JPH06329905A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To improve the mechanical properties such as impact resistance and tensile elongation of a poly(arylene sulfide) resin without using a reinforcement, e.g. glass fiber, by incorporating a specific olefin copolymer and a specific thermoplastic resin into the resin. CONSTITUTION:A poly(arylene sulfide) resin is mixed with an olefin copolymer (a) having glycidyl groups and with at least one thermoplastic resin selected from olefin copolymers other than the copolymer (a), acrylic rubbers, and hydrogenated conjugated-diene polymers. The copolymer (a) comprises 10-50wt.% units (1) derived from an alpha-olefin, 50-90wt.% units (2) derived from an alkyl ester of an alpha,beta-unsaturated carboxylic acid, and 0.5-30wt.% units derived from a glycidyl ester of an alpha,beta-unsaturated acid, with the sum of units (1) and (2) being 70-99.5wt.%.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermoplastic resin composition containing a polyarylene sulfide resin as an essential component and having excellent toughness such as impact resistance and tensile elongation.

[0002]

2. Description of the Related Art Polyphenylene sulfide (hereinafter referred to as PP
Polyarylene sulfide (hereinafter abbreviated as PAS) resin represented by S) has excellent heat resistance and chemical resistance in itself, and a molding material reinforced with a reinforcing material such as glass fiber is , Is being used as a metal substitute in the fields of automobile parts and electronics-related parts,
In recent years, demand has greatly increased.

However, the unreinforced PAS resin which is not reinforced with a reinforcing material such as glass fiber is inferior in extrusion stability and moldability, and the obtained molded product is not only black and has a poor appearance but also has a high impact resistance. It lacks toughness due to insufficient mechanical properties such as mechanical properties and tensile elongation. Therefore, in the field of injection molding, the use as a non-reinforcing molding material is limited, and a material using a reinforcing material has been the mainstream.

[0004]

As a method for improving the toughness of a PAS resin typified by a PPS resin, a method of adding a hydrogenated SBR copolymer (JP-A-59-167040) and a dicarboxylic acid anhydride hydrogenated SBR copolymer are known. There is a method of adding (JP-A-56-115355), but these SBR
The system copolymer has poor compatibility with the PPS resin, has a poor appearance, and is not sufficiently improved in impact resistance. Further, the addition of an ionomer (Japanese Patent Laid-Open No. 2-49062) has a poor heat resistance of the ionomer and is apt to cause a burn during molding. Furthermore, α
-Addition of an olefin copolymer consisting of 70 to 99% by weight of olefin and 1 to 30% by weight of glycidyl ester of α, β-unsaturated acid (JP-A-58-154757), α-
Addition of a copolymer obtained by graft-polymerizing a vinyl monomer to a copolymer of an olefin and a glycidyl ester of an α, β-unsaturated acid (JP-A-1-198664), ethylene 50
.About.90% by weight, .alpha.,. Beta.-unsaturated carboxylic acid alkyl ester 5 to 49% by weight, and maleic anhydride 0.5 to 10% by weight added ethylene copolymer (JP-A-62-1)
51460) and the like. These copolymers have good compatibility with PAS resins, but when these copolymers are substantially added, the appearance is deteriorated, and the impact resistance and tensile elongation tend to be low. Further α-
When a large amount of a copolymer of an olefin and a glycidyl ester of an α, β-unsaturated acid was added to a PAS resin, the PAS resin became a gel and the amount used was limited.

[0005]

Therefore, the present inventors have improved mechanical properties such as impact resistance and tensile elongation of PPS resin without using a reinforcing material such as glass fiber.
It is intended to provide a high toughness PPS resin composition.

[0006]

Means for Solving the Problems In examining the improvement of impact resistance and tensile toughness of PAS resin, the present inventors have found that PAS resin contains a specific olefin copolymer and a specific thermoplastic resin. It has been found that the compounding of and improves the various properties of the above object in balance while maintaining the excellent heat resistance of the PAS resin, and the toughness is improved, thereby completing the present invention.

That is, the present invention provides (A) a polyarylene sulfide resin, (B) an α-olefin (1), and α, β.
-The ratio with the unsaturated carboxylic acid alkyl ester (2) is (1): (2) = 10 to 50% by weight: 50 to 90% by weight.
And the sum of these ((1) + (2)) 70 to 9
A glycidyl group-containing olefin copolymer in which the glycidyl ester (3) of an α, β-unsaturated acid is 0.5 to 30% by weight with respect to 9.5% by weight, and (C) other than (B) above. A thermoplastic resin composition comprising an olefin copolymer, an acrylic rubber, and one or more thermoplastic resins selected from hydrogenated polymers of conjugated dienes. is there.

The PAS resin (A) used as the substrate in the present invention has a general formula [-Ar-S-] (wherein -Ar- is a divalent aromatic group containing at least one carbon 6-membered ring). A polymer containing 70 mol% or more of the repeating unit represented by the formula (1), a typical substance thereof is [-φ-S-] (however,
-Φ- is a repeating unit represented by a phenylene group) 70
It is a PPS resin containing more than mol%.

PAS resins are generally known to have a substantially linear molecular structure having no branched or crosslinked structure and one having a branched or crosslinked structure depending on the production method.
In the present invention, both types are effective.

The preferred PAS resin for use in the present invention is the repeating unit [-φ-S-] (provided that-
φ- is phenylene group) PPS containing 70 mol% or more
It is a resin. When this repeating unit is 70 mol% or more, sufficient strength, which is a characteristic of a crystalline polymer, can be obtained, and toughness and chemical resistance are excellent.

Other copolymerizable structural units that may be contained in the PPS resin include, for example,

[0012]

[Chemical 1]

[0013]

[Chemical 2]

[0014]

[Chemical 3]

[0015]

[Chemical 4]

[0016]

[Chemical 5]

[0017]

[Chemical 6]

And the like. Of these, the trifunctional unit is 1
It is also preferable that the content is mol% or less from the viewpoint of not lowering the crystallinity.

In the present invention, a PPS resin having a sodium content of 1000 ppm or less is used as a more preferable PPS resin in order to sufficiently exert the effects of improving the toughness such as impact resistance and tensile elongation of the PPS resin. PPS with such a sodium content of 1000 ppm or less
Examples of the method for obtaining the resin include acid treatment, hot water treatment, organic solvent washing and the like. Known methods can be used as these methods. For example, the hot water treatment method described in JP-A No. 62-153344 and the organic solvent washing method described in JP-A No. 64-26670 can be mentioned, but the methods are not particularly limited to these.

Next, the glycidyl group-containing olefin copolymer (B) used as the component (B) in the present invention means the α-olefin (1) and the α, β-unsaturated alkyl carboxylate. The ratio with the ester (2) is (1) :( 2) = 10 to 50% by weight: 50 to 90% by weight
And the sum of these ((1) + (2)) 70 to 9
A glycidyl group-containing olefin-based copolymer in which the glycidyl ester (3) of an α, β-unsaturated acid is 0.5 to 30% by weight with respect to 9.5% by weight. The copolymer (B) is a random or / and block copolymer or / and a graft copolymer.

Here, as the α-olefin which is a monomer component of the copolymer (B), ethylene, propylene,
Butene-1,4-methylpentene-1, hexene-1,
One or more kinds selected from decene-1, octene-1, etc. are used. Ethylene is preferably used.

Further, the α, β-unsaturated carboxylic acid alkyl ester is an unsaturated carboxylic acid having 3 to 8 carbon atoms, for example, an alkyl ester such as acrylic acid or methacrylic acid, and specific examples thereof include Methyl acrylate,
Ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t acrylate
-Butyl, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-methacrylate
There are butyl, t-butyl methacrylate, isobutyl methacrylate, and the like. Of these, methyl acrylate, ethyl acrylate, and n-butyl acrylate are particularly preferably used. Further, these α, β-unsaturated carboxylic acid alkyl esters may be used alone or in combination of two or more.

Further, the glycidyl ester of α, β-unsaturated acid has the following general formula:

[0024]

[Chemical 7]

(Wherein R1 represents a hydrogen atom or a lower alkyl group), and for example, glycidyl acrylate, glycidyl methacrylate, and particularly glycidyl methacrylate are preferably used.

Further, these olefin copolymers (B)
As described above, the composition of α-olefin (1) and α,
The ratio with the β-unsaturated carboxylic acid alkyl ester (2) is (1) :( 2) = 10 to 50% by weight: 50 to 90% by weight, and the α, β-unsaturated carboxylic acid alkyl ester is in excess. , And the sum of these ((1) + (2)) 70-
It is formed by copolymerizing 0.5 to 30% by weight of glycidyl ester (3) of α, β-unsaturated acid with respect to 99.5% by weight. Preferably, (1) :( 2) = 20 to 45% by weight: 55 to 80% by weight, and the total of (1) + (2) 85 to 99% by weight, α, β-unsaturated acid 1 to 15% by weight of the glycidyl ester (3) is copolymerized. When the composition of the olefin-based copolymer (B) is within such a range, the PAS resin is not gelled and excellent in compatibility, and the heat resistance of the PAS resin is not impaired.

Next, the thermoplastic resin (C) used together with the above (A) and (B) will be described below.

The thermoplastic resin (C) used in the composition of the present invention is one or more selected from olefin copolymers other than the above (B), acrylic rubber, and hydrogenated polymers of conjugated dienes. It is the above thermoplastic resin.

The olefin copolymer other than the above (B) in this (C) is specifically a copolymer composed of α-olefin and α, β-unsaturated carboxylic acid alkyl ester, for example, α-. Copolymer consisting of 5 to 95% by weight of olefin and 5 to 95% by weight of α, β-unsaturated carboxylic acid alkyl ester, the α-olefin and α, β-
In addition to unsaturated carboxylic acid alkyl ester, unsaturated carboxylic acid or its acid anhydride is 10% by weight or less, preferably 1
An acid-modified copolymer having 8 to 8% by weight as an essential component; an acid group-containing olefin-based copolymer obtained by copolymerizing an α-olefin as a main component with an unsaturated carboxylic acid or an acid anhydride thereof as a modifier component, For example, an olefin-based copolymer such as an acid-modified copolymer obtained by copolymerizing an α-olefin (co) polymer with an unsaturated carboxylic acid or an acid anhydride thereof in an amount of 10% by weight or less, preferably 1 to 8% by weight; To be In addition, in such a copolymer, a small amount of a monomer other than the above-mentioned essential monomer components may be added within a range not departing from the gist of the present invention. The copolymer described here includes all of random copolymers, block copolymers, and graft copolymers.

As the α-olefin and the α, β-unsaturated carboxylic acid alkyl ester used in such an olefin-based copolymer, any of those described in the above (B) olefin-based copolymer can be used. α-
In the case of an acid group-containing olefin-based copolymer obtained by copolymerizing an olefin as a main component and an unsaturated carboxylic acid or an acid anhydride thereof as a modifier component, it is also preferable to use propylene in addition to ethylene as the α-olefin. .

The unsaturated carboxylic acid or its acid anhydride used as the modifier component includes acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, methylmaleic acid, methylfumaric acid, mesaconic acid, Examples include citraconic acid, glutaconic acid, monomethyl maleate, monoethyl maleate, monoethyl fumarate, methyl itaconate, methylmaleic anhydride, maleic anhydride, methylmaleic anhydride, citraconic anhydride, and the like. Used above. Although these derivatives can be used, maleic anhydride is more preferably used.

The acrylic rubber in (C) is
Specifically, for acrylic rubber 90 to 100% by weight,
0 to 10% by weight of unsaturated carboxylic acid or its acid anhydride
It is obtained by copolymerizing. Preferably, the acrylic rubber is copolymerized with 92 to 99% by weight and 1 to 7% by weight of an unsaturated carboxylic acid or an acid anhydride thereof is copolymerized. The acrylic rubber described here includes all of random type, block type, and graft type. Preferred as the acrylic rubber used in the present invention is the following general formula

[0033]

[Chemical 8]

(In the formula, R ₁ represents a hydrogen atom or a lower alkyl group, and R ₂ represents an alkyl group having 1 to 12 carbon atoms.)
Which is a copolymer obtained from a monomer unit containing an α, β-unsaturated carboxylic acid alkyl ester as a main component. Specifically, it is an unsaturated carboxylic acid having 1 to 12 carbon atoms, for example, an alkyl ester such as acrylic acid or methacrylic acid, and specific examples include methyl acrylate,
Ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t acrylate
-Butyl, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-methacrylate
There are butyl, t-butyl methacrylate, isobutyl methacrylate, and the like. Of these, methyl acrylate, ethyl acrylate, and n-butyl acrylate are particularly preferably used. Two or more kinds of these α, β-unsaturated carboxylic acid alkyl esters are mainly used. .

Examples of the unsaturated carboxylic acid or its acid anhydride which may be copolymerized with the acrylic rubber include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, methylmaleic acid and methylfumaric acid. acid,
Mesaconic acid, citraconic acid, glutaconic acid, monomethyl maleate, monoethyl maleate, monoethyl fumarate, methyl itaconate, methylmaleic anhydride, maleic anhydride, methylmaleic anhydride, citraconic anhydride, etc. Or used in two or more kinds. Although these derivatives can be used, maleic anhydride is more preferably used.

The amount of the unsaturated carboxylic acid or its acid anhydride used is preferably 0.5 to 10% by weight, more preferably 1 to 7% by weight.

Next, the hydrogenated polymer of the conjugated diene in (C) is a hydrogenated polymer of the conjugated diene or a hydrogenated copolymer of the conjugated diene and the aromatic vinyl hydrocarbon, and preferably the conjugated It is preferable that the hydrogenated (co) polymer of a diene is further reacted with an unsaturated carboxylic acid or its acid anhydride and a glycidyl ester of an α, β-unsaturated acid. The reaction amount of the unsaturated carboxylic acid or its acid anhydride and the glycidyl ester of the α, β-unsaturated acid is 0.01 to 10 parts by weight with respect to 100 parts by weight of the hydrogenated (co) polymer of the conjugated diene. is there.

The hydrogenated polymer of a conjugated diene as used herein means a polymer derived from at least one conjugated diene monomer, that is, a single conjugated diene such as 1,3-butadiene homopolymer or two or more thereof. The above conjugated dienes, for example 1,
3-butadiene, isoprene, 2,3-dimethyl-1,
At least 80 of the unsaturated content of the copolymer of 3-butadiene, 1,3-butadiene and 1,3-pentadiene
% Refers to the one reduced by hydrogenation (hydrogenation).

The hydrogenated copolymer of conjugated diene and aromatic vinyl hydrocarbon means that the unsaturated content of the block copolymer or random copolymer having various ratios of conjugated diene and aromatic vinyl hydrocarbon is different. At least 80% refers to those that have been reduced by hydrogenation. in this case,
A block copolymer of a conjugated diene and an aromatic vinyl hydrocarbon is preferably used. The double bond of the aromatic nucleus is excluded from the target of unsaturated bond that is reduced by hydrogenation.

The conjugated diene used as a raw material for hydrogenated polymers and hydrogenated copolymers is 1,3-butadiene, isoprene and 1,3-pentadiene, preferably 1,3-butadiene and isoprene. .

Aromatic vinyl hydrocarbons used as raw materials for hydrogenated copolymers include styrene, α-methylstyrene, O-methylstyrene, P-methylstyrene, 1,3.
-Dimethylstyrene and vinylnaphthalene, and styrene is preferably used.

Among the hydrogenated (co) polymers, preferred specific examples are hydrogenated polybutadiene, styrene / butadiene / styrene triblock hydrogenated copolymers, styrene / isoprene /
Styrene triblock hydrogenated copolymers and the like, and among them, styrene / butadiene / styrene triblock hydrogenated copolymers and styrene / isoprene / styrene triblock hydrogenated copolymers are preferably used from the viewpoint of heat resistance.

As the unsaturated carboxylic acid or its acid anhydride or the glycidyl ester of the α, β-unsaturated acid used as the modifier of the hydrogenated (co) polymer of the conjugated diene, any of those described above is used. it can.

In the composition of the present invention, first, the PAS resin (A) and the glycidyl group-containing olefin copolymer (B) are used.
The use ratio of (A) is 60 to 99% by weight (B) 1 to 4
0% by weight, preferably 80 to 92% by weight of (A) and 2 to 20% by weight of (B). Further, the addition amount of the thermoplastic resin (C) is 10 to 9 which is the total amount of (A) and (B).
It is preferably 10 to 90% by weight with respect to 9% by weight.

In the present invention, the epoxy curing catalyst (D) can be used for the purpose of further enhancing the reactivity between the PPS resin and the glycidyl group-containing polyolefin resin.

As the epoxy curing catalyst (D) used in the composition of the present invention, known ones are used, but tertiary amine, quaternary ammonium salt and tertiary phosphine are preferable. Examples include triphenyl phosphate, dimethyllaurylamine, dimethylstearylamine, N-butylmorpholine, N, N-dimethylcyclohexylamine, benzyldimethylamine, pyridine, dimethylamino-4-pyridine, methyl-1-imidazole, tetramethyi. Ruethylenediamine, tetramethyleneguanidine, triethylenediamine, tetramethylenehydrazine, N, N-dimethylpiperazine, tetramethylammonium chloride, benzyltrimethylammonium chloride, tetra-N-butylammonium bromide, tetramethylammonium bromide, tetraethylammonium bromide, cesyltrimethylammonium Examples thereof include bromide and tetrapropylammonium bromide.

The addition amount of the epoxy resin curing catalyst (D) is
The total amount of (A), (B) and (C) is 98 to 99.9.
It is 0.01 to 2% by weight with respect to 9% by weight.

Further, in the present invention, an isocyanate compound, an isocyanurate compound, a bisoxazoline compound for the purpose of increasing the compatibility of the PAS resin (A), the glycidyl group-containing olefinic copolymer (B) and the thermoplastic resin (C). , Epoxy resin, epoxy group-containing polymer, oxazoline group-containing polymer and the like may be blended.

Furthermore, if necessary, the composition of the present invention may contain the following reinforcing material and / or filler. Examples of these reinforcing materials and / or fillers include powdery, flat, scale-like, needle-like, spherical or hollow and fibrous forms. Specifically, calcium sulfate, calcium silicate, clay, talc, alumina, silica sand, glass powder, metal powder, graphite, silicon carbide, silicon nitride, silica, boron nitride, aluminum nitride,
Granular filler such as carbon black, mica, glass plate, sericite, metal foil such as aluminum flake, flat or scale-like filler such as graphite, shirasu balloon, metal balloon, hollow filler such as glass balloon, Examples thereof include organic fibrous fillers such as glass fibers, carbon fibers, graphite fibers, whiskers, metal fibers, asbestos, wosnite, fibrous fillers and aromatic polyamide fibers.

Further, other thermoplastic resins may be added to the composition of the present invention within a range not departing from the gist of the present invention. Other thermoplastic resins include polyethylene, polypropylene, polystyrene, imide-modified polystyrene, polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyamide, polycarbonate, ABS resin. , Imide-modified ABS resin, AES resin,
Polysulfone, polyphenylene ether, copolymer and / or mixture of polyphenylene ether and polystyrene, thermoplastic resin such as polyethersulfone, polysulfide ketone, polysulfide sulfone, polyether ether ketone, polyamideimide, polyester system, Examples include thermoplastic elastomers such as polyamide type, polyurethane type, polyolefin type and polystyrene type. Preferably, polypropylene, polybutylene terephthalate, polyamide, polyphenylene ether,
It is a copolymer and / or mixture of polyphenylene ether and polystyrene.

In the present invention, an inorganic flame retardant such as magnesium hydroxide, aluminum hydroxide and antimony trioxide, a halogen-based compound, a halogen-based compound, and
Additives such as phosphorus-based organic flame retardants, antioxidants, UV inhibitors, lubricants, dispersants, coupling agents, foaming agents, cross-linking agents, and coloring agents can be added.

As a method for producing the composition of the present invention, a general method is used. The most general method is to uniformly mix the compound with a suitable mixer such as a tumbler, a Henschel mixer, a tumbler, etc., and supply the mixture to an extruder for melt-kneading.
The extruded product in the form of a strand is cooled and cut into a product for a molding material. More simply, a method of melting and kneading the compound of the present invention directly in a molding machine and omitting the extrusion step may be used, but the method is not particularly limited thereto.

[0053]

The present invention will be further described with reference to examples.

Measurement of Melt Index (MI) After drying about 6 g of a sample at 120 ° C. for 3 hours, a predetermined temperature (315.6 ° C.) was set using an orifice having a diameter of 2.096 mm and a length of 8.001 mm. It is put into a melt indexer (T01 type manufactured by Toyo Seiki Co., Ltd.) to remove air bubbles, apply a predetermined load (5000 g), preheat for 5 minutes, and then measure.

[0055] Tensile conduct a tensile test under the following conditions and the resulting tensile test dumbbell by testing injection molding.

Measuring instrument Shimadzu Autograph IS-2000 Pulling speed 10 mm / min Distance between marked lines 25 mm Distance between grips 50 mm

Izod Impact Test A test piece for measuring Izod impact value obtained by injection molding is subjected to a tensile test under the following conditions.

Test piece dimensions Length 63.5 mm x width 1
2.7mm × thickness 3.17mm Cutting notch measuring device Universal impact tester Universal type Toyo Seiki hammer load 30Kg-cm

Examples 1 to 4, Comparative Examples 1 to 5 As PAS resin (A), a substantially linear PPS resin having MI of 300 g / 10 min and a sodium content of 235 ppm, glycidyl methacrylic acid 2.3 wt. %, Methyl acrylate 59% by weight, ethylene 38.7% by weight, glycidyl group-containing olefinic copolymer (B),
As the thermoplastic resin (C), an olefinic copolymer composed of 85% by weight of ethylene and 15% by weight of ethyl acrylate was used, and blended by using a tumbler with the composition shown in Table 1. Then, the mixture was kneaded with a twin-screw extruder (TEM-35B manufactured by Toshiba Machine Co., Ltd.) having a barrel temperature of 290 ° C., and the extruded strand was cooled and solidified, and then pelletized. After drying the obtained pellets at 120 ° C. for 4 hours,
Molded with an injection molding machine (IS-50AM: Toshiba Machine Co., Ltd.) at a cylinder temperature of 290 ° C. and a mold temperature of 120 ° C., and a tensile test dumbbell (ASTM IV thickness 1.6 m.
m) and Izod test specimens were obtained. A tensile test and an Izod test were performed using this test piece.
The results are shown in Table-1.

As is clear from the results, the glycidyl group-containing olefin-based copolymer (B) alone becomes a gel when used in a large amount, but the present invention does not thicken and the physical properties do not deteriorate.

[0061]

[Table 1]

Examples 5 to 8 and Comparative Examples 6 to 8 The PAS resin (A) and the glycidyl group-containing olefin copolymer (B) used are the same as in Example 1, and the thermoplastic resin (C) is used. Is an acid group-containing olefinic copolymer composed of maleic anhydride 2.0% by weight, ethyl acrylate 31% by weight, and ethylene 67% by weight, mixed in the composition shown in Table 2 and treated in the same manner as in Example 1. Pelletization and injection molding were performed, and physical properties were measured. The results are shown in Table-2.
Shown in. As is clear from the results, the composition of the present invention has excellent tensile elongation and impact resistance.

[0063]

[Table 2]

Examples 9 to 12, Comparative Examples 9 to 11 The PAS resin (A) and the glycidyl group-containing olefinic copolymer (B) used are the same as in Example 1, and the thermoplastic resin (C) is used. The ethylene-propylene rubber containing 1.8% by weight of maleic anhydride was mixed in the composition shown in Table 3, and the physical properties were measured in the same manner as in Example 1. The results are shown in Table-3. As is clear from the results, the composition of the present invention is excellent in impact resistance and elongation and has a good surface condition.

[0065]

[Table 3]

Examples 13 to 16 and Comparative Examples 12 to 14 The PAS resin (A) and the glycidyl group-containing olefin copolymer (B) used are the same as in Example 1, and the thermoplastic resin (C) is used. The acrylic rubber containing 1.8% by weight of maleic anhydride was mixed in the composition shown in Table 4, and the physical properties were measured in the same manner as in Example 1. Table of results
4 shows.

[0067]

[Table 4]

Examples 17 to 20, Comparative Examples 15 to 17 The PAS resin (A) and the glycidyl group-containing olefin copolymer (B) used are the same as in Example 1, and the thermoplastic resin (C) is used. A hydrogenated styrene-budadiene copolymer containing 30% by weight of styrene and 70% by weight of butadiene was reacted with 1.8% by weight of maleic anhydride to use a hydrogenated styrene-butadiene copolymer containing an acid group.
The mixture was mixed in the composition shown in Example 5, and the physical properties were measured in the same manner as in Example 1. The results are shown in Table-5.

[0069]

[Table 5]

Examples 21 to 27 As the PPS resin (A), a substantially linear PPS resin having an MI of 20 to 30 g / 10 minutes and a sodium content shown in Table 6 was used. The same olefin copolymer (B) as that used in Example 1 and the same thermoplastic resin (C) as that used in Example 5 are used, as well as those using an epoxy curing catalyst.
Were mixed in the proportions shown in, and the physical properties were measured in the same manner as in Example 1.

[0071]

[Table 6]

[0072]

INDUSTRIAL APPLICABILITY The composition of the present invention is superior in impact resistance and tensile elongation to the conventional PAS resin composition, and is thickened,
It can be molded without gelation and has excellent moldability. For this reason, it can be used as it is as various functional parts without any particular reinforcement with reinforcing materials. For example, injection molded products are automobile parts, electric machines, electronic parts, sealing materials, and extrusion molded products are irregularly shaped. It is useful as a material for extrusion, tubes, hoses, pipes, fibers, films and the like.

Claims (11)

[Claims] 1. The ratio of (A) polyarylene sulfide resin to (B) α-olefin (1) and α, β-unsaturated carboxylic acid alkyl ester (2) is (1):
(2) = 10 to 50% by weight: 50 to 90% by weight,
Further, the glycidyl group-containing olefin in which the glycidyl ester (3) of the α, β-unsaturated acid is 0.5 to 30% by weight based on 70 to 99.5% by weight of the total of these ((1) + (2)). -Based copolymer and (C) one or more thermoplastic resins selected from the group consisting of olefin-based copolymers other than (B), acrylic rubber, and hydrogenated polymers of conjugated dienes A thermoplastic resin composition comprising: 2. The olefin copolymer in (C) comprises an α-olefin and an α, β-unsaturated carboxylic acid alkyl ester as an essential monomer component, and further an unsaturated carboxylic acid or an acid anhydride thereof as a modifier component. The composition according to claim 1, which is an α-olefin copolymer which may be copolymerized. 3. The composition according to claim 2, which is an olefin-based copolymer obtained by copolymerizing an unsaturated carboxylic acid or an acid anhydride thereof. 4. An olefin-based copolymer of (C), which comprises an α-olefin as a main component and is copolymerized with an unsaturated carboxylic acid or an acid anhydride thereof as a modifier component. The composition of claim 1 which is 5. The composition according to claim 1, wherein the acrylic rubber in (C) is an acrylic rubber obtained by copolymerizing an unsaturated carboxylic acid or an acid anhydride thereof. 6. The composition according to claim 1, wherein the hydrogenated polymer of the conjugated diene in (C) is a hydrogenated polymer of a conjugated diene or a hydrogenated copolymer of a conjugated diene and an aromatic vinyl hydrocarbon. 7. The hydrogenated polymer of a conjugated diene in (C) is obtained by reacting an unsaturated carboxylic acid or an acid anhydride thereof, and a glycidyl ester of an α, β-unsaturated acid with a hydrogenated (co-modified conjugated diene. ) The composition according to claim 1 or 6, which is a polymer. 8. The sodium content of the polyarylene sulfide resin (A) is 1000 ppm or less.
The composition as described. 9. A thermoplastic resin composition comprising an epoxy resin curing catalyst (D) in addition to the components (A), (B) and (C) described above. 10. The resin composition according to claim 9, wherein the epoxy resin curing catalyst (D) is a tertiary amine. 11. The epoxy resin curing catalyst (D) is added in a total amount of 98 to 9 (A), (B) and (C).
The composition according to claim 9, which is 0.01 to 2% by weight with respect to 9.99% by weight.