bromide and 2-mercaptobenzimidazole in a molar ratio of 1: 2.
Nylon 6 resin chips were coated so as to be, and spun and dyed in the same manner as in Examples. Table 1 shows the evaluation results of the clogging of the spinning nozzle filter and the judgment results of the light fastness.

Comparative Example 3 2-Mercaptobenzimidazole was adjusted to 470 ppm, and cuprous bromide was adjusted to 100 ppm as the amount of copper (cuprous bromide / 2-mercaptobenzimidazole = 1 /
(2 mol ratio), and applied to a resin tip of nylon 6 and spun and dyed in the same manner as in the example. Table 1 shows the evaluation results of the clogging of the spinning nozzle filter and the judgment results of the light fastness.

Comparative Example 4 2-Mercaptobenzimidazole was adjusted to 240 ppm and cuprous iodide was adjusted to 100 ppm as the amount of copper (cuprous iodide / 2-mercaptobenzimidazole =
(1/1 molar ratio), apply it to a nylon 6 resin tip,
Spinning and dyeing were carried out in the same manner as in the examples. Table 1 shows the evaluation results of the clogging of the spinning nozzle filter and the judgment results of the light fastness.

Comparative Example 5 Cuprous iodide: 25 g and 2-mercaptobenzimidazole: 3
Dissolve 9.4 g in 300 ml of N, N-dimethylformamide and remove the solvent with a rotary evaporator. The residue was vacuum dried to obtain a complex consisting of cuprous iodide and 2-mercaptobenzimidazole in a molar ratio of 1: 2. The melting point of this copper complex is about 250 ° C.

A complex consisting of cuprous iodide and 2-mercaptobenzimidazole in a molar ratio of 1: 2 was used as a copper amount of 100 p.
Apply it to a nylon 6 resin tip to reach pm,
Spinning and dyeing were carried out in the same manner as in the examples. Table 1 shows the evaluation results of the clogging of the spinning nozzle filter and the judgment results of the light fastness.

[0028]

[Table 1]

Example 6 Nylon 6-6 resin chips (water content: 0.05%) were coated with a polymeric nonionic surfactant in an amount of 0.05 wt% based on the weight of the chips,
Then, using a resin chip coated with the copper complex in Example 1 so that the amount of copper is 100 ppm, a dumbbell-shaped test piece (thickness: 2 mm) at a resin temperature of 265 ° C. with an injection molding machine (Nissan NS 75 type). ) Was molded. Insoluble particles were not observed in this test piece, and the appearance was good. When the light resistance of this test piece was evaluated in the same manner as in Example 1, the light resistance was grade 4. In addition, the light resistance of the blank test piece not coated with the copper complex was first grade.

[0030]

INDUSTRIAL APPLICABILITY According to the present invention, insoluble matter is not generated during melt spinning, extrusion molding, injection molding, etc., and the operability such as clogging of nozzle filter is remarkably improved, and the light resistance and heat resistance are excellent. It is possible to provide such polyamide compositions, fibers and molded articles.

[Brief description of drawings]

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

2 is a diagram showing an infrared absorption spectrum of the copper complex used in Example 5. FIG.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Etsuichi Sekita 1-1 Kurehacho, Tsuruga City, Fukui Prefecture Toyobo Co., Ltd. Tsuruga nylon factory (72) Inventor Toshio Matsushima 1st Kurehacho, Tsuruga City, Fukui Prefecture No. 1 Toyobo Co., Ltd. Inside the Tsuruga nylon factory (72) Inventor Hideo Sekiya 2-8 Dojimahama, Kita-ku, Osaka Toyobo Co., Ltd.

Claims (3)

[Claims] 1. A light- and heat-resistant material, characterized in that it contains 10 ppm to 1000 ppm of copper as a weight of copper with respect to a polyamide, the complex being composed of a monovalent copper compound and a compound containing a thiol group in a molar ratio of 1: 3. Excellent polyamide composition. 2. A polyamide fiber comprising the polyamide composition according to claim 1. 3. A polyamide molded product comprising the polyamide composition according to claim 1.