JPH05148419A - Polyarylene sulfide resin composition - Google Patents

Abstract

PURPOSE:To provide a composition largely improved in the processability without deteriorating the solvent resistance and the flame resistance by adding an olefinic copolymer to a specific polyarylene sulfide resin. CONSTITUTION:100 pts.wt. of a polyarylene sulfide having repeating units of formula -Ar-S- (Ar is a divalent aromatic residue containing at least one six- membered carbon ring), and 0.25-0.45 pt.wt. of an olefinic copolymer comprising 70-99wt.% of an alpha-olefin and 30-1wt.% of an,-unsaturated acid glycidyl ester to provide a composition having a non-Newtonian index of >=1.05 measured with a die having an L/D of 60/1 (mm/mm) at 300 deg.C. A non-cured polyphenylene sulfide having a mol.wt. of 20000-100000 is preferable as the polyarylene sulfide. A copolymer comprising ethylene and glycidyl methacrylate is employed as the olefinic copolymer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyarylene sulfide resin composition, more specifically, 30
A polyarylene sulfide resin composition having a non-Newtonian index of 1.05 or more measured at 0 ° C. and improved processability.

Polyarylene sulfide has been attracting attention as a member for electric / electronic equipment and a member for automobile equipment due to its excellent heat resistance and solvent resistance.

Further, it can be molded into various molded parts, films, sheets, fibers, etc. by injection molding, extrusion molding, etc.
It is widely used in fields requiring heat resistance and solvent resistance.

[0004]

2. Description of the Related Art As typical polyarylene sulfides, Japanese Patent Publication No. 45-3368 and Japanese Patent Publication No. 52-12.
This is due to each manufacturing method disclosed in Japanese Patent No. 240.

The polyarylene sulfide obtained according to JP-B-45-3368 has a substantially low molecular weight and is inferior in mechanical properties.

The polyarylene sulfide resin obtained according to Japanese Patent Publication No. 12240/1987 has a substantially linear high molecular weight polymer, and therefore its mechanical properties are somewhat improved. However, since it is substantially linear, the melt viscosity has a low shear rate dependence and is inferior in workability.

Further, as the composition of the polyarylene sulfide resin, there are disclosed in JP-A-58-154757, JP-A-62-153343 and JP-A-62-15334.
No. 4 and JP-A No. 62-153345 disclose compositions of polyarylene sulfide resin and olefin copolymer.

However, the compositions prepared by these methods are mainly intended to improve impact resistance, and therefore the amount of the olefinic copolymer added is large. Therefore, the solvent resistance and flame retardancy, which are the characteristics of the polyarylene sulfide resin, are significantly reduced.

[0009]

DISCLOSURE OF THE INVENTION The present invention is a polyarylene sulfide in which the processability known as a drawback of polyarylene sulfide is improved without impairing the solvent resistance and flame retardancy which are the characteristics of polyarylene sulfide. A resin composition is provided.

[0010]

That is, according to the present invention, with respect to 100 parts by weight of a polyarylene sulfide resin containing a repeating unit of the following structural formula as a main component, --Ar--S-- (1) (where Ar is 2 containing at least one 6-carbon ring
A olefinic copolymer consisting of 70 to 99% by weight of α-olefin and 30 to 1% by weight of α, β-unsaturated glycidyl ester.
A polyarylene sulfide resin composition having a non-Newtonian index of 1.05 or more measured at 300 ° C. by using a die having L / D = 60/1 (mm / mm) by weight. Is.

The details will be described below.

The polyarylene sulfide resin containing the repeating unit represented by the structural formula (1) as a main structural unit in the present invention can be obtained by a known technique.

Specifically, polyphenylene sulfide,
Examples thereof include polyphenylene sulfide sulfone and polyphenylene sulfide ketone. Preferred is polyphenylene sulfide, and particularly preferred is uncured polyphenylene sulfide.

These polyarylene sulfide resins have a molecular weight of 10,000 or more, particularly 20,000 to 100,000.
Are preferred.

The olefin copolymer used in the present invention is a copolymer of α-olefin and α, β-unsaturated acid glycidyl ester. Examples of the α-olefin here include ethylene, propylene, butene-1, and the like, with ethylene being particularly preferable. Examples of the α, β-unsaturated acid glycidyl ester include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and the like, and glycidyl methacrylate is particularly preferable.

The amount of the α, β-unsaturated acid glycidyl ester copolymer in the olefin copolymer is preferably 1 to 30% by weight, more preferably 2 to 20% by weight. This amount is 1% by weight
When the amount is less than the above, the intended effect is difficult to appear. Further, if it exceeds 30% by weight, gelation occurs during melt-kneading with the polyarylene sulfide resin, which is not preferable for extrusion stability, moldability and the like.

In the olefinic copolymer according to the present invention, other copolymerizable unsaturated monomers such as vinyl acetate can be used as long as the content is 40% by weight or less and the object of the present invention is not impaired. Vinyl propionate, acrylic acid ester, methacrylic acid ester, acrylonitrile, styrene and the like may be copolymerized.

The amount of the above-mentioned olefinic copolymer to be blended is 0.10 with respect to 100 parts by weight of the polyarylene sulfide resin.
25 to 0.45 parts by weight. If the amount is less than 0.25 part by weight, a composition having a non-Newtonian index of 1.05 or more cannot be obtained and the processability is not improved. On the other hand, if the amount exceeds 0.45 parts by weight, the flame retardancy and solvent resistance, which are the characteristics of the polyarylene sulfide resin, are lowered, and the melt viscosity is remarkably increased, which is not preferable because the processability may be impaired. ..

For the composition of the present invention, L / D = 60
The non-Newton's index measured at 300 ° C. using a die of 1/1 (mm / mm) is 1.05 or more, preferably 1.2 or more. When the non-Newton index is less than 1.05, burrs are likely to occur and the workability is poor because the melt viscosity has a small shear rate dependency during molding.

The effect of the present invention is specifically obtained when a glycidyl group-containing copolymer is used as the olefin-based copolymer, and the same effect is obtained when another well-known olefin polymer is used. I can't get it. The reason for this is not clear, but it is considered that it is probably because the olefin-based copolymer itself containing a glycidyl group exhibits thickening during melt-kneading.

In the resin composition of the present invention, as long as the object of the present invention is not impaired, conventional additives such as antioxidants, heat stabilizers, ultraviolet absorbers, lubricants, colorants, flame retardants, Antistatic agents, crystallization accelerators, fibrous and powdery reinforcing agents and other thermoplastic or thermosetting resins can be further compounded.

The method for preparing the resin composition of the present invention is not particularly limited, but the polyarylene sulfide resin and the olefin copolymer are melt-kneaded in the extruder at a temperature higher than the melting point of the polyarylene sulfide resin, and then pelletized. The method of doing is typical.

The melt-kneading temperature is preferably 280 to 340 ° C., and the polyarylene sulfide resin may become unmelted below 280 ° C., and the olefinic copolymer may be decomposed above 340 ° C. There is a risk.

[0024]

The present invention will be described below with reference to examples. It should be understood that these examples are illustrative and not limiting.

The non-Newton index is measured by a Capillograph (manufactured by Toyo Seiki) using a die having a length of 60 mm and a diameter of 1 mm.

The melt viscosity was measured by a high-performance flow tester using a die having a length of 2 mm and a diameter of 0.5 mm at a shear rate of 200 (sec) ⁻¹ and 300 ° C.

Regarding the evaluation of the burr length, the burr length in the vicinity of the gate portion of the injection molded product was measured and evaluated.

The solvent resistance was evaluated by holding the injection-molded product in gasohol (gasoline / methanol = 95/5 weight ratio) at 120 ° C. for 120 hours and then measuring the weight change within 1 hour after taking it out. ..

Reference Example 1 N-methyl-2-pyrrolidone 2 was added to a 50 l autoclave.
1 l was charged and the temperature was raised to 120 ° C., 8078.1 g of 2.8 sodium hydrosulfate and 1247.4 g of lithium acetate were charged, and the temperature was gradually raised to 204 ° C. while distilling water.
When the temperature reached 204 ° C., 1776 g of water was distilled off. At this time, the molar ratio of water to sodium sulfide was 1.22.

Next, the system was cooled to 140 ° C., 9123 g of p-dichlorobenzene was added and the temperature was raised to 250 ° C.
Polymerization was carried out for a time. After cooling the reaction system after polymerization, the polymer was recovered from the polymerization slurry.

The melt viscosity of the obtained polymer is 2800.
Poise and non-Newtonian index was 1.00.

Example 1 100 parts by weight of the polyphenylene sulfide obtained in Reference Example 1 was blended at a ratio of 0.25 parts by weight of an ethylene-methacrylic acid glycidyl ester copolymer (87/13 parts by weight) to prepare 300 parts by weight. Sample pellets were prepared by cutting the strands while melt-kneading with a twin-screw kneading extruder at 0 ° C.

The composition obtained had a melt viscosity of 2850 poise and a non-Newtonian index of 1.18.

Next, the obtained pellets were molded into a test piece by an injection molding machine. The molding conditions are: cylinder temperature 300 ° C., injection pressure 800 kg / cm ² , mold temperature 1
It was set to 45 ° C.

As a result, the releasability of the test piece was good,
The burr length of the obtained test piece was as short as 76 μm.

The tensile strength of the obtained test piece was measured according to the ASTM-638 method. Regarding the solvent resistance, the weight change was good with an increase of 0.9%. The respective results are shown in Table 1.

Example 2 100 parts by weight of the polyphenylene sulfide obtained in Reference Example 1 was blended in an amount of 0.45 parts by weight of an ethylene-methacrylic acid glycidyl ester copolymer (87/13 parts by weight) to carry out. Preparation was carried out in the same manner as in Example 1.

The composition obtained had a melt viscosity of 2910 poise and a non-Newtonian index of 1.29.

Test pieces were prepared in the same manner as in Example 1 and evaluated. The respective results are shown in Table 1.

Comparative Example 1 The polyphenylene sulfide obtained in Reference Example 1 was prepared in the same manner as in Example 1 using only polyphenylene sulfide.

Test pieces were prepared in the same manner as in Example 1 and evaluated. The respective results are shown in Table 1.

Comparative Example 2 100 parts by weight of the polyphenylene sulfide obtained in Reference Example 1 was blended at a ratio of 40 parts by weight of an ethylene-methacrylic acid glycidyl ester copolymer (87/13 parts by weight) to prepare Example 1 Preparation was performed in the same manner.

The composition obtained had a melt viscosity of 55,000 poise and a non-Newtonian index of 2.59.

Test pieces were prepared in the same manner as in Example 1 and evaluated. However, the cylinder temperature is 320
° C., and the injection pressure 1500 kg / cm ^2. The respective results are shown in Table 1.

Table 1

[0046]

As described above, the polyarylene sulfide resin composition of the present invention is excellent in processability.

Claims (1)

[Claims] 1. Ar-S- (1) (where Ar is at least one carbon 6) based on 100 parts by weight of a polyarylene sulfide resin having a repeating unit of the following structural formula (1) as a main structural unit. 2 including member ring
A olefinic copolymer consisting of 70 to 99% by weight of α-olefin and 30 to 1% by weight of α, β-unsaturated glycidyl ester).
A polyarylene sulfide resin composition having a non-Newtonian index of 1.05 or more measured at 300 ° C. using a die having L / D = 60/1 (mm / mm) by weight.