JPH04277528A - Sulfur-containing aromatic resin molding - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molded article of a sulfur-containing aromatic resin.

More specifically, the present invention relates to molded sulfur-containing aromatic resins having high resistance to heat and light.

0003

[Prior Art] Sulfur-containing aromatic resin molded products having sulfur in the main chain, such as polyphenylene sulfide, have excellent chemical resistance, heat resistance, flame retardancy, and excellent mechanical and electrical properties. It is beginning to be used widely. However, on the other hand, it is known that the sulfur-containing aromatic resin molded product is easily discolored by heat and deteriorates by light.

[0004] Therefore, several techniques have been disclosed in an attempt to improve these drawbacks. Representative examples are listed below.

[0005] One of the techniques is to add a special stabilizer, which is a technique disclosed in Japanese Patent Publication No. 1-23500, etc., in which a special aminotriazole is added to the resin to stabilize the resin. This technology aims to improve the thermal stability of Similar technology is disclosed in Japanese Patent Application Laid-Open No. 2-73
This technique is also disclosed in Japanese Patent No. 859, and attempts to improve the stability of the resin by using a hindered phenol compound and a phosphorus compound in combination.

[0006] Furthermore, JP-A-62-288630 discloses a technique for bonding a stabilizer into molecules.

[0007] However, according to the findings of the present inventors, although all of these techniques are more effective than those in which nothing is added, the current situation is that they are still not sufficient.

[0008]

[Problems to be Solved by the Invention] In view of the above-mentioned points, an object of the present invention is to create a sulfur-containing aromatic resin molded product that is less susceptible to deterioration due to heat or light while retaining the good qualities of the sulfur-containing aromatic resin molded product. The purpose is to provide resin molded products.

[0009]

[Means for Solving the Problems] In order to achieve the above-mentioned object, the present invention has the following configuration.

That is, it is a molded product made of a sulfur-containing aromatic resin containing at least sulfur in the bonds in the main chain, and the molded product contains 2-(2-hydroxy-5-methyl-phenyl)-2H-benzo This is a sulfur-containing aromatic resin molded product containing triazole and pentaerythrityl-tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate].

[0011]

[Operation] The present invention will be explained in more detail below. First, the sulfur-containing aromatic resin according to the present invention will be described.

The sulfur-containing aromatic resin of the present invention contains at least sulfur in the bonds in its main chain. Typical examples include aromatic resins having sulfide bonds, sulfone bonds, sulfoxide bonds, etc. in the main chain.

Typical such resins include polyphenylene sulfide, polyxylylene sulfide, polynaphthalene sulfide, polyphenylene sulfide sulfone, polyphenylene sulfide ketone, polyether sulfone, polyphenylene sulfone, and various aromatic sulfone resins.

Among such resins, particularly preferred in the present invention are polyphenylene sulfide and polyphenylene sulfide sulfone. Such resins are preferred because they have excellent melt moldability, high chemical resistance, high heat resistance and mechanical strength, and are inexpensive.

Although the molded product of the present invention is made of such a resin, it may be copolymerized with other components within the range that does not impair the effects of the present invention, or may be copolymerized with other components. may be graft polymerized, or the resin of the present invention may be partially modified.

[0016] In the present invention, a specific compound is contained in the molded product of the resin.

That is, 2-(2-hydroxy-5-methyl-phenyl)-2H-benzotriazole and pentaerythrityl-tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] is included.

Furthermore, the 2-(2-hydroxy-5-methyl-phenyl)-2H-benzotriazole and 2-(
2-hydroxy-5-methyl-phenyl)-2H-benzotriazole and pentaerythrityl-tetrakis [
When 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] is contained in the sulfur-containing aromatic resin molded product, the heat resistance and light resistance of the molded product of the present invention are further improved. .

Although not the compound according to the present invention itself, various compounds similar to it are known. However, these similar compounds are less effective. That is, the compound of the present invention exhibits a specific effect. Although the details of the reason are not necessarily clear, the following reasons may be considered, for example. That is,
Sulfur-containing aromatic resins deteriorate due to heat and light. The details of the mechanism are also unknown, but basically the resin deteriorates due to decomposition and crosslinking. In contrast, in the present invention, the deterioration of the resin can be prevented only by using the above-mentioned compounds together as a unique synergistic effect.
The mechanism is presumed to be that deterioration of the resin due to crosslinking and decomposition due to heat and light is effectively prevented in a synergistic manner.

Next, the addition rate of the compound to achieve the effect varies depending on the type of resin, its form, etc.
Although this cannot necessarily be said, it is preferable that the content is 0.05% by weight or more. More preferably 0.1% by weight or more
It is 10% by weight. If the amount exceeds 10% by weight, the inherent properties of the resin will often be impaired, so it is generally not suitable.

This is a combination of 2-(2-hydroxy-5-methyl-phenyl)-2H-benzotriazole and pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate. ] These are individual values for each, but if the total amount of both added exceeds 10% by weight, the original characteristics of the resin may be impaired.
Problems may occur due to the compound falling off, so care must be taken.

[0022] It is particularly preferred that such compounds are uniformly distributed in the molded article or distributed on its surface.

Next, the molded product of the present invention will be described.

[0024] The molded product according to the present invention may be made of only the resin according to the present invention, or may contain a part of other resins or be composited with other resins. Good too.

[0025] Furthermore, the form of the molded product is not particularly limited, and any form can be taken.

Typical examples include fibers, films, chips, injection molded products of various shapes, and particles.

[0027]Fibers include thick monofilaments, ultrafine fibers, porous fibers, and composite fibers with other resins. Various types of composite fibers can be used, but particularly preferred are fibers in which at least the surface thereof is made up of the resin according to the present invention. Fibers having the resin of the present invention on their surfaces have particularly excellent chemical resistance and flame retardancy, so using the resin of the present invention on the surface of composite fibers will improve the chemical resistance and flame retardancy of other resins. It has the advantage of being able to produce fibers with high properties even if the properties are low.

The same applies when the molded product is a film, including thick and thin films, as well as composite films made of various resins. In the case of a composite film, it is preferable that the surface thereof be made of the resin according to the present invention, as in the case of fibers.

The same applies to various injection molded products.

The sulfur-containing aromatic resin molded product of the present invention has the above-mentioned structure, but it does not matter if it contains other substances.

For example, if the molded product according to the present invention is an injection molded product, glass fibers, various fillers, fine particles such as titanium oxide, carbon black, etc., and the molded product according to the present invention may be made of fibers or films. In this case, it does not matter if it contains various fine particles such as titanium oxide or carbon black, various coloring agents, antistatic agents, etc.

The molded product according to the present invention has heat coloring resistance, that is, does not easily color even when exposed to heat, and light coloring resistance, that is, it does not easily color even when exposed to light, which conventional sulfur-containing aromatic resin molded products do not have. It has characteristics such as not being easily colored and its mechanical properties not easily fading even when exposed to heat or light, so it can be widely used in the following applications, for example.

That is, for example, electrical materials, various housings, parts for bathtubs, curtains, sheets, ordinary clothes, curtains, sheets, clothes, and carpets for hospitals, curtains, sheets, and clothes for experiments, children's clothes, etc. Curtains, sheets, clothing, sinks, laboratory sinks, various pipes, aircraft wall materials, wall materials, base materials for printed circuit boards, filters, filter reinforcement materials, tension members for reinforcing high-voltage wires, screen gauze, fishing line. , marine materials, cement reinforcement materials, construction materials, vehicle materials, protective clothing, various reinforcing fibers,
Heat-resistant and chemical-resistant cloth, FRP materials, fishing nets, reinforcing materials for optical fibers, plywood materials, wood reinforcing materials, prestressing materials, linear motor materials, rebar substitutes, wire mesh substitutes, nets, geogrit base materials , tunnel wall reinforcement net, tunnel wall reinforcement material, protective materials for construction, ropes, materials for skiing, materials for aircraft, materials for partitions,
Ceiling materials, floor materials, tension members, geofront-related materials, high-temperature insulation materials, pipe reinforcement materials, car materials, brake-related materials, asbestos substitutes, concrete reinforcement materials, autoclave-cured concrete reinforcement materials, spraying It can be used for various purposes such as cement reinforcement materials, raised floor materials, raised ceiling materials, furniture materials, radome materials, rubber reinforcement materials, and vibration materials for speakers. Of course, the composite fiber of the present invention can also be used in other fields, as long as the characteristics of the composite fiber according to the present invention can be fully utilized.

[0034]

[Examples] The present invention will be explained in more detail with reference to Examples below. Note that the present invention is not limited to these.

Example 1 2-(2-hydroxy-5-methyl-phenyl)-2H-benzotriazole and pentaerythrityl-tetrakis [3-(3 , 5-di-t-butyl-4-hydroxyphenyl)propionate] were added to the polyphenylene sulfide in an amount of 2% by weight, passed through a pelletizer at 310°C, then weighed with a gear pump, and passed through a nozzle at 295°C. , to obtain an undrawn yarn. Next, the undrawn yarn was stretched 3 times at 120°C, and the single yarn fineness was 3.
A yarn with a denier, a strength of 7 g/d, and an elongation of 11% was obtained. The color was milky white, but close to white.

When the yarn thus obtained was high-pressure dyed with a red disperse dye, it was dyed well. When this yarn was treated with a weatherometer for 100 hours, the strength retention rate was 8.
The rate was extremely high at 7%. In addition, the coloring was slightly faded, but it was still sufficiently colored.

Comparative Example 1 When the same test as in Example 1 was carried out except that no stabilizer was included, the undrawn yarn obtained was colored slightly pale yellow. Further, even when the fibers were stretched in the same manner, the light yellow coloring did not disappear, and a light yellow colored fiber was obtained. This fiber had a strength of 5.7 g/d and an elongation of 16%. In addition,
Even when trying to lower the elongation, single yarn breakage occurred, and it was not possible to create a yarn with greater strength. This thread is 1
When treated for 00 hours, the strength retention rate decreased to 54%, and it was colored yellowish brown.

Example 2 Composite fibers were obtained using the polyphenylene sulfide of Example 1 as shown in A and B below and polypropylene in accordance with C below.

A. Polyphenylene Sulfide The polyphenylene sulfide of Example 1 was added with 2-(2-hydroxy-
5-Methyl-phenyl)-2H-benzotriazole and pentaerythrityl-tetrakis[3-(3,5-di-
t-butyl-4-hydroxyphenyl)propionate] was added to the polyphenylene sulfide in an amount of 2% by weight, and passed through a pelletizer to form chips. Note that there was almost no coloring of the resin in this step.

B. Polypropylene Polypropylene “Hypol” manufactured by Mitsui Petrochemicals Co., Ltd.
C. Spinning ■Spinning method: core-sheath spinning method ■Core/sheath = polypropylene “Hypol” manufactured by Mitsui Petrochemicals/the above polyphenylene sulfide Core/sheath ratio = 50/50 (weight ratio) The above polyphenylene sulfide of items A and B, and polypropylene were independently melted in an extruder, merged at the mouthpiece so that the core was polypropylene, and the sheath was polyphenylene sulfide, discharged from the mouthpiece at 300° C., and wound up at a take-up speed of 1500 m/min.

Next, the composite fiber was drawn 3.5 times to obtain a yarn having a strength of 4.8 g/d. When the yarn was treated with a weatherometer for 100 hours, the strength retention rate was as high as 84%. Moreover, it was hardly colored. Moreover, there was no change even after 10 days of immersion in 90% sulfuric acid.

Example 3 The stabilizer-added chip used in Example 2 was passed through an extruder, and a T-shaped tube with a length of 200 mm and a spacing of 1.0 mm
Extruded from die, cast on metal drum, width 180
A polyphenylene sulfide film with a thickness of 0.3 mm and a thickness of 0.3 mm was obtained. Next, the film was biaxially stretched 3.5 times vertically and horizontally using a film stretcher, and then subjected to constant length heat treatment at 280° C. for 30 seconds to obtain a polyphenylene sulfide film with a thickness of 25 microns.

The strength of the film thus obtained was 18K.
g/mm. When this film was treated with a weatherometer for 100 hours, the strength retention rate was as high as 75%, and there was almost no coloration.

[0044]

Effects of the Invention The sulfur-containing aromatic resin molded product according to the present invention does not lose its original characteristics as a sulfur-containing aromatic resin molded product, and exhibits high resistance to heat discoloration and high resistance to light discoloration.

[0045] Therefore, the present invention can be applied to various fields that could not be applied to conventional sulfur-containing aromatic resin molded products. In addition, it is difficult to discolor, so it can be colored well.

Claims (4)

[Claims] Claim 1: A molded article made of a sulfur-containing aromatic resin containing at least sulfur in the bonds of the main chain, the molded article comprising:
-(2-hydroxy-5-methyl-phenyl)-2H-
A sulfur-containing aromatic resin molded product containing benzotriazole and pentaerythrityl-tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]. 2. The sulfur-containing aromatic resin molded article according to claim 1, wherein the sulfur-containing aromatic resin molded article containing at least sulfur in the bond of the main chain is made of one of the following resins. A. polyphenylene sulfide, B. polyphenylene sulfide sulfone 3. The sulfur-containing aromatic resin molded product according to claim 1, wherein the sulfur-containing aromatic resin molded product containing at least sulfur in the bond of the main chain is any of the following fibers. A. Fiber made of sulfur-containing aromatic resin alone, B. A composite sulfur-containing aromatic fiber in which a sulfur-containing aromatic resin constitutes at least a part of the surface of the fiber; 4. The sulfur-containing aromatic resin molded product according to claim 1, wherein the sulfur-containing aromatic resin molded product containing at least sulfur in the bond of the main chain is one of the following films. A. A film consisting of a sulfur-containing aromatic resin alone, B. A composite sulfur-containing aromatic film in which a sulfur-containing aromatic resin constitutes at least a part of the surface of the fiber,