JPH0733980A - Light stabilizer for polyamide, light-resistant polyamide composition, and light-resistant polyamide fiber - Google Patents

Abstract

PURPOSE:To obtain the title stabilizer which imparts excellent resistance to light, heat, and yellowing to a polyamide by constituting it of a specific copper complex. CONSTITUTION:The stabilizer comprises a copper complex represented by the formula wherein X is a benzotriazolyl or benzoyl group in which the benzene ring may have one substituent, and A and B each is H or an alkyl (e.g. 2-(5'-t- butyl-2'-hydroxyphenyl)benzotriazole/copper complex). This stabilizer is incorporated into a polyamide preferably in an amount of 10-1,000ppm in terms of copper amount based on the polyamide to produce the title composition.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a light-resistant agent which gives polyamide excellent light resistance and yellowing resistance, and a light-resistant polyamide composition containing the light-resistant agent in polyamide.
It also relates to a polyamide fiber using the polyamide composition.

[0002]

2. Description of the Related Art Polyamide has excellent strength, abrasion resistance, impact resistance and dyeability, so that it is used in the form of fibers or films in the clothing and interior fields. Widely used in various industrial fields.
However, polyamide has the drawback of insufficient oxidation resistance and heat resistance when exposed to high temperatures.
Various methods have been attempted as improvement measures. A typical method among them is a method of incorporating an antioxidant or a light resistance agent in the polymer polymerization step or the processing step into a fiber or the like, and particularly, as a light resistance / heat resistance improver, a copper-based compound and 2-
A number of methods for incorporating mercaptobenzimidazoles or their complex compounds have been proposed (Japanese Patent Publication No. Sho 38).
-22720, 48-7858, 48-7859,
48-7860, 60-17309, 61-45662, etc.).

[0003]

However, the conventional copper complex salt-based heat and light resistance improvers have insufficient heat resistance themselves and cause thermal decomposition when the polyamide is melted to form an insoluble compound. However, for example, during melt spinning, there may be problems in operation such as an increase in back pressure of the spinning nozzle and yarn breakage, and it can be said that the coloring and sharpness during dyeing and the high temperature light resistance after dyeing are also satisfactory. Absent.

The present invention has been made by paying attention to the above circumstances, and its purpose is to have good heat resistance of itself and to form an insoluble matter even when blended in a polyamide and melted. A light resistant agent that does not generate, and can give excellent oxidation resistance and heat resistance to polyamide,
And a polyamide composition having excellent light resistance, and a polyamide fiber.

[0005]

The constitution of the lightproofing agent for polyamide according to the present invention, which has been able to solve the above-mentioned problems, has a gist in that it comprises a copper complex salt represented by the following general formula [1]. .

[0006]

[Chemical 2]

A polyamide composition containing the light-proofing agent in an amount of 10 to 1000 ppm in terms of copper based on the polyamide, and a polyamide fiber obtained by processing the composition into a fibrous form have very excellent light-proofing and heat-resisting properties. Demonstrate.

[0008]

The present inventors, under the above-mentioned conventional technology,
In order to find a modifier that is stable even in the melting temperature range of polyamide, and that can give excellent light resistance and heat resistance to polyamide, its thermal stability for various copper complex compounds and light resistance and heat resistance to polyamide The improvement effect was investigated. As a result, among the innumerable copper complex compounds, the compound represented by the above general formula [1] has very good thermal stability and does not generate insoluble matter, and for example, melt spinning or injection molding. It was confirmed that, even when the above procedure was performed, problems such as nozzle clogging did not occur, and furthermore, excellent light resistance and heat resistance improving effects were exhibited for polyamide.

In the copper complex salt of the general formula [1], the group represented by X is a benzotriazolyl group or benzotriazolyl having one substituent (eg, halogen, alkyl, alkoxy, etc.) on the benzene ring. Group, and specific examples of the benzotriazolyl group having one substituent on the benzene ring include 5-methylbenzotriazolyl group, 5-emethylbenzotriazolyl group and 5-methylbenzotriazolyl group.
Propylbenzotriazolyl group, 5-t-butylbenzotriazolyl group, 5-chlorobenzotriazolyl group, 5
-A fluorobenzotriazolyl group and the like can be mentioned.

Other groups represented by X include a benzoyl group or a benzoyl group having one substituent (alkyl, halogen, alkoxy, etc.) on the benzene ring, and one substituent on the benzene ring may be used. Specific examples of the benzoyl group have include 4-methylbenzoyl group, 4
-Methoxybenzoyl group, 4-octoxybenzoyl group, 4-chlorobenzoyl group and the like can be mentioned.

Further, as the substituents represented by A and B,
Hydrogen, cumyl, —CH ₂ —CH ₂ COOR (R: alkyl, representing polyethylene glycol), and C _{1 to} C ₁₈ straight chain or branched alkyl can be mentioned, with preference given to methyl, ethyl, propyl and n-butyl. , T-butyl, sec-
Examples include pentyl, hexyl, heptyl, heptyl and the like. Examples of the copper salt used in the synthesis of the copper complex salt include copper halides such as copper chloride and copper iodide, copper sulfate, and copper acetate. Of these, copper sulfate is particularly preferable.

The copper complex salt represented by the general formula [1] is
It can be easily obtained by reacting the copper salt with hydroxyphenyltriazole or hydroxybenzophenone represented by the following general formula.

[0013]

[Chemical 3]

When the copper complex salt is used as a light stabilizer for polyamide, the preferable content is 10 to 1000 in terms of copper.
ppm, more preferably in the range of 20 to 300 ppm, and if the content is less than 10 ppm, sufficient heat resistance and light resistance cannot be imparted to the polyamide.
If it exceeds 00 ppm, not only the polyamide tends to be colored and the color tone of the dyeing tends to deteriorate, but also yarn breakage tends to occur during melt spinning.

As the polyamide to which the above-mentioned light-proofing agent is added, an aliphatic or aromatic polyamide such as nylon 6, nylon 12, nylon 46, nylon 66, nylon 610, polyxylene adipamide, or a polyamide of these Examples thereof include a mixture or a copolyamide.

The method of blending the light-proofing agent with the polyamide is not particularly limited, and if the copper complex salt or hydroxyphenylbenzotriazole which is the source thereof and the copper salt are blended at the polyamide polymerizing stage or the resin chip stage. From the viewpoint of more effectively preventing thermal decomposition of the copper complex salt, a method of blending the copper complex salt fine particles with a polyamide resin chip before melt spinning, injection molding, or the like is preferable.

The polyamide composition can be processed into an arbitrary shape such as a sheet or a film by a usual injection molding method or the like, and when it is made into a fibrous shape, a desired denier, a desired denier, can be obtained by a usual melt spinning method. It is sufficient to use a polyamide fiber having a cross-sectional shape, crimping characteristics and fiber physical properties. This polyamide fiber may be twisted, if necessary, and then processed into a predetermined woven fabric such as carpet, and then treated with an acid dye or a metal-containing complex salt dye. It can be dyed in a desired hue.

If necessary, the polyamide composition or polyamide fiber may further contain other components such as titanium oxide or other dull agents, pigments, dyes, antioxidants, ultraviolet absorbers,
Of course, it is also possible to include a functional modifier such as an antibacterial agent or an aromatic agent in a range that does not impair the light resistance, the dyeability, the spinning operability and the like.

[0019]

EXAMPLES Next, examples of the present invention will be shown, but the present invention is not limited by the following examples, and may be carried out with appropriate modifications within a range compatible with the gist of the preceding and following description. Of course, it is possible, and all of them are included in the technical scope of the present invention.

Example 1 2- (5'-t-butyl-2'-hydroxyphenyl)
Benzotriazole (100 g), was dissolved in 1N-NaOH aqueous solution 400 ml, CuSO ₄ · copper sulfate (50g
5H ₂ O dissolved in 600 ml) was slowly added dropwise to form a precipitate, and the mixture was stirred at 70 ° C. for 1 hour. After cooling, the precipitate was collected by filtration, sufficiently washed with distilled water, and then vacuum dried to give a 2- (5′-t-butyl-2′-hydroxyphenyl) benzotriazole copper complex (104 g: 94% yield). )was gotten. The infrared absorption spectrum of this copper complex is as shown in FIG. 1 and has the following structural formula.
When the temperature was raised to 20 ° C per minute at a rate of 20 ° C, the weight loss was 1% by weight or less, and the heat resistance was very excellent.

[0021]

[Chemical 4]

On the other hand, dried nylon 6 resin chips (water content: 0.05 to 0.20% by weight) are heated to 50 to 80 ° C. while being mixed in a nitrogen atmosphere, and a polymeric nonionic surfactant is added to the resin. After adding 0.05% by weight to the above, the particulate copper complex obtained above was added to the resin so as to be 25 ppm in terms of copper, and mixed for 1 hour. This mixture is heated and melted, and then the extruder (temperature: 260 to 280
), A beam branched for multiple spindles (temperature: 250-280)
℃), discharge the filament from the spinning nozzle through the metering pump, and then wind it at 200-800 m / min, and further 2
It was drawn up to 5 times, heated and buckled to be wound on cheese as crimped processed yarn.

At this time, the back pressure of the initial nozzle during melt spinning is 1
It was 45 kg / cm ² , and the back pressure of the spinning nozzle hardly increased even when melt spinning was continuously performed for 2 weeks. In addition, 3 g of the obtained nylon thread is used as 1,1,3,3,3-hexafluoro-2-
After dissolving in propyl alcohol and collecting coarse copper particles in nylon with a Teflon filter having an average pore size of 5 μm, a fluorescent X-ray analyzer (RIGAKU X-RAY SPECTROMETER 32
70) was used to analyze copper, and as a fluorescent X-ray analysis value, a value of 0.17 kilocounts / second (kcps) per 1 g of nylon was obtained. The magnitude of this value corresponds to the relative amount of coarse copper particles in nylon.

Next, the light resistance of the polyamide fiber was examined by the following method. That is, a modified nylon having 1000 denier 65 filaments (triangular cross-section yarn) and a crimp amount (CC) of 20% and a crimp stability (CD) of 15% was set in 2 plies by a conventional method, and a safty type as a tuft. (Basis weight 1300 g / m ² ) is prepared and dyed with a Wins dyeing machine according to the following 1/2 type gold-containing complex salt dye for 60 minutes by boiling, washing with water, washing with water and drying, and then a polyethylene film is applied to the back surface of the carpet by a conventional method. After fusing and packing, a 10 mm thick coarse felt was adhered to obtain a sample for light resistance test.

(Dyeing Formula) Irgalan Yellow GRL 200% (1) 0.04% owf Irgalan Red Brown RL 200% (1) 0.06% owf Irgalan Gray GL 200% (1) 0.34% owf Albegal SW (CIBA-GY dyeing Auxiliary agent) 1.0% owf Albegal FFD (CIBA-GY dyeing auxiliary agent) 0.1 g / liter Meisan PC (Meisei Chemicals pH adjuster) 0.5 g / liter Soda ash (pH adjuster) 0.3 g / liter However ( 1) is a CIBA-GY 1/2 type gold dye fastness test: UV long life fade meter (compliant with JIS B 7751, model: FAL-5H) made by Suga Test Instruments Co., Ltd.
B / BR, vertical type holder), black panel temperature 8
After irradiating at 3 ± 3 ℃ for 200 hours (changing the vertical position of the holder every 20 hours), gray scale for discoloration / fading (JIS
According to L 0804), the grade was evaluated in 9 steps from No. 5 to No. 1. The shape of the irradiated sample was assumed to be used in an automobile, and a low density polyethylene film was fused on the back surface of the irradiated sample, and
A 0 mm thick felt was also used as a sample. The results are shown in Table 1 and FIG.

Example 2 Nylon 6 resin chips were melt-spun by adding the same copper complex as in Example 1 to nylon in an amount of 100 ppm in terms of copper. The initial nozzle back pressure during spinning was measured. Was 146 kg / cm ² , and even if melt spinning was continuously performed for 2 weeks, an increase in the back pressure of the nozzle was hardly observed. When the obtained nylon yarn was dyed in the same manner as in Example 1 and subjected to a light fastness test and the like, good results were obtained as shown in Table 1 and FIG.

Comparative Example 1 Cuprous iodide was converted to 1 in terms of copper with respect to a nylon resin chip.
Melt spinnability, copper coarse particle evaluation, and light fastness evaluation were carried out in the same manner as in Example 1 except that the content was set to 00 ppm, and the results shown in Table 1 and FIG. 2 were obtained.

Comparative Example 2 With respect to a nylon resin chip, 240 ppm of 2-mercaptobenzimidazole and 100 parts of cuprous iodide were converted to copper.
Melt spinnability, copper coarse particle evaluation, and light fastness evaluation were performed in exactly the same manner as in Example 1 except that the content was ppm, and the results shown in Table 1 and FIG. 2 were obtained.

[0029]

[Table 1]

As is clear from Table 1 and FIG.
The polyamide containing the light-proofing agent of the present invention has an extremely small amount of coarse copper particles produced during melt spinning as compared with the comparative example, has a small increase in back pressure of the nozzle filter, and is also excellent in light fastness. It turns out to be a thing.

[0031]

EFFECTS OF THE INVENTION The present invention is constituted as described above, and provides a light fastness agent which is excellent in heat resistance and can impart excellent light fastness to polyamide without deteriorating melt spinning operability and the like. It is possible to obtain a polyamide composition and a polyamide fiber having excellent light resistance by adding an appropriate amount of the light stabilizer to the polyamide.

[Brief description of drawings]

FIG. 1 is a diagram showing an infrared absorption spectrum of a copper complex obtained in an example.

FIG. 2 is a graph showing a change in back pressure of a filter during melt spinning.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tadao Shibayama 1-1, Kureha-cho, Tsuruga-shi, Fukui Prefecture Toyobo Co., Ltd. Tsuruga nylon factory (72) Inventor Hironori Tanaka 1-1, Kureha-cho, Tsuruga-shi, Fukui Toyobo Co., Ltd. Inside the Tsuruga nylon factory (72) Inventor Hideo Sekiya 2-2-8 Dojimahama, Kita-ku, Osaka Toyobo Co., Ltd.

Claims (3)

[Claims] 1. A light stabilizer for polyamide, comprising a copper complex represented by the following general formula [1]. [Chemical 1] 2. A light-resistant polyamide composition comprising the light-resistant agent according to claim 1 in an amount of 10 to 1000 ppm in terms of copper based on polyamide. 3. A light-resistant polyamide fiber, characterized in that the light-resistant agent according to claim 1 is contained in an amount of 10 to 1000 ppm in terms of copper with respect to polyamide.