JP2001172500A - Polyarylene sulfide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyarylene sulfide resin composition scarcely generating a flash and excellent in flowability (moldability) and mechanical properties. SOLUTION: This polyarylene sulfide resin composition is obtained by compounding (A) a polyarylene sulfide resin, (B) a polyarylene sulfide oligomer having at least one SH terminal and <=2,000 molecular weight in an amount of 0.01-20 pts.wt. and (C) an alkoxysilane compound in an amount of 0.01-20 pts.wt. based on the 100 pts.wt. of (A) the polyarylene sulfide resin.

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 which is free from burrs and has excellent moldability and mechanical properties.

[0002]

2. Description of the Related Art Polyphenylene sulfide (hereinafter referred to as PP)
A polyarylene sulfide (hereinafter sometimes abbreviated as PAS) resin represented by a resin (may be abbreviated as S)
High heat resistance, mechanical properties, chemical resistance, dimensional stability,
Due to its flame retardancy, it is widely used in electrical and electronic equipment parts materials, automotive equipment parts materials, chemical equipment parts materials and the like. However, since there are many burrs in a molded product obtained by injection molding, there is a fundamental disadvantage that post-finishing is required to remove burrs.

Conventional methods for solving this problem include:
It is known to add various alkoxysilane compounds (JP-A-55-29526, JP-A-63-2926).
No. 51430, Japanese Patent Application Laid-Open No. 1-146955, etc.). Various alkoxysilane compounds and PAS resin
The reactivity is high, and the effects of improving the mechanical properties, suppressing the generation of burrs, and the like are recognized. However, in the alkoxysilane compounds used in these publications, PAS
It is difficult to control the reactivity at the time of melt-kneading the resin and the alkoxysilane compound, and as a result, there is a problem that a remarkable increase in melt viscosity occurs and the moldability is reduced. Also, melt viscosity,
There is also a problem that the mechanical characteristics vary widely.

[0004]

SUMMARY OF THE INVENTION In view of the above problems, an object of the present invention is to provide a PAS resin composition which is free from burrs and which is excellent in fluidity (moldability) and mechanical properties.

[0005]

Means for Solving the Problems As a result of repeated studies to achieve the above object, the present inventors have found that a polyarylene sulfide oligomer having an SH terminal and having a molecular weight of 2000 or less and an alkoxysilane compound are added to a PAS resin. It has been found that by blending, it is possible to provide a material which is less likely to generate burrs and has good fluidity (moldability) and mechanical properties, and has completed the present invention. It is known that burr can be reduced by adding a specific aromatic group-containing oligomer to polyphenylene sulfide (Japanese Unexamined Patent Publication No. Hei.
No. 0-292114), the present inventors have found that the effect is extremely remarkable especially in the case of a polyarylene sulfide oligomer having an SH terminal and having a molecular weight of 2000 or less.

That is, the present invention relates to (A) 100 to 100 parts by weight of a polyarylene sulfide resin, (B) 0.01 to 20 parts by weight of a polyarylene sulfide oligomer having at least one SH terminal and having a molecular weight of 2,000 or less. A polyarylene sulfide resin composition containing 0.01 to 20 parts by weight of a silane compound.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the components of the present invention will be described in detail. PA as component (A) used in the present invention
The S resin is mainly composed of-(Ar-S)-(where Ar is an arylene group) as a repeating unit. Examples of the arylene group include p-phenylene group, m-phenylene group, o-phenylene group, substituted phenylene group, p, p ′
-Diphenylene sulfone group, p, p'-biphenylene group,
A p, p'-diphenylene ether group, a p, p'-diphenylenecarbonyl group, a naphthalene group and the like can be used. In this case, among the arylene sulfide groups composed of the above-mentioned arylene groups, in addition to a polymer using the same repeating unit, that is, a homopolymer, a copolymer containing a heterogeneous repeating unit from the viewpoint of processability of the composition Is sometimes preferred. As the homopolymer, one having a p-phenylene sulfide group as a repeating unit using a p-phenylene group as an arylene group is particularly preferably used. Further, as the copolymer, among the arylene sulfide groups consisting of the above-described arylene groups, two or more different combinations can be used. Among them, a combination containing a p-phenylene sulfide group and an m-phenylene sulfide group is particularly preferably used. Can be In this, p
Those containing 70% by mole or more, preferably 80% by mole or more of a phenylene sulfide group are suitable from the viewpoint of physical properties such as heat resistance, fluidity (moldability), and mechanical properties.

Among these PAS resins, a high molecular weight polymer having a substantially linear structure obtained by condensation polymerization from a monomer mainly comprising a bifunctional halogen aromatic compound can be particularly preferably used. PAS with linear structure
In addition to the resin, when polycondensation is performed, a polymer having a partially branched or cross-linked structure can be used by using a small amount of a monomer such as a polyhalo aromatic compound having three or more halogen substituents, A polymer having a relatively low molecular weight linear structure polymer heated at a high temperature in the presence of oxygen or an oxidizing agent to increase the melt viscosity by oxidative crosslinking or thermal crosslinking and to improve the moldability can also be used.

The PAS resin as the component (A) is mainly composed of the linear PAS (having a viscosity of 10 to 300 Pa · s at a temperature of 310 ° C. and a shear rate of 1200 sec ⁻¹ ).
30% by weight, preferably 2 to 25% by weight) has a relatively high viscosity (300 to 3000 Pa · s, preferably 500 to 2
A mixed system with a branched or crosslinked PAS resin of 2,000 Pa · s) may be used. Further, the PAS resin used in the present invention is preferably a resin obtained by removing acid by-product, washing with hot water, washing with an organic solvent (or a combination thereof) after polymerization to remove by-product impurities and the like.

Next, the polyarylene sulfide oligomer having at least one SH terminal and having a molecular weight of 2000 or less of the component (B) used in the present invention will be described. The method for preparing the polyarylene sulfide oligomer (B) is not limited, and examples thereof include a method by depolymerization of a high molecular weight polyarylene sulfide and a known synthesis method (for example, Tetrahedron Letters 39 (1988) 543-546). ). The process of depolymerization of a high-molecular-weight polyarylene sulfide is as follows. 1) A high-molecular-weight (for example, high-temperature G
(PC measurement: Mw = 6 × 10 ^{4 in} terms of polystyrene)
Polyarylene sulfide and sodium sulfide (Na
Both reacted in ₂ S) or high temperature sodium hydrosulfide and (NaSH) in N- methylpyrrolidinone (e.g. 250 ° C.),
2) A method of washing the obtained compound with an acid (for example, hydrochloric acid). The characterization of the polyarylene sulfide oligomer (B) (confirmation of the molecular weight and SH terminal group) was carried out, for example, by Hitachi M-2.
Electrolysis Desorption Method (Fiel
d Desorption). Further, from the infrared spectrum (IR) spectrum, attention can be paid to the absorption peak at 2500-2600 cm ⁻¹ to confirm whether or not the compound has an SH terminal group.

As the polyarylene sulfide oligomer (B), a linear polyarylene sulfide oligomer having SH groups at both ends is particularly preferably used. Further, as the polyarylene sulfide oligomer (B), one kind or two or more kinds of polyarylene sulfide oligomers having different molecular weights may be used.

The amount of the component (B) is 0.01 to 20 parts by weight, preferably 0.1 to 100 parts by weight of the PAS resin (A).
~ 10 parts by weight. If the amount is less than 0.01 part by weight, the desired effect cannot be obtained. If the amount exceeds 20 parts by weight, the mechanical effect is only reduced, and the desired effect cannot be further improved.

Next, the alkoxysilane compound (C) used in the present invention is a silane compound having at least two alkoxy groups in one molecule, and one or more kinds may be used. Alkoxysilane compound used in the present invention
Examples of (C) include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-isocyanatopropyltriethoxysilane, and the like. . Further, the alkoxysilane compound referred to in the present invention includes a hydrolysis product and / or a polymer of the alkoxysilane.

The compounding amount of the alkoxysilane compound (C) is 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the PAS resin (A). If the amount is less than 0.01 part by weight, the desired effect cannot be obtained. If the amount exceeds 20 parts by weight, the amount of gas generated during molding only increases, and the desired effect cannot be further improved.

The resin composition of the present invention may contain an inorganic or organic filler for improving performance such as mechanical strength, heat resistance, dimensional stability (deformation resistance and warpage), and electrical properties. For this purpose, a fibrous, powdery or plate-like filler is used depending on the purpose. Examples of the fibrous filler include glass fiber, asbestos fiber, carbon fiber, silica fiber, silica / alumina fiber, zirconia fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, stainless steel, aluminum, titanium, copper, and brass. And inorganic fibrous substances such as metallic fibrous materials. Particularly typical fibrous fillers are glass fibers and carbon fibers. In addition, a high-melting organic fibrous substance such as polyamide, fluororesin, and acrylic resin can also be used. On the other hand, as the particulate filler, carbon black, silica, quartz powder, glass beads, glass powder, calcium silicate, aluminum silicate, kaolin, talc, clay, diatomaceous earth, silicate such as wollastonite, oxide Metal oxides such as iron, titanium oxide, zinc oxide and alumina; metal carbonates such as calcium carbonate and magnesium carbonate; metal sulfates such as calcium sulfate and barium sulfate; other silicon carbide, boron nitride, silicon nitride; Various metal powders are included. Examples of the plate-like filler include mica, glass flake, various metal foils, and the like. These fillers can be used alone or in combination of two or more. When using these fillers, if necessary, it is desirable to use a surface treatment with a sizing agent or a surface treatment agent or to use the filler after convergence. Examples of the treating agent include functional compounds such as an epoxy compound, an isocyanate compound, a silane compound and a titanate compound. These compounds may be used after being subjected to a surface treatment or a convergence treatment in advance, or may be added simultaneously with the preparation of the material.

The amount of the filler used is 10 to 300 parts by weight per 100 parts by weight of the (A) PAS resin. If the amount is too small, the mechanical strength is slightly inferior. If the amount is too large, the molding operation becomes difficult, and the mechanical strength of the molded article also poses a problem.

The resin composition of the present invention may optionally contain a small amount of another thermoplastic resin in addition to the above components, depending on the purpose. The other plastic resin used here may be any thermoplastic resin that is stable at high temperatures. For example, polyethylene, polypropylene, or an olefin-based resin such as a modified copolymer thereof, polyethylene terephthalate, aromatic dicarboxylic acid such as polybutylene terephthalate and an aromatic polyester such as a diol or oxycarboxylic acid, nylon 66, nylon 6, Nylon 12, nylon
Polystyrene such as 46, styrene resin such as polystyrene, AS, ABS, polyphenylene oxide, polycarbonate, polyalkyl acrylate, polyacetal,
Examples include polysulfone, polyethersulfone, polyetherimide, polyetherketone, and the like.
These thermoplastic resins can be used as a mixture of two or more kinds.

Further, the resin composition of the present invention may contain known substances generally added to thermoplastic resins, that is, flame retardants, coloring agents such as dyes and pigments, stabilizers such as antioxidants and ultraviolet absorbers, Lubricants, crystallization promoters, nucleating agents, and the like can also be appropriately added according to required performance.

The resin composition of the present invention can be prepared by equipment and methods generally used for preparing a synthetic resin composition. Generally, necessary components are mixed, melt-kneaded using a single-screw or twin-screw extruder, and extruded to form molding pellets. It is also a preferable method to melt-extrude the resin component and add and blend an inorganic component such as glass fiber during the extrusion.

The pellets thus obtained can be molded by a generally known thermoplastic resin molding method such as injection molding, extrusion molding, vacuum molding or compression molding.
Most preferred is injection molding.

[0021]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
The specific substances of each component used in Examples and Comparative Examples are as follows. (A) Component Polyphenylene sulfide (PPS) resin; Fortron KPS manufactured by Kureha Chemical Industry Co., Ltd. (B) Component Polyphenylene sulfide (P) having SH groups at both ends
PS) • oligomer; average molecular weight 950, maximum molecular weight 154
6. Prepared by the depolymerization method described above. (B ') component (aromatic group-containing oligomer) (B'-1) 5.0 mol of terephthalic acid dichloride and aniline 10.1
Mole of reactant (average molecular weight 316, melting point 349 ° C) (B'-2) Reactant of 5.0 mole of terephthalic dichloride and 10.1 mole of paraphenylenediamine (average molecular weight 554, melting point 34)
(C) Component (C-1) γ-aminopropyltriethoxysilane (C-2) γ-glycidoxypropyltriethoxysilane Inorganic filler Glass fiber: 13 μm φ, manufactured by NEC Corporation
Fiber length 3 mm, chopped glass fiber The evaluation methods evaluated in Examples and Comparative Examples are as follows. (Burr characteristics) A 20 μm-thick burr was formed on the circumference of a disk (central pin gate) having a thickness of 3 mm and a diameter of 80 mm, and was molded under the following molding conditions. The length of the burr was measured with a 2.5D dimension measuring machine.・ Molding condition Mold temperature; 150 ° C Cylinder temperature; 320 ° C Injection pressure; Minimum pressure to complete filling of molded product Injection speed; 3m / min (Flow length) 0.2mm length, 5mm width bar flow The flow length was measured. The molding conditions are as follows.

Mold temperature; 150 ° C. Cylinder temperature; 310 ° C. Injection pressure; 98 Ma (tensile strength) The tensile strength was measured according to ASTM D-638. Examples 1 to 4 and Comparative Examples 1 to 6 The components shown in Table 1 were melt-kneaded with a twin-screw extruder at a cylinder temperature of 320 ° C. to form pellets of the resin composition, and the above evaluation was performed. Table 1 shows the results.

[0023]

[Table 1]

Claims (3)

[Claims] (A) Polyarylene sulfide resin 100
(B) 0.01-20 parts by weight of a polyarylene sulfide oligomer having at least one SH terminal and having a molecular weight of 2,000 or less (C) 0.01-20 parts by weight of an alkoxysilane compound Composition. 2. The polyarylene sulfide oligomer according to claim 1, wherein (B) the polyarylene sulfide oligomer having at least one SH terminal and having a molecular weight of 2,000 or less is a linear polyarylene sulfide oligomer having SH groups at both ends. Arylene sulfide resin composition. 3. The polyarylene sulfide oligomer having at least one SH terminal and having a molecular weight of 2,000 or less, which is obtained by depolymerizing a high-molecular-weight polyarylene sulfide. Polyarylene sulfide resin composition.