JP7608853B2 - Polyarylene sulfide composition - Google Patents

Description

The present invention relates to a polyarylene sulfide composition that has excellent heat cycle resistance and dimensional accuracy, and in particular to a polyarylene sulfide composition that is highly filled with a filler and has heat cycle resistance and dimensional accuracy that are particularly useful for electrical component applications such as electrical and electronic components or automotive electrical components, by exhibiting a specific weld rupture energy.

Polyarylene sulfide is a resin that exhibits excellent properties such as heat resistance, chemical resistance, and dimensional stability, and taking advantage of these excellent properties, it is widely used in electrical and electronic equipment components, automotive equipment components, and office equipment components. In recent years, as automobiles have become more powerful, higher dimensional precision is required for automotive equipment components. Furthermore, as they are increasingly used under more severe heat cycle conditions, they are also required to have excellent heat cycle resistance (toughness), etc.

Attempts to improve the dimensional accuracy of polyarylene sulfide have been proposed, for example, a resin composition consisting of (a) polyphenylene sulfide resin, (b) polyphenylene ether resin, (c) glass fiber, and (d) calcium carbonate (see, for example, Patent Document 1), and a resin composition consisting of (a) polyphenylene sulfide resin, (b) polyphenylene ether resin, (c) glass fiber, and (d) kaolin (see, for example, Patent Document 2), all of which are characterized by being highly filled with filler.

Attempts to improve the toughness of polyarylene sulfide have been proposed, for example, a resin composition consisting of (a) polyarylene sulfide and (e) an ethylene-α,β-unsaturated carboxylic acid alkyl ester copolymer (see, for example, Patent Document 3); a resin composition consisting of (a) a composition obtained by melt-kneading polyphenylene sulfide and a non-blocked polyfunctional isocyanate compound and (e) an ethylene-α,β-unsaturated carboxylic acid alkyl ester copolymer (see, for example, Patent Document 4); a resin composition consisting of (a) polyarylene sulfide, (e) an ethylene-α,β-unsaturated carboxylic acid alkyl ester copolymer, and (f) a specific type of alkoxysilane compound (see, for example, Patent Document 5); and a resin composition consisting of (a) polyarylene sulfide, (e) a polyolefin resin, and (f) a polymer containing an alkoxysilane group (see, for example, Patent Document 6).

JP 2008-007758 A Japanese Patent Application Publication No. 09-157525 Japanese Unexamined Patent Publication No. 151460/1983 Japanese Patent Application Publication No. 02-255862 Japanese Patent Application Publication No. 05-202245 Japanese Patent Application Publication No. 04-164962

However, the resin compositions proposed in Patent Documents 1 and 2 have problems with heat cycle resistance and toughness, and the resin compositions proposed in Patent Documents 3 to 6 have problems with dimensional accuracy, and therefore have problems in achieving both high dimensional accuracy and heat cycle resistance.

The present invention aims to provide a polyarylene sulfide composition that is highly filled with filler and has both high dimensional accuracy and heat cycle resistance.

As a result of intensive research aimed at solving the above problems, the inventors discovered that by blending at least a specific polyarylene sulfide, a specific carboxylate butyl ester group-containing polyethylene, a fibrous filler, and a powdered filler in specific amounts and achieving a specific weld rupture energy, a polyarylene sulfide composition can be obtained that achieves both high dimensional accuracy and heat cycle resistance, and thus completed the present invention.

That is, the present invention relates to a polyarylene sulfide composition comprising 35 to 50% by weight of an amino group-modified polyarylene sulfide (A) having 0.05 to 3 mol% of amino groups per arylene sulfide unit and a melt viscosity of 200 to 1000 poise measured under conditions of a measuring temperature of 315°C and a load of 10 kg using a high-performance flow tester equipped with a die having a diameter of 1 mm and a length of 2 mm, 2 to 9% by weight of an ethylene-α,β-unsaturated carboxylic acid glycidyl ester-α,β-unsaturated carboxylic acid butyl ester copolymer (B), 35 to 60% by weight of a fibrous filler (C), and 1 to 20% by weight of a granular filler (D), the total proportion of the fibrous filler (C) and the granular filler (D) being 45% by weight or more, and the weld rupture energy evaluated using a dumbbell test piece conforming to the ASTM D638 test piece (Type-1) being 0.34 J or more.

The present invention will be described in detail below.

The amino group-modified polyarylene sulfide (A) constituting the polyarylene sulfide composition of the present invention is generally in the category of polyarylene sulfide, and may include those containing units having amino groups at the terminal units or in-chain units of the polyarylene sulfide. The units of the polyarylene sulfide constituting the amino group-modified polyarylene sulfide may include, for example, p-phenylene sulfide units, m-phenylene sulfide units, o-phenylene sulfide units, phenylene sulfide sulfone units, phenylene sulfide ketone units, phenylene sulfide ether units, biphenylene sulfide units, etc., and the polyarylene sulfide is a homopolymer or copolymer of these units. Specific examples of the amino group-modified polyarylene sulfide include, for example, amino group-modified polyphenylene sulfide, amino group-modified polyphenylene sulfide sulfone, amino group-modified polyphenylene sulfide ketone, amino group-modified polyphenylene sulfide ether, etc., and among these, amino group-modified poly(p-phenylene sulfide) is preferable because it results in a polyarylene sulfide composition that is particularly excellent in heat resistance and strength properties.

The amino group-modified polyarylene sulfide (A) constituting the present invention has 0.05 to 3 mol % of amino groups per arylene sulfide unit, and preferably 0.1 to 2 mol % since it is a polyarylene sulfide composition with particularly excellent heat cycle resistance. In the preparation example of the amino group-modified polyarylene sulfide described later, the amino group-containing dihalogen aromatic compound can be added in an amount of 0.05 to 3 mol %, preferably 0.1 to 2 mol %, based on the total amount of the polyhalogenated aromatic compound and the amino group-containing dihalogen aromatic compound to produce the compound.

The amino group-modified polyarylene sulfide (A) constituting the present invention is a high-quality polyarylene sulfide composition with few impurities, and therefore, when producing the amino group-modified polyarylene sulfide, it is preferable to carry out high-pressure hot water treatment and washing after polymerization. The high-pressure hot water treatment conditions at this time include washing in a water system with a temperature of 150°C or higher and 240°C or lower.

There are no particular limitations on the method for producing the amino group-modified polyarylene sulfide (A), and it may be produced by a method generally known as a method for producing polyarylene sulfide using an amino group-containing polyhalogenated aromatic compound. For example, it can be produced by a method of reacting an alkali metal sulfide with a polyhalogenated aromatic compound and an amino group-containing polyhalogenated aromatic compound in a polymerization solvent.

In this case, the polymerization solvent is preferably a polar solvent, and particularly preferably an organic amide solvent that is aprotic and stable to high-temperature alkali. Any organic amide solvent that falls within the category of organic amide solvents can be used, such as N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphoramide, N-methyl-ε-caprolactam, N-ethyl-2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, dimethylsulfoxide, sulfolane, tetramethylurea, and mixtures thereof. As the polyhalogenated aromatic compound, any compound that belongs to the category of polyhalogenated aromatic compounds can be used. Examples of the polyhalogenated aromatic compound include p-dichlorobenzene, m-dichlorobenzene, o-dichlorobenzene, p-dibromobenzene, m-dibromobenzene, o-dibromobenzene, p,p'-dichlorodiphenyl, p,p'-dibromodiphenyl, 2,6-dichloronaphthalene, 2,6-dibromonaphthalene, 1,3,5-trichlorobenzene, and 1,2,4-trichlorobenzene. Among these, p-dichlorobenzene is preferred because it is easier to obtain a polyarylene sulfide having a high molecular weight and excellent mechanical properties. Examples of the amino group-containing polyhalogenated aromatic compound include 2,5-dichloroaniline, 2,6-di Examples of the alkali metal sulfide include chloroaniline, 3,5-dichloroaniline, 3,5-diaminochlorobenzene, 2-amino-4-chlorotoluene, 2-amino-6-chlorotoluene, 4-amino-2-chlorotoluene, 3-chloro-m-phenylenediamine, 2,5-dibromoaniline, 2,6-dibromoaniline, 3,5-dibromoaniline, and mixtures thereof. In particular, 3,5-dichloroaniline and 3,5-diaminochlorobenzene are preferred. As the alkali metal sulfide, any substance that falls within the category of alkali metal sulfides can be used. For example, sodium sulfide such as anhydrous sodium sulfide, sodium sulfide 2.8 hydrate, and sodium sulfide pentahydrate, lithium sulfide, rubidium sulfide, sodium hydrogen sulfide, and lithium hydrogen sulfide can be used.

The amino group-modified polyarylene sulfide (A) constituting the present invention is preferably heat-treated under an inert gas atmosphere at a temperature of 150°C to 260°C, and more preferably at a temperature of 170°C to 250°C. Examples of the inert gas include nitrogen and argon.

The amino-modified polyarylene sulfide (A) constituting the present invention has a melt viscosity of 200 to 1000 poise, measured using a high-temperature flow tester equipped with a die having a diameter of 1 mm and a length of 2 mm, at a measurement temperature of 315°C and a load of 10 kg. If the viscosity is less than 200 poise, the resulting composition will have poor heat cycle resistance. On the other hand, if the viscosity exceeds 1000 poise, the resulting composition will have poor melt fluidity and poor moldability.

The amount of amino-modified polyarylene sulfide (A) constituting the polyarylene sulfide composition of the present invention is 35 to 50% by weight. If the amount of amino-modified polyarylene sulfide (A) is less than 35% by weight, the resulting composition will have poor molding flowability. On the other hand, if it exceeds 50% by weight, the resulting composition will have poor dimensional accuracy.

As the ethylene-α,β-unsaturated carboxylic acid glycidyl ester-α,β-unsaturated carboxylic acid butyl ester copolymer (B) constituting the polyarylene sulfide composition of the present invention, any one that belongs to this category may be used, and among them, since the obtained polyarylene sulfide composition is also excellent in toughness, it is preferable that it is composed of ethylene residue units: α,β-unsaturated carboxylic acid glycidyl ester residue units: α,β-unsaturated carboxylic acid butyl ester residue units (weight ratio) in the range of 60 to 93: 2 to 10: 5 to 30. Specific examples of the ethylene-α,β-unsaturated carboxylic acid glycidyl ester-α,β-unsaturated carboxylic acid butyl ester copolymer include, for example, (trade name) LOTADER AX8700 (manufactured by Arkema Co., Ltd.) and (trade name) LOTADER AX8750 (manufactured by Arkema Co., Ltd.). The present invention has discovered that by combining an amino group-modified polyarylene sulfide with the ethylene-α,β-unsaturated carboxylic acid glycidyl-α,β-unsaturated carboxylic acid butyl ester copolymer, a composition is obtained that exhibits superior heat cycle resistance to conventionally proposed compositions, such as polyarylene sulfide and ethylene-α,β-unsaturated carboxylic acid glycidyl ester copolymer, ethylene-α,β-unsaturated carboxylic acid glycidyl ester-vinyl ester copolymer, ethylene-α,β-unsaturated carboxylic acid glycidyl ester-α,β-unsaturated carboxylic acid methyl ester copolymer, ethylene-α,β-unsaturated carboxylic acid ester-maleic anhydride copolymer, ethylene-α-olefin-maleic anhydride copolymer, etc.

The polyarylene sulfide composition of the present invention contains 2 to 9 weight percent of ethylene-α,β-unsaturated carboxylic acid glycidyl ester-α,β-unsaturated carboxylic acid butyl ester copolymer (B). If the amount of ethylene-α,β-unsaturated carboxylic acid glycidyl ester-α,β-unsaturated carboxylic acid butyl ester copolymer (B) is less than 2 weight percent, the resulting composition will have poor heat cycle resistance. If the amount exceeds 9 weight percent, the resulting composition will have poor molding flowability.

Examples of the fibrous filler (C) constituting the polyarylene sulfide composition of the present invention include glass fibers such as chopped strands, milled fibers, and rovings having an average fiber diameter of 8 to 15 μm; carbon fibers such as PAN-based carbon fibers and pitch-based carbon fibers; whiskers such as graphitized fibers, silicon nitride whiskers, basic magnesium sulfate whiskers, barium titanate whiskers, potassium titanate whiskers, silicon carbide whiskers, boron whiskers, and zinc oxide whiskers; metal fibers such as stainless steel fibers; inorganic fibers such as rock wool, zirconia, alumina silica, barium titanate, silicon carbide, alumina, silica, and blast furnace slag; organic fibers such as fully aromatic polyamide fibers, phenolic resin fibers, and fully aromatic polyester fibers; and mineral fibers such as wollastonite and magnesium oxysulfate. In particular, glass fibers having an average fiber diameter of 8 to 15 μm and a round cross-sectional shape are preferred because they result in a polyarylene sulfide composition with excellent heat cycle resistance. Two or more of these may be used in combination, and if necessary, the surface may be pre-treated with a functional compound or polymer such as an epoxy compound, an isocyanate compound, a silane compound, or a titanate compound.

The polyarylene sulfide composition of the present invention contains 35 to 60% by weight of fibrous filler (C). If the amount of fibrous filler (C) is less than 35% by weight, the resulting composition will have poor heat cycle resistance and dimensional accuracy. If the amount exceeds 60% by weight, the resulting composition will not only have poor heat cycle resistance but also poor molding fluidity.

Examples of the powdered and granular filler (D) constituting the polyarylene sulfide composition of the present invention include, for example, calcium carbonate, lithium carbonate, magnesium carbonate, zinc carbonate, mica, silica, talc, clay, calcium sulfate, kaolin, wollastonite, zeolite, glass powder, alumina, silicon oxide, magnesium oxide, zirconium oxide, iron oxide, tin oxide, magnesium silicate, calcium silicate, calcium phosphate, magnesium phosphate, graphite, carbon black, glass powder, glass balloons, glass flakes, hydrotalcite, and powdered and granular materials such as metal foil. Among these, calcium carbonate having an average particle size of 1 to 7 μm is preferred because it provides a polyarylene sulfide composition with an excellent balance of mechanical strength and excellent heat cycle resistance. Two or more of these may be used in combination, and if necessary, the surface may be previously treated with a functional compound or polymer such as an epoxy compound, an isocyanate compound, a silane compound, or a titanate compound.

The polyarylene sulfide composition of the present invention contains 1 to 20% by weight of powdered granular filler (D). If the amount of powdered granular filler (D) exceeds 20% by weight, the resulting composition will have poor heat cycle resistance. If the amount is less than 1% by weight, the dimensional accuracy, particularly the anisotropy, will be poor.

The polyarylene sulfide composition of the present invention contains the fibrous filler (C) and the granular filler (D) in a total blend ratio of 45% by weight or more. If the total blend ratio of the fibrous filler (C) and the granular filler (D) is less than 45% by weight, the resulting composition will have poor dimensional accuracy.

The polyarylene sulfide composition of the present invention has a weld rupture energy of 0.34 J or more, as evaluated using a dumbbell test piece conforming to the ASTM D638 test piece (Type-1). If the composition has a weld rupture energy of less than 0.34 J, when it is made into a composite with a metal member, it will have poor heat cycle resistance and will be prone to problems such as cracking and destruction. The weld rupture energy can be calculated as the area enclosed by the stress-strain curve obtained by conducting a weld strength test.

Furthermore, since the polyarylene sulfide composition of the present invention is particularly excellent in heat cycle resistance, it may contain a silane coupling agent (E) consisting of a trialkoxysilane coupling agent having a glycidyl group and/or a trialkoxysilane coupling agent having an amino group, a dialkoxysilane coupling agent and/or a dialkoxysilane coupling agent having an amino group. In this case, the silane capping agent (E) is not particularly limited as long as it is a trialkoxysilane coupling agent having a glycidyl group or an amino group, and specific examples of those belonging to this category include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, etc. The amount of the silane coupling agent (E) is preferably 0.01 to 0.5% by weight.

The polyarylene sulfide composition of the present invention may contain a release agent for improving the mold releasability and appearance when molded into a molded product, within the scope of the object of the present invention. As the release agent, for example, polyethylene wax, polypropylene wax, and fatty acid amide wax are preferably used. As the polyethylene wax and polypropylene wax, general commercial products can be used. In addition, the fatty acid amide wax is a polycondensation product of higher aliphatic monocarboxylic acid, polybasic acid, and diamine, and any wax that falls within this category can be used. For example, a polycondensation product of stearic acid, sebacic acid, and ethylenediamine, such as (product name) Light Amide WH-255 (manufactured by Kyoeisha Chemical Co., Ltd.), can be mentioned.

Furthermore, the polyarylene sulfide composition of the present invention can be used in combination with one or more of various thermosetting resins and thermoplastic resins, such as epoxy resins, cyanate ester resins, phenolic resins, polyimides, silicone resins, polyesters, polyamides, polyphenylene oxides, polycarbonates, polysulfones, polyetherimides, polyethersulfones, polyetherketones, and polyetheretherketones, within the scope of the object of the present invention.

The polyarylene sulfide composition of the present invention may also contain one or more additives, such as heat stabilizers, antioxidants, ultraviolet absorbers, crystal nucleating agents, foaming agents, mold corrosion inhibitors, flame retardants, flame retardant assistants, colorants such as dyes and pigments, and antistatic agents, within the scope of the object of the present invention.

The polyarylene sulfide composition of the present invention can be produced by a conventional heating, melting and kneading method. For example, a heating, melting and kneading method using a single-screw or twin-screw extruder, a kneader, a mill, a Brabender, or the like can be used. In particular, a melting and kneading method using a twin-screw extruder, which has excellent kneading capabilities, is preferred. The kneading temperature is not particularly limited, and can usually be selected from the range of 280 to 400°C. The polyarylene sulfide composition of the present invention can be molded into any shape using an injection molding machine, an extrusion molding machine, a transfer molding machine, a compression molding machine, or the like.

The polyarylene sulfide composition of the present invention is characterized by having both high dimensional accuracy and excellent heat cycle resistance. Furthermore, the polyarylene sulfide composition of the present invention can be used as an insert-molded composite member by insert molding it into other members, particularly metal members, etc.

The insert metal member used in the insert molded composite member may be made of any metal as long as it belongs to the category of metals. Among them, steel, copper, stainless steel, aluminum, magnesium, brass, and nickel are preferred, and steel and copper are particularly preferred, since the resulting insert molded composite member can be adapted to various applications. The insert metal member may be either rolled or cast.

There are no particular limitations on the shape of the insert metal member as long as it is a shape that can be insert molded. Also, one or more insert metal members may be used.

In insert molding, the insert metal member is attached to a mold, and the polyarylene sulfide composition that has been heated and melted at 290 to 340°C can be molded under normal molding conditions using an injection molding machine, extrusion molding machine, compression molding machine, etc., and injection insert molding using an injection molding machine is particularly preferred from the standpoint of production efficiency.

The polyarylene sulfide composition of the present invention and the insert-molded composite member made therefrom have high dimensional accuracy and heat cycle resistance, and can be applied to electrical and electronic parts such as sensors, connectors, relay cases, coil bobbins, capacitors, various terminal boards, small motors, motor brush holders, computer-related parts, and the like; valve alternator terminals, alternator connectors, IC regulators, exhaust gas sensors, coolant sensors, oil temperature sensors, throttle position sensors, crankshaft position sensors, brake pad wear sensors, radiator motor brush holders, water pump impellers, water pump inlets, starter relays, wire harnesses, fuse connectors, horn terminals, electrical component insulating plates, step motor rotors, solenoid bobbins, ignition device cases, vehicle speed sensors, capacitor cases, ECU cases, power module cases, power control units, coil bobbins, motor terminal blocks, reactors, batteries, bus bars, inverters, insulators, and other automotive parts.

The present invention relates to a polyarylene sulfide composition that achieves high dimensional accuracy by being highly filled with a filler and has excellent heat cycle resistance, and is particularly useful for electrical parts such as electric and electronic parts and automotive electrical parts.

Next, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Details of the polyarylene sulfide, fibrous filler, powdered granular filler, ethylene-α,β-unsaturated carboxylic acid glycidyl ester-α,β-unsaturated carboxylic acid butyl ester copolymer, and silane coupling agent used in the examples and comparative examples are shown below.

<Polyarylene sulfide (A)>
Amino group-modified poly(p-phenylene sulfide) (A1-2) (hereinafter simply referred to as PPS (A1-2)): melt viscosity 480 poise. Amino group content 0.15% by weight.
Poly(p-phenylene sulfide) (hereinafter simply referred to as PPS (A2-2)): melt viscosity 560 poise.

<Ethylene-α,β-unsaturated carboxylic acid glycidyl ester-α,β-unsaturated carboxylic acid butyl ester copolymer (B)>
Ethylene-α,β-unsaturated carboxylic acid glycidyl ester-α,β-unsaturated carboxylic acid butyl ester copolymer (B-1) (hereinafter simply referred to as polyethylene copolymer (B-1)): manufactured by Arkema K.K., (product name) LOTADER AX8700, ethylene residue unit: methacrylic acid glycidyl ester residue unit: acrylic acid butyl ester residue unit (weight ratio) = 67:8:25.
Ethylene-α,β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer (B-2) (hereinafter simply referred to as ethylene copolymer (B-2)): Bondine AX8390 (product name), manufactured by Arkema K.K., ethylene residue unit: maleic anhydride residue unit: acrylic acid ester residue unit (weight ratio) = 68: 1.5: 30.5.
Ethylene-α,β-unsaturated carboxylic acid glycidyl ester-α,β-unsaturated carboxylic acid vinyl ester copolymer (B-3) (hereinafter simply referred to as polyethylene copolymer (B-3)): Sumitomo Chemical Co., Ltd., (product name) Bondfast 2B, ethylene residue unit: methacrylic acid glycidyl ester residue unit: vinyl acetate ester residue unit (weight ratio) = 83:12:5
<Fibrous filler (C)>
Glass fiber (C-1): Nippon Electric Glass Co., Ltd., (product name) ECS03T-760H (fiber length 10.5 μm, round cross-sectional shape)
<Powdered filler (D)>
Calcium carbonate (D-1): Shiraishi Kogyo Co., Ltd., (trade name) Whiten P-30; average particle size: 4 μm.
Calcium carbonate (D-2): Shiraishi Kogyo Co., Ltd., (trade name) Whiten P-10; average particle size: 2 μm.

<Silane Coupling Agent (E)>
Trialkoxysilane coupling agent having a glycidyl group (E-1): manufactured by Shin-Etsu Chemical Co., Ltd., (trade name) KBM-403; 3-glycidoxypropyltrimethoxysilane.
Trialkoxysilane coupling agent having an amino group (E-2): Shin-Etsu Chemical Co., Ltd., (trade name) KBM-603; N-2-(aminoethyl)-3-aminopropyltrimethoxysilane.

Synthesis Example 1
In a 50-liter autoclave equipped with a stirrer, 6214 g of Na ₂ S·2.9H ₂ O and 17,000 g of N-methyl-2-pyrrolidone were charged, and the temperature was gradually raised to 205° C. while stirring under a nitrogen stream, and 1,355 g of water was distilled off. After cooling this system to 140° C., 7,120 g of p-dichlorobenzene, 12 g of 3,5-dichloroaniline (about 0.15 mol % relative to the total amount of p-dichlorobenzene and 3,5-dichloroaniline), and 5,000 g of N-methyl-2-pyrrolidone were added, and the system was sealed under a nitrogen stream. The system was heated to 225° C. over 2 hours, polymerized at 225° C. for 2 hours, then heated to 250° C. over 30 minutes, and further polymerized at 250° C. for 3 hours. After the polymerization was completed, the system was cooled to room temperature, and the solid content was isolated by a centrifuge. The solid was washed with hot water at 225° C. and dried at 100° C. for one day to obtain amino group-modified poly(p-phenylene sulfide) (hereinafter referred to as PPS (A1-1)).

This PPS (A1-1) was cured at 250°C for 4 hours in a nitrogen atmosphere to obtain amino group-modified poly(p-phenylene sulfide) (hereinafter referred to as PPS (A1-2)). The melt viscosity of PPS (A1-2) was 480 poise, and the amino group content was 0.15% by weight.

The evaluation and measurement methods for the obtained polyarylene sulfide are shown below.

～Melt viscosity measurement～
The melt viscosity was measured using a high-temperature flow tester (manufactured by Shimadzu Corporation, product name CFT-500) equipped with a die having a diameter of 1 mm and a length of 2 mm, under conditions of a measurement temperature of 315° C. and a load of 10 kg.

～Measurement of weld rupture energy～
Test pieces were prepared using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., product name: SE-75S), and measurements were performed using a tensile tester (manufactured by Shimadzu Corporation, product name: Autograph AG-5000B) in accordance with ASTM D638.

-Heat cycle resistance-
A test piece for heat cycle resistance was prepared by insert molding using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., (product name) SE-75S) to insert a rectangular parallelepiped steel material (carbon steel) of 30 mm x 20 mm x 10 mm, and covering it with a polyarylene sulfide composition having a thickness of 1 mm. The obtained test piece was subjected to a heat cycle in which one cycle consisted of holding at 150°C for 30 minutes and then holding at -40°C for 30 minutes, and the cycle was continued until cracks were visually observed to occur, and the number of heat cycle treatments at which cracks were observed to occur was evaluated as heat cycle resistance. A test piece with a heat cycle treatment number of 100 cycles or more was judged to have excellent heat cycle resistance.

～Dimensional accuracy～
Dumbbell test pieces were prepared in accordance with the test piece (Type-1) using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., product name: SE-75S), and the dimensions in the width direction were measured. Those with a shrinkage rate of 0.2% or less were deemed to have excellent dimensional accuracy.

Example 1
PPS (A1-2) 84.3 wt%, polyethylene copolymer (B-1) 9.4 wt%, calcium carbonate (D-1) 5.7 wt%, and silane coupling agent (E-1) 0.6 wt% were mixed and charged into the hopper of a twin-screw extruder (Toshiba Machine, (product name) TEM-35-102B) heated to a cylinder temperature of 310° C. Meanwhile, glass fiber (C-1) was charged into the hopper of the side feeder of the twin-screw extruder, melt-kneaded at a screw rotation speed of 180 rpm, and the molten composition flowing out of the die was cooled and then cut to prepare a pellet-shaped polyarylene sulfide composition. The composition ratio of the polyarylene sulfide composition at that time was 44.7% by weight of PPS (A1-2), 5% by weight of polyethylene copolymer (B-1), 47% by weight of glass fiber (C-1), 3% by weight of calcium carbonate (D-1), and 0.3% by weight of silane coupling agent (E-1).

The polyarylene sulfide composition was placed in the hopper of an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., product name: SE75) with the cylinder temperature heated to 310°C, and test pieces for measuring the weld rupture energy and heat cycle resistance were molded and evaluated. The results are shown in Table 1.

The resulting polyarylene sulfide composition had excellent dimensional accuracy, weld rupture energy, and heat cycle resistance.

Examples 2 to 7
A polyarylene sulfide composition was prepared in the same manner as in Example 1, except that the PPS (A1-2), the polyethylene copolymer (B-1), the glass fiber (C-1), the calcium carbonate (D-1), and the silane coupling agents (E-1, E-2) were mixed in the proportions shown in Table 1, and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

All of the resulting polyarylene sulfide compositions had high dimensional accuracy, a weld rupture energy of 0.34 J or more, and excellent heat cycle resistance.

Comparative Examples 1 to 8
Polyarylene sulfide compositions were prepared in the same manner as in Example 1, except that the PPS (A1-2, A2-2), polyethylene copolymers (B-1, B-2, B-3), glass fiber (C-1), calcium carbonate (D-1, D-2), and silane coupling agent (E-1) were mixed in the proportions shown in Table 2, and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

The compositions obtained in the comparative examples had poor heat cycle resistance and/or dimensional accuracy.

The polyarylene sulfide composition of the present invention is a polyarylene sulfide composition that achieves high dimensional accuracy by being highly filled with a filler and has excellent heat cycle resistance, and is particularly useful for electrical component applications such as electric and electronic components or automotive electrical components.

Claims (4)

35 to 50% by weight of an amino group-modified polyarylene sulfide (A) having 0.05 to 3 mol % of amino groups per arylene sulfide unit and having a melt viscosity of 200 to 1,000 poise measured under conditions of a measuring temperature of 315° C. and a load of 10 kg using a high-performance flow tester equipped with a die having a diameter of 1 mm and a length of 2 mm, 2 to 9% by weight of an ethylene-α,β-unsaturated carboxylic acid glycidyl ester-α,β-unsaturated carboxylic acid butyl ester copolymer (B), and 35 to 60% by weight of a fibrous filler (C). and 1 to 20% by weight of a powdery filler (D), the total ratio of the fibrous filler (C) and the powdery filler (D) being 45% by weight or more, and further comprising 0.01 to 0.5% by weight of at least one silane coupling agent (E) selected from the group consisting of a trialkoxysilane coupling agent having a glycidyl group, a trialkoxysilane coupling agent having an amino group, a dialkoxysilane coupling agent having a glycidyl group, and a dialkoxysilane coupling agent having an amino group, wherein the polyarylene sulfide composition has a weld rupture energy of 0.34 J or more and a shrinkage rate in the width direction of 0.2% or less, as evaluated using a dumbbell test piece in accordance with the test piece (Type-1) of ASTM D638. The polyarylene sulfide composition according to claim 1, characterized in that the amino group-modified polyarylene sulfide (A) is a high-pressure hot water washed amino group-modified polyarylene sulfide. The polyarylene sulfide composition according to claim 1 or 2, characterized in that the fibrous filler (C) is glass fiber having an average fiber diameter of 8 to 15 μm and a round cross-sectional shape, and the powdered granular filler (D) is calcium carbonate having an average particle diameter of 1 to 10 μm. 4. An insert-molded composite member, which is an insert-molded product of the polyarylene sulfide resin composition according to claim 1 and a metal member .