JPS58154757A - Polyarylene sulfide resin composition - Google Patents

Abstract

PURPOSE:To provide a polyarylene sulfide resin compsn. having well-balanced excellent resistance to heat and impact, extrusion stability, moldability, color tone and appearance of moldings obtained therefrom, by blending a specified olefin copolymer in a specified amount. CONSTITUTION:0.5-50, pref. 5-30pts.wt. olefin copolymer composed of 70- 99wt% alpha-olefin and 30-1wt% alpha,beta-unsaturated acid glycidyl ester, such as ethylene/glycidyl methacrylate copolymer, is incorporated in 100pts.wt. polyarylene sulfide resin having, as a main structural unit, a repeating unit of the formula (wherein Ar is a bivalent arom. residue contg. at least one six-membered carbon ring) to obtain the titled polyarylene sulfide resin compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyarylene sulfide resin composition that is well-balanced in heat resistance, impact resistance, extrusion stability, moldability, color tone, and appearance of molded products.

Polyarylene sulfide resin, represented by polyphenylene sulfide, itself has excellent heat resistance, and molding materials reinforced with reinforcing agents such as glass fiber are used in fields such as automobile parts and electronics-related parts. It is being used as a metal substitute and is attracting attention as a material that has the potential to grow into large-scale NIPPL.

However, unreinforced poly-117-rylene sulfide resin has poor extrusion stability and moldability, and the molded products obtained are not only black and have poor appearance, but also have insufficient mechanical properties such as impact resistance. Therefore, the reality is that it is still not used as a molding material.

Therefore, the present inventors conducted intensive studies with the aim of improving the impact resistance, extrusion stability, moldability, and appearance of molded products of polyarylene sulfide resin without using reinforcing agents such as glass fibers. By blending a specific amount of a specific olefin copolymer into a sulfide resin, the above-mentioned properties are improved in a balanced manner while maintaining the excellent heat resistance of the polyarylene sulfide resin, and the color tone of the molded product is improved. The present invention has been achieved based on the discovery that this can be improved.

That is, the present invention uses polyarylene sulfide resin 100
Based on the weight part, 70 to 99% by weight of σ-olefino and α,
Provided is a polyarylene sulfide resin composition, characterized in that it contains 0.5 to 50 parts by weight of an olefin copolymer consisting of 1 to 30 parts by weight of puridyl ester of a β-unsaturated acid. .

The polyarylene sulfide resin used in the present invention is a polymer whose main structural unit is a repeating unit of the general formula +Ar-5-), where Ar in the above formula is a divalent aromatic compound containing at least one 6-membered carbon ring. etc. (X is F, CI, Br or CH3, m is 1-3). Among them, a typical polyarylene sulfide resin has the general formula wide, and for example, one commercially available from Trollium Co., Ltd. in the United States under the trade name 1Rydon' can be used.

These polyarylene sulfide resins preferably have a molecular weight of 10,000 or more, particularly 20,000 to 50,000, and a melting point of 270 to 290°C.

The above-mentioned 1lite 7' usually has a molecular weight of 20,000 or less, but for example, according to the method described in Japanese Patent Publication No. 12240/1989, a high molecular weight polyphenylene sulfide having a molecular weight of 20,000 or more can be easily obtained. .

The olefin copolymer used in the present invention is a copolymer consisting of α-t lefin and glycidyl ester of α, β-unsaturated acid, and the α-olefins herein include ethylene, propylene, buteno-1, etc. are mentioned, but ethylene is preferably used. Glycidyl esters of α,β-unsaturated acids are compounds represented by the general formula or lower alkyl group, and specific examples include glycyrel acrylate, glycidyl methacrylate, and glycidyl ethacrylate. However, among these, glycidyl methacrylate is preferably used. The copolymerized amount of α,β-unsaturated glycidyl ester in the olefin copolymer is preferably 1 to 30% by weight, particularly 3 to 20% by weight, and if it is less than 1% by weight, the desired improvement effect cannot be obtained. If the amount exceeds 30% by weight, gelation occurs during melt mixing with the polyarylene sulfide resin, which further deteriorates extrusion stability, moldability, mechanical properties, etc., which is not preferable. In addition, the olefin copolymer may contain other copolymerizable unsaturated monomers, such as vinyl ether, vinyl acetate, vinyl probionate, acrylic acid, in an amount of 40% by weight or less and within a range that does not impede the purpose of the present invention. Methyl, methyl methacrylate, acrylonitrile, styrene, etc. may be copolymerized.

The amount of the olefin copolymer blended is preferably 0.5 to 50 parts by weight, particularly 5 to 30 parts by weight, based on 100 parts by weight of the polyarylene sulfide resin, and if it is less than 0.5 parts by weight, the desired improvement effect cannot be achieved. If the amount exceeds 50 parts by weight, not only will the excellent heat resistance of the polyarylene sulfide resin itself deteriorate, but also gelation will occur during melt mixing, resulting in poor mechanical properties, extrusion stability, moldability, etc. This is not desirable because it becomes

By blending the olefin copolymer with the above copolymerization composition into the polyarylene sulfide resin at the above blending ratio, the extrusion stability during melt extrusion and the moldability represented by the lower limit pressure of injection molding are significantly improved. A resin composition is obtained that gives a molded article with excellent balance in impact resistance, appearance, and color tone. Such effects of the present invention can be specifically obtained when using the glinosyl group-containing copolymer mentioned above as the olefin copolymer, and when using other well-known olefin copolymers, such as ethylene-vinyl acetate copolymer. Similar effects cannot be obtained when using polymers or ethyleneno-propylene copolymers. The reason for this is not clear, but it is thought that in the composition of the present invention, the glycidyl group in the olefin (1,!) body acts specifically with the polyphenylene resin.

i The resin composition of the present invention may contain conventional additives such as antioxidants, heat stabilizers, ultraviolet absorbers, lubricants, mold release agents, fillers, fibrous or Powder-like reinforcing agents, coloring agents, flame retardants, flame retardant aids, antistatic agents, crystallization accelerators, and other thermoplastic or thermosetting resins can be further blended.

Although there are no particular limitations on the means for preparing the resin composition of the present invention, a typical method is to melt and mix the polyarylenosulfide resin and the olefin copolymer and then pelletize the mixture.

, the melting crosstalk temperature is desirably 280 to 320°C, and 2
If it is less than 80°C, the polyarylene sulfide resin will not be sufficiently melted, and if it exceeds 320°C, it will cause crosslinking reaction or thermal decomposition reaction of the olefin copolymer, so care must be taken.

The resin composition of the present invention, which is formed by a wall, can be easily molded into a film by ordinary methods such as injection molding or extrusion molding, and the resulting molded product exhibits excellent performance as described above. .

The effects of the present invention will be further explained below with reference to Examples.

Reference Example 1 (Preparation of polyphenylene sulfide) 5 moles of sodium sulfide, 1.2 moles of N-methylpyrrolidone A4 and lithium acetate dihydrate as shown in Table 1 were charged into an autoclave equipped with a stirrer, and while removing the distillate. It was heated to 205° C. for 2 hours. Then to this system 1,4-
Prepared 5.1 mol of dichlorbenozeno, 245 in 20 minutes
℃, the reaction was further carried out at 245° C. and a pressure of 5 to 8 kg/c4 gauge. The reaction products were washed several times with hot water and dried to obtain two types of high molecular weight polyphenylene sulfides A and B having the weight average molecular weights and melting points shown in Table 1.

Table 1 shows Rydon R-4' (polyphenylene sulfide manufactured by Phillips Petroleum) as a polymer f.
They are also shown as V&lc.

Table 1 Example 1 Various polyphenylene sulfides (A to C
) and ethylene glycidyl methacrylate (90/
10 weight ratio) copolymers were triblended in the proportions shown in Table 2, and melt-mixed using a T-niscrew extruder at a temperature of 290 to 310°C. The mixture was then extruded in the form of guts and pelletized using a strand cutter. As a guideline for extrusion stability during gut extrusion, the ratio of pelletizable guts to all guts is evaluated, and the pellet color tone is
Judgment was made based on the value.

Next, each pellet was placed in a 5-ounce screw innoline injection molding machine set at 290 to 300°C, and the mold temperature was 140°C to produce Izot impact test pieces, dumbbell test pieces, and heat distortion temperature measurement test pieces. Molded.

When molding a dumbbell test piece, the lower limit pressure for molding, which is a guideline for moldability, was measured, and the mold releasability, degree of flaking, and appearance (surface gloss) of the molded product were evaluated.

The Izot impact strength of each of the obtained test pieces was measured according to ASTM D-256. These results are shown in Table 2.

As is clear from the results in Table 2, the composition of the present invention (&1
~3) is a single borifuenylene sulfide (Nn4~6)
The extrusion stability is significantly improved compared to the pellet color tone (L
Not only does it have a large effect on improving moldability (value) and moldability, it also provides molded products with extremely excellent impact resistance and surface gloss.

Furthermore, if the amount of the ethylene-glycidyl methacrylate copolymer is less than 0.5 parts by weight (lI & 1L7), the desired effect will hardly be obtained, and if it exceeds 50 parts by weight (lV & 1L7),
8) Gelation occurs in the extruder, making extrusion impossible.

Comparative Example 1 Polyphenylene sulfide (IV&
IB) 100 parts by weight and ethylene-vinyl acetate copolymer [
Copolymerization ratio 80:20 (weight ratio), DQ manufactured by Nippon Unicar
DJ-3868] 10 parts by weight was triblended and then extruded in the same manner as in Example 1, and then molded, but the extrusion stability was rather poor and the pellet color tone and moldability were hardly improved. The Izo impact strength (with notches) of the molded product was 2.6 #/α, which was hardly improved.

Patent applicant Higashi Shikikai Co., Ltd. E

Claims (1)

[Claims] 100 parts by weight of polyarylene sulfide resin whose main structural unit is a repeating unit of the general formula +Ar-5-3- (Ar in the formula represents a divalent aromatic residue containing at least one carbon 6-membered ring) 70-99% by weight of α-olefino and 1-30% by weight of glycidyl ester of α,β-unsaturated acid.
1. A polyarylene sulfide parabolite, characterized in that it contains 0.5 to 50 parts by weight of an olefin copolymer of t% by weight.