JPH06345965A - Poly(phenylene sulfide) resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition which not only is excellent in mechanical strength, heat resistance, impact resistance, etc., but also has excellent resistance to chemicals represented by an antifreeze. CONSTITUTION:This resin composition comprises 90-10wt.% poly(phenylene sulfide) resin and 10-90wt.% noncrystalline cyclic olefin copolymer having a glass transition point of 120 deg.C or higher.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to heat resistance, dimensional stability,
The present invention relates to a polyphenylene sulfide resin composition which has excellent properties such as chemical resistance and mechanical strength and is also excellent in molding processability. More specifically, it relates to a polyphenylene sulfide resin, an amorphous material having a glass transition point of 120 ° C. or higher. The present invention relates to a polyphenylene sulfide resin composition composed of a cyclic olefin copolymer and an optional thermoplastic elastomer.

[0002]

2. Description of the Related Art Polyphenylene sulfide resin (hereinafter P
PS resin) has a high melting point and has excellent flame retardancy, rigidity, chemical resistance, and other properties suitable for engineering plastics. Used in automobile parts. However, since PPS resin is hard and brittle, and its glass transition point is low at around 90 ° C, strength, dimensional stability, and heat resistance of resin alone are insufficient, and it is usually a reinforcing material such as glass fiber or carbon fiber or other materials. It is used by being reinforced with the filling material. On the other hand, a method of blending an amorphous polymer having a high glass transition point is being studied without using a reinforcing material or a filler for the purpose of improving heat resistance and strength which are insufficient with PPS resin alone. A method of blending a PPS resin and a polyphenylene oxide resin (for example, JP-B-56-34032), a method of blending a PPS resin and a polycarbonate resin (for example, JP-B-53-13468), a PPS resin and a polysulfone. Or a method of blending a polyethersulfone resin (for example, JP-A-59-164360 or JP-A-61-34068), PPS resin and polythioether.
A method of blending tersulfone or a polyethersulfone / polythioethersulfone copolymer (for example, JP-A-63-256653) has been proposed. However, in the resin compositions obtained by these conventional techniques, the effects of improving the dimensional stability and heat resistance of the PPS resin are recognized, but the polyphenylene oxide resin and the polycarbonate are improved.
Bone resin has insufficient heat resistance stability during melt-kneading with PPS having a high melting point and melt molding processing, and super engineering plastics such as polysulfone and polyether sulfone resin are expensive and economical. However, the widespread use as an injection molding resin material has to be limited to some extent.

[0003]

Therefore, according to the present invention, the PP
A resin composition that has excellent molded product characteristics such as strength, dimensional stability, and heat resistance in the category of the combination of S resin and amorphous polymer, and also has both excellent heat stability and surface appearance of the molded product. Is an issue.

[0004]

That is, the present invention is as follows.
(A) Polyphenylene sulfide resin 90 to 10% by weight
And (B) a polyphenylene sulfide resin composition comprising 10 to 90% by weight of an amorphous cyclic olefin copolymer having a glass transition point of 120 ° C. or higher, (A) a polyphenylene sulfide resin of 90 to 9% by weight, and (B) a glass transition point of Amorphous cyclic olefin copolymers 9 to 9 above 120 ° C
The present invention provides a polyphenylene sulfide resin composition comprising 0% by weight and (C) 1 to 40% by weight of a thermoplastic elastomer.

The polyphenylene sulfide resin (A) used in the present invention has a repeating unit represented by the structural formula (1).

[Chemical 1] It is a polymer containing 70 mol% or more, more preferably 90 mol% or more, and if the repeating unit is less than 70 mol%, heat resistance is impaired, which is not preferable. Also PPS
The resin can comprise less than 30 mol% of its repeating unit with a repeating unit having the following structural formula.

[0006]

[Chemical 2] The melt viscosity of the PPS resin used in the present invention is not particularly limited as long as it can be melt-kneaded, but is usually 50 to 20,0.
A 00 poise (310 ° C., shear rate 10 sec ⁻¹ ) is used.

Such PPS resin is a known method, that is, a method for obtaining a polymer having a relatively small molecular weight as described in JP-B-45-3368, or JP-B-52-12240 and JP-A-61-7332. It can be produced by the method described in the publication for obtaining a polymer having a relatively large molecular weight. In the present invention, the PPS resin obtained as described above is crosslinked / polymerized by heating in air, washed with an organic solvent, hot water, an aqueous acid solution, an acid anhydride, an epoxy, an amine,
It is of course possible to use after various treatments such as activation with a functional group-containing compound such as isocyanate.

The amorphous cyclic olefin copolymer (B) used in the present invention includes ethylene, propylene, butene-
A copolymer of an α-olefin such as 1,4-methylpentene-1 and at least one cyclic olefin and having a glass transition temperature of 120 ° C. or higher. Specific examples of the cyclic olefin include bicyclo [2.2.1] hept-
2 ene derivative, tetracyclo [4.4.0.1 ^2.5 . 1
^7.10 ] -3-Dedecene derivative, hexacyclo [6.6.
1.1 ^3.6 . 1 ^10.13 . 0 ^2.7 . 0 ^9.14 ] -4-heptadecene derivative, octacyclo [8.8.0.1 ^2.9 . 1
^4.7 . 1 ^11.18 . 1 ^13.16 . 0 ^3.8 . 0 ^12.17 ] -5-
Docosene derivative, pentacyclo [6.6.1.1 ^3.6 .
0 ^2.7 . 0 ^9.14 ] -4-Hexadecene derivative, heptacyclo-5-icosene derivative, heptacyclo-5-heneicosene derivative, tricyclo [4.3.0.1 ^2.5 ]-
3-decene derivative, tricyclo [4.3.0.1 ^2.5 ]
-3-Undecene derivative, pentacyclo [6.5.1.
1 ^3.6 . 0 ^2.7 . 0 ^9.14 ] -4-Pentadecene derivative,
Pentacyclopentadecadiene derivative, pentacyclo [4.7.0.1 ^2.5 . 0 ^8.13 . 1 ^9.12] -3-pentadecene derivatives and Nonashikuro [9.10.1.
1 ^4.7 . 1 ^13.20 . 1 ^15.18 . 0 ^2.10 . 0 ^12.21 . 0
^14.19 ] -5-Pentacocene derivative and the like can be mentioned.

As the method for polymerizing the above α-olefin and at least one cyclic olefin, hexane, heptane, octane, cyclohexane, benzene, toluene,
A preferable example is a method in which a catalyst such as a vanadium compound or an organoaluminum compound is used in a hydrocarbon solvent such as xylene.

Among the amorphous cyclic olefin copolymers thus obtained, those used in the present invention are required to have a glass transition temperature of 120 ° C. or higher. If the glass transition temperature of the copolymer is less than 120 ° C., the resulting resin composition is insufficient in dimensional stability and heat resistance, which is not preferable. A specific example of the amorphous cyclic olefin copolymer satisfying such characteristics is the amorphous cyclic olefin copolymer manufactured and sold by Mitsui Petrochemical Co., Ltd. under the trade name of "APEL". To be

In the present invention, (A) PPS resin and (B)
Mixing ratio with amorphous cyclic olefin copolymer is 90/1
Within the range of 0 to 10/90% by weight, 80/20 to 2
It is preferably in the range of 0/80% by weight. If the amount is out of the above-mentioned proper range, the effects of improving the strength and heat resistance may be impaired, and the chemical resistance and the fluidity may be remarkably lowered, which is not preferable.

The thermoplastic elastomer (C) optionally used in the present invention is a polyolefin elastomer such as ethylene-propylene copolymer, ethylene-butene copolymer or ethylene-propylene-diene copolymer,
Examples thereof include styrene-diene elastomers such as butadiene block copolymers, silicone elastomers, and the like. Among the elastomers, at least one functional group selected from carboxylic acid groups and their derivatives and epoxy groups is particularly preferable. A thermoplastic elastomer and / or an AB type or ABA 'type block copolymer elastomer having in the molecule (wherein A and A'are vinyl aromatic hydrocarbon blocks and B is a polymerized block). A conjugated diene block) is preferred.

The modified polyolefin modified with a carboxylic acid group and its derivative means ethylene, propylene, butene-1, pentene-1, 4-methylpentene-1, isobutylene, 1,4-hexadiene, dicyclopentadiene, 2, 5-norbornenadiene, 5-ethylidene norbornene, 5-ethyl-2,5-norbornadiene, 5-
A carboxylic acid group, a carboxylic acid ester group, a carboxylic acid metal base, a carboxylic acid anhydride group is added to a polyolefin obtained by radically polymerizing at least one olefin selected from (1′-propenyl) -2-norbornene and styrene. A modified polyolefin obtained by introducing a monomer component having at least one functional group selected from imide groups (hereinafter referred to as a functional group-containing component).

Examples of the functional group-containing component include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, methylmaleic acid, methylfumaric acid,
Mesaconic acid, citraconic acid, glutaconic acid, and metal salts of these carboxylic acids, methyl hydrogen maleate, methyl hydrogen itaconate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, Ethyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, aminoethyl methacrylate, dimethyl maleate, dimethyl itaconate, maleic anhydride, itaconic anhydride, citraconic anhydride, endobicyclo- (2.2.
1) -5-heptene-2,3-dicarboxylic acid, endobicyclo- (2.2.1) -5-heptene-2,3-dicarboxylic acid anhydride, maleimide, N-ethylmaleimide,
Examples include N-butyl maleimide and N-phenyl maleimide.

The method of introducing these functional group-containing components is not particularly limited, and a method of mixing with the main component olefins for copolymerization, or a method of graft-introducing the polyolefin with a radical initiator can be used. . The amount of the functional group component introduced was 0.
001 to 40 mol%, preferably 0.01 to 35 mol%
It is suitable to be within the range.

Specific examples of the modified polyolefin particularly useful in the present invention include ethylene / acrylic acid copolymers, ethylene / methacrylic acid copolymers, and a part or all of the carboxylic acid moieties in these copolymers. Lithium, potassium, calcium, magnesium, zinc salt, ethylene / ethyl acrylate copolymer,
Ethylene / methyl methacrylate copolymer, ethylene /
Ethyl methacrylic acid copolymer, ethylene / ethyl methacrylic acid-g-maleic anhydride copolymer ("g" represents a graft, the same applies hereinafter), ethylene / methyl methacrylate-g-maleic anhydride copolymer Polymer, ethylene / ethyl acrylate-g-maleic anhydride copolymer, ethylene / ethyl acrylate-g-maleimidic acid copolymer, ethylene / ethyl acrylate-g-N-phenylmaleimidic acid copolymer and these copolymers Partially saponified polymer, ethylene / propylene-g-maleic anhydride copolymer, ethylene / butene-1-g-maleic anhydride copolymer, ethylene / propylene / dicyclopentadiene-g-maleic anhydride copolymer Combined, ethylene / propylene / 1,4-hexaquinene-g-maleic anhydride copolymer, ethylene /
Propylene / 2,5-norbornadiene-g-maleic anhydride copolymer, ethylene / propylene-g-N-phenylmaleimide acid copolymer, ethylene / butene-1-g
Examples thereof include -N-phenylmaleimidic acid copolymer.

The modified polyolefin modified with an epoxy group is an olefin polymer having an epoxy group in its side chain or main chain, and does not include a usual thermosetting epoxy resin. Examples of the epoxy group-containing olefin polymer include olefin polymers having a glycidyl group such as glycidyl ester, glycidyl ether, and glycidyl amine in the side chain. In the present invention, among these epoxy group-modified polyolefins, a copolymer composed of α-olefin and glycidyl ester of α, β-unsaturated acid is preferably used. Examples of the α-olefin include ethylene, propylene, butene-1 and the like. Further, the glycidyl ester of α, β-unsaturated acid is represented by the following general formula

[Chemical 3] (R represents a hydrogen atom or a lower alkyl group), specifically, glycidyl acrylate,
Examples thereof include glycidyl methacrylate and glycidyl ethacrylate. The content of the epoxy group in the epoxy group-containing olefin polymer is preferably 0.1 to 30% by weight, particularly preferably 0.2 to 20% by weight, and if the content is less than 0.1% by weight, the desired effect cannot be obtained. P is exceeded when the weight% is exceeded
Gelation occurs during melt-kneading with PS and the amorphous cyclic olefin copolymer, and extrusion stability and molding processability are deteriorated, which is not preferable.

The AB type or A used in the present invention
The -BA 'type block copolymer elastic material is an AB type or A- type composed of a vinyl aromatic hydrocarbon and a conjugated diene.
It is a B-A 'type block copolymer elastic body, and the terminal blocks A and A'may be the same or different, and the aromatic moiety is derived from a vinyl aromatic hydrocarbon which may be monocyclic or polycyclic. And thermoplastic homopolymers or copolymers. Examples of such vinyl aromatic hydrocarbons include styrene, α-methylstyrene, vinyltoluene, vinylxylene, ethylvinylxylene, vinylnaphthalene and mixtures thereof. The intermediate polymer block B is composed of a conjugated diene hydrocarbon, for example, 1,
Examples include polymers derived from 3-butadiene, 2,3-dimethylbutadiene, isoprene, 1,3-pentadiene and mixtures thereof.

The block copolymer elastic material used in the present invention includes those obtained by subjecting the intermediate block B of the above block copolymer to the hydrogenation treatment, and these block copolymers or their hydrogenated products are also included. Those in which the above-mentioned components having a functional group such as a carboxylic acid derivative or an epoxy group are introduced by a method such as graft polymerization or copolymerization are also included.

When the thermoplastic elastomer (C) is used in the present invention, the blending ratio of the components (A) to (C) is PPS.
Resin 90 to 9% by weight, preferably 80 to 30% by weight, amorphous cyclic olefin copolymer 9 to 90% by weight, preferably 20 to 70% by weight, and thermoplastic elastomer 1 to 4
0% by weight, preferably 5 to 35% by weight,
Within this compounding composition range, it can be selected according to characteristic goals such as heat resistance, strength, impact resistance, and chemical resistance. PP
If the content of S resin exceeds 90% by weight, the heat resistance and rigidity at high temperature of the resin composition will be insufficient, which is not preferable. On the other hand, if the content of PPS resin is less than 9% by weight, the fluidity and the surface appearance of the molded product will be poor. It is not preferable because it is significantly impaired.

If the content of the thermoplastic elastomer as the component (C) is less than 1% by weight, the impact resistance of the resin composition tends to be insufficient, while the content of the thermoplastic elastomer is 40%.
If it exceeds 5% by weight, not only the heat resistance of the resin composition and the rigidity at high temperature but also the fluidity are deteriorated, which is not preferable.

In the present invention, the fibrous and / or non-fibrous filler is not an essential component, but if necessary PP
When the S resin, the amorphous cyclic olefin copolymer and the thermoplastic elastomer are further compounded, it is possible to compound them in the range of up to 400 parts by weight based on 100 parts by weight of the polyphenylene sulfide resin composition comprising the thermoplastic elastomer. In the sense of obtaining high mechanical properties, dimensional stability, etc., when compounding a PPS resin, an amorphous cyclic olefin copolymer, and a thermoplastic elastomer, 100 parts by weight of a polyphenylene sulfide resin composition composed of the thermoplastic elastomer is used. It is preferable to add 30 to 300 parts by weight of the granular and / or non-fibrous filler.

Examples of the fibrous and / or non-fibrous filler to be blended in the present invention as required include glass fibers, carbon fibers, potassium whisker titanate, zinc oxide whiskers, alumina fibers, silicon carbide fibers, ceramic fibers, Fibrous fillers such as asbestos fibers, gypsum fibers, aramid fibers, metal fibers, wollastonite, sericite, kaolin, mica, clay, bentonite, asbestos, talc, silicates such as alumina silicate, alumina, silicon oxide, oxidation Metal compounds such as magnesium, zirconium oxide, titanium oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, glass beads, ceramic beads, boron nitride and silicon carbide. , Such as calcium phosphate and silica Fibrous fillers and the like, which may be hollow, it is also possible to further combination of these fillers 2 or more. In addition, these fibrous and / or non-fibrous fillers are used as silane-based or titanium
Pre-treatment with a coupling agent such as a genotype is more preferable from the viewpoint of mechanical strength and the like.

The PPS resin composition of the present invention contains an antioxidant, a heat stabilizer, and a stabilizer within a range that does not impair the effects of the present invention.
Usual additives such as a lubricant, a plasticizer, a crystal nucleating agent, an anti-UV agent, a coloring agent and a flame retardant can be added. Also,
The PPS resin composition of the present invention is a polyamide, a tetrafluorinated polyethylene, and a polyethylenic resin within a range that does not impair the effects of the present invention.
Telimide, polyamide imide, polyimide, polycarbonate
Resins such as carbon dioxide, polyetheretherketone, polyetheretherketone, epoxy resin, phenol resin, polyethylene, polystyrene, polypropylene, ABS resin, polyester, polyamide elastomer, polyester elastomer may be contained.

In the PPS resin composition of the present invention, γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane are used for the purpose of improving the mechanical strength and the moldability of burrs and the like within a range not impairing the effects of the present invention. Glycidoxypropyltriethoxysisilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ- (2-aminoethyl) aminopropyl Trimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysisilane and γ- (2-ureidoethyl) ) Aminopropyltrimethoxysilane, γ-a Cyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyl Organosilane compounds such as diethoxysilane and γ-isocyanatopropyltrichlorosilane can be added.

The method of preparing the composition of the present invention is not particularly limited, but the mixture of the raw materials is usually melted by a known method such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader, and a mixing ball. The method of supplying to a mixer and kneading at a temperature of 280 to 380 ° C. can be mentioned as an example. The order of mixing the raw materials is not particularly limited, and the PPS resin,
Amorphous cyclic olefin copolymer, thermoplastic elastomer, and optionally fibrous and / or non-fibrous filler are dry-blended together, and then melt-kneaded by the above-mentioned method, or PPS resin, amorphous Cyclic olefin copolymers, thermoplastic elastomers, fibrous and / or
Alternatively, two or three of the non-fibrous fillers are dry blended, melt-kneaded, and then the remaining one or two.
A typical method is to melt and knead the same.

The PPS resin composition obtained by the present invention has a molding property having excellent molded product characteristics such as strength, dimensional stability and heat resistance, and also has both excellent fluidity and surface appearance of the molded product. A resin composition with excellent properties, such as sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, optical pickups, oscillators, various terminal boards, transformers, plugs, and prints. Board, tuner,
Speaker, microphone, headphone, small motor, magnetic head base, power module, semiconductor,
Electric / electronic parts such as liquid crystal, FDD carriage, FDD chassis, motor brush holder, parabolic antenna, computer related parts; VTR parts,
Representative of TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, audio parts, audio equipment parts such as audio / laser disks / compact disks, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, etc. Household and office electrical products parts; office computer related parts, telephone related parts, facsimile related parts, copier related parts,
Machine-related parts such as cleaning jigs, motor parts, lighters, and typewriters: optical devices such as microscopes, binoculars, cameras, watches, and precision-machine related parts;
Alternator terminal, alternator connector, IC regulator, potentiometer base for light deer, various valves such as exhaust gas valve, fuel-related / exhaust system / intake system various pipes, air intake nozzle snorkel, intake manifold, fuel pump, engine cooling water Joint, carburetor main body, carburetor spacer, exhaust gas sensor,
Cooling water sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter,
Brake pad wear sensor, air conditioner thermostat base, heating hot air flow control valve, radiator motor brush holder, water pump impeller, turbine vane, wiper motor related parts, detributor, starter switch, starter relay, transmission wire harness, Window washer nozzles, air conditioner panel switch boards, fuel-related electromagnetic valve coils, fuse connectors, horn terminals, electrical component insulating plates, step motor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters. It is useful for automobiles, vehicle-related parts such as ignition device cases, and various other applications.

Hereinafter, the present invention will be described in more detail with reference to examples.

[0029]

EXAMPLES The surface appearance, tensile strength, bending strength, heat distortion temperature, and chemical resistance of the molded products described in Examples and Comparative Examples were measured according to the following methods.

Surface appearance of molded product: A square plate with ribs of 40 × 15 × 1 mm was injection-molded at different mold temperatures, and the surface appearance of the obtained square plate was visually judged.

Tensile strength: ASTM-D638 Bending strength: ASTM-D790 Heat distortion temperature: ASTM-D648 (18.6 kg / cm)
² load) Chemical resistance: A tensile-damping piece was immersed in a 50% aqueous solution of long-life coolant, and the retention rate of tensile strength before and after treatment at 130 ° C / 1000 hours was calculated to be used as a guideline for chemical resistance. Flowability: 315 according to ASTM D1238-86.
The melt flow rate was measured under the condition of 5 ° C. and a load of 5000 g and used as a measure of melt fluidity.

Reference Example 1 (Synthesis Method of Polyphenylene Sulfide) PPS-1: Sodium Sulfide 3.26 in Autoclave
Kg (including 25 mol, water of crystallization 40%), sodium hydroxide 4 g, sodium acetate trihydrate 1.19 Kg (about 8.8 mol) and N-methylpyrrolidone (hereinafter NMP).
Abbreviated as).
Distilled water containing 1.36 kg of water heated to 5 ° C.
L was removed. To the remaining mixture, 3.75 Kg of 1,4-dichlorobenzene (25.5 mol) and NMP2K
g, and heated at 265 ° C. for 5 hours. 7 reaction products
It was washed 5 times with warm water at 0 ° C and dried under reduced pressure at 80 ° C for 24 hours to obtain a melt viscosity of about 1500 poise (310 ° C, shear rate 1
0 sec ^-1 ) powdery polyphenylene sulfide (PPS-
1) About 2 kg was obtained.

PPS-2: 3.26 Kg of sodium sulfide (25 mol, containing 40% of water of crystallization) in an autoclave,
Sodium hydroxide 4g, sodium acetate trihydrate 1.2
Charge 2 Kg (about 9 mol) and NMP 7.9 Kg,
Gradually raise the temperature to 205 ° C with stirring, and water 1.36K
About 1.5 liters of distilled water containing g was removed. The residual mixture contained 3.75 kg of 1,4-dichlorobenzene (25.5 kg).
Mol) and 2 Kg of NMP were added and heated at 265 ° C. for 3.5 hours. The reaction product was washed 5 times with warm water at 70 ° C.,
After drying under reduced pressure at 80 ° C. for 24 hours, about 2 kg of powdery polyphenylene sulfide (PPS-2) having a melt viscosity of about 900 poise (310 ° C., shear rate 10 sec ⁻¹ ) was obtained.

As PPS-3, manufactured by Toray Industries, Inc.,
M2100 was used.

Example 1 70% by weight of PPS resin (PPS-1) and 30% by weight of "APEL" APL5018 manufactured by Mitsui Petrochemical Co., Ltd.
After dry blending with a Henschel mixer,
The mixture was melt-kneaded and pelletized by a screw type twin-screw extruder set to a cylinder temperature of ° C. After drying the obtained pellets, using an injection molding machine, a cylinder temperature of 310 ° C.,
A predetermined test piece for property evaluation was obtained by injection molding at a mold temperature of 150 ° C. The measurement results of the obtained test pieces are summarized in Table 1. The resin composition obtained here had a good surface appearance and excellent heat resistance, and was of high practical value.

[0036]

[Table 1] Comparative Example 1 The PPS resin used in Example 1 was melt pelletized alone, and the resulting pellets were dried and injection-molded using an injection molding machine in the same manner as in Example 1 to measure the properties of the test piece. However, the heat distortion temperature of this product was 120 ° C., and the heat resistance was insufficient.

Comparative Example 2 The amorphous cyclic olefin copolymer used in Example 1 was dried alone and injection-molded in the same manner as in Example 1 using an injection molding machine to measure the characteristics of the test piece. . This product showed good heat resistance at a heat distortion temperature of 170 ° C, but required a high molding pressure due to its low melt flow rate value of 10 g / 10 min or less, resulting in insufficient moldability. Met.

Examples 2 to 4 PPS resins and amorphous cyclic olefin copolymers were mixed in various proportions shown in Table 1 and melted in a twin-screw extruder having a cylinder temperature of 300 to 320 ° C. Pelletized after kneading. The results of injection molding and measurement performed on the obtained pellets in the same manner as in Example 1 are summarized in Table 1. All of these had high practical value with excellent strength and heat resistance.

Examples 5-7 PPS resin (PPS-2), the amorphous cyclic olefin copolymer used in Example 1 and ethylene / glycidyl methacrylate (88/12 weight ratio) copolymer were prepared in several amounts. The mixture compounded in a ratio was melt-kneaded and pelletized by a twin-screw extruder having a cylinder temperature of 320 ° C. The results of injection molding and characteristic measurement performed on the obtained pellets in the same manner as in Example 1 are summarized in Table 2. All of these were excellent in strength, heat resistance, and impact resistance and were of high practical value.

[0040]

[Table 2] Examples 8-10, Comparative Example 3 PPS resin, the amorphous cyclic olefin copolymer used in Example 1, the glass fiber and the inorganic filler were dry blended in a Henschel mixer in several proportions, and then 320
The mixture was melt-kneaded and pelletized by a screw type single-screw extruder set to a cylinder temperature of ° C. After drying the obtained pellets, using an injection molding machine, a cylinder temperature of 320 ° C.,
A predetermined test piece for property evaluation was obtained by injection molding at a mold temperature of 150 ° C. The measurement results of the obtained test pieces are summarized in Table 3. The resin composition obtained here was excellent in strength and impact resistance, and also showed extremely excellent antifreeze resistance, and was suitable for automobile under hood parts. On the other hand, when no amorphous cyclic olefin copolymer is used, antifreeze resistance is 5
There was a shortage of 3%.

[0041]

[Table 3]

[0042]

The polyphenylene sulfide resin composition of the present invention is a resin composition having excellent properties such as high mechanical strength, heat resistance and impact resistance, and excellent chemical resistance represented by good antifreeze resistance. It is a thing.

Claims (3)

[Claims] 1. (A) Polyphenylene sulfide resin 9
A polyphenylene sulfide resin composition comprising 0 to 10% by weight and (B) 10 to 90% by weight of an amorphous cyclic olefin copolymer having a glass transition point of 120 ° C or higher. 2. (A) Polyphenylene sulfide resin 9
A polyphenylene sulfide resin composition comprising 0 to 9% by weight, (B) 9 to 90% by weight of an amorphous cyclic olefin copolymer having a glass transition point of 120 ° C. or higher, and (C) 1 to 40% by weight of a thermoplastic elastomer. 3. A thermoplastic elastomer and / or an A-B type or A-B-A thermoplastic elastomer having in the molecule at least one functional group selected from a carboxylic acid group and its derivative and an epoxy group. The polyphenylene sulfide resin composition according to claim 2, wherein the polyphenylene sulfide resin composition is a'-type block copolymer elastic body (wherein A and A'are vinyl aromatic hydrocarbon blocks and B is a polymerized conjugated diene block).