JPH09302215A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition excellent not only in moldability, flame retardancy, and heat resistance but also in mechanical properties including tensile strength, flexural strength, modulus in flexure, and impact strength and to provide a molding made from the composition. SOLUTION: This composition comprises 100 pts.wt. resin blend consisting of 10-90 pts.wt. polyphenylene ether resin and 90-10 pts.wt. polyphenylene sulfide resin and 0.1-20 pts.wt. block copolymer. The copolymer comprises one or more polymer blocks (A) consisting of 30-100mol% units derived from an aromatic vinyl monomer and 70-0mol% units derived from a vinyl monomer copolymerizable therewith and one or more polymer blocks (B) consisting of 0.1-100mol% units derived from a vinyl monomer having at least one functional group selected among carboxyl, epoxy, and carboxylic anhydride groups and 99.9-0mol% units derived from a vinyl monomer copolymerizable therewith. A molding is formed from the composition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition comprising a polyphenylene ether resin, a polyphenylene sulfide resin and a block copolymer having a specific functional group, and a molded article comprising the thermoplastic resin composition. Regarding The thermoplastic resin composition of the present invention is excellent in moldability, flame retardancy, heat resistance, mechanical properties, etc.,
It can be suitably used as a molding material for industrial materials, industrial materials, household products and the like.

[0002]

2. Description of the Related Art Polyphenylene sulfide resins are excellent in heat resistance, flame retardancy, chemical resistance, etc., but their melting temperature is as high as 300 to 350 ° C., so that they are extremely inferior in moldability. In order to improve this drawback, attempts have been made to blend various resins with the polyphenylene sulfide resin. For example, JP-A-50-156561
The publication describes that a resin composition having good moldability was obtained by blending a polyphenylene sulfide resin with a polyphenylene ether resin.

[Problems to be Solved by the Invention]

However, since the polyphenylene sulfide resin and the polyphenylene ether resin are essentially incompatible, tensile strength and bending strength can be obtained by simply blending these resins as in JP-A-50-156561. Only those with significantly inferior mechanical properties such as flexural modulus and impact strength can be obtained.

[0004] An object of the present invention is to provide a thermosetting material having not only excellent moldability, flame retardancy and heat resistance but also excellent mechanical properties such as tensile strength, flexural strength, flexural modulus and impact strength. An object of the present invention is to provide a thermoplastic resin composition and a molded article comprising the thermoplastic resin composition.

[0005]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that a polymer block (A) containing 30 mol% or more of an aromatic vinyl monomer unit, A block copolymer composed of a polymer block (B) containing 0.1 to 100 mol% of a vinyl monomer unit having at least one functional group selected from a carboxyl group, an epoxy group and a carboxylic acid anhydride group. By blending the coalesce in a specific amount in a resin mixture consisting of a polyphenylene sulfide-based resin and a polyphenylene ether-based resin, the compatibility of both resins is significantly improved, and the properties of both resins are sufficiently expressed. Heading, completed the present invention.

That is, the present invention is based on 100 parts by weight of a resin mixture consisting of 10 to 90 parts by weight of a polyphenylene ether resin (I) and 90 to 10 parts by weight of a polyphenylene sulfide resin (II). A polymer block (A) comprising 30 to 100 mol% of a monomer unit and 70 to 0 mol% of a vinyl-based monomer unit copolymerizable therewith, and selected from a carboxyl group, an epoxy group and a carboxylic acid anhydride group. From a polymer block (B) comprising 0.1 to 100 mol% of a vinyl monomer unit having at least one kind of functional group and 99.9 to 0 mol% of a vinyl monomer unit copolymerizable therewith The present invention relates to a thermoplastic resin composition containing 0.1 to 20 parts by weight of the constituent block copolymer (III). Further, the present invention relates to a molded article comprising the above-mentioned thermoplastic resin composition.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The polyphenylene ether resin (I) used in the present invention is a polymer having a phenylene ether unit, and examples thereof include poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,6-dimethyl-1,4-phenylene) ether. (2-methyl-
6-ethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether,
Poly (2, ethyl-6-npropyl-1,4-phenylene) ether, poly (2-methyl-6-nbutyl-1,
4-phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-phenylene) ether, poly (2
-Methyl-6-chloro-1,4-phenylene) ether, poly (2-methyl-6-hydroxyethyl-1,4)
-Phenylene) ether, poly (2-methyl-6-chloroethyl-1,4-phenylene) ether and the like can be mentioned, and of these, one kind or two or more kinds can be used.

The polyphenylene sulfide resin (II) used in the present invention contains the structural unit represented by the following general formula (1) in an amount of 70 mol% or more, more preferably 90 mol% or more, based on the total structural units. The following general formulas (2) to (8) are used as long as the crystallinity and stretch orientation of the resin are not impaired (usually 30 mol% or less relative to all structural units). ) May be included in the structural unit.

[0009]

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[0010]

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[0011]

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[0012]

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[0013]

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[0014]

[Chemical 6]

[0015]

[Chemical 7]

[0016]

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[In the formula, R represents a metal salt of an alkyl group, a nitro group, an alkoxy group, a carboxyl group, or a carboxyl group]

The block copolymer (II) used in the present invention
I) is composed of a polymer block (A) and a polymer block (B) described below. For example, an AB type diblock copolymer, an ABA type triblock copolymer,
Examples thereof include BAB type triblock copolymers. Of these, AB type diblock copolymers are preferable.

The block copolymer (II) used in the present invention
The polymer block (A) constituting I) contains an aromatic vinyl monomer unit in an amount of 30 to 100 mol%, preferably 55 to 100 mol%, based on all structural units. Preferably, it is contained in an amount of 70 to 100 mol%, more preferably 95 to 100 mol%. As the aromatic vinyl monomer unit, for example,
Styrene; α-methylstyrene, p-methylstyrene,
Examples thereof include units derived from alkyl-substituted styrenes such as p-tert-butylstyrene and 3,4-dimethylstyrene; halogen-substituted styrenes such as chlorostyrene, and one or more of them are used. You can Of these, units derived from styrene are preferred.

As the structural unit of the polymer block (A),
If necessary, 70 mol% or less, preferably 45 mol% or less, more preferably 30 mol% or less, and still more preferably 5 mol%, of a vinyl monomer unit copolymerizable with an aromatic vinyl monomer. The following ratio may be included. Examples of the vinyl monomer unit copolymerizable with the aromatic vinyl monomer include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, Examples include units derived from N, N-dimethylacrylamide and the like.

The block copolymer (II) used in the present invention
The polymer block (B) constituting I) includes a vinyl monomer unit having at least one functional group selected from a carboxyl group, an epoxy group and a carboxylic anhydride group,
The content is 0.1 to 100 mol%, preferably 0.1 to 50 mol%, based on all structural units,
More preferably, the content is 0.1 to 30 mol%.

Examples of the vinyl monomer unit having a carboxyl group include units derived from acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, itaconic acid, maleic acid and the like. One or two or more of them can be used. Of these, units derived from acrylic acid and methacrylic acid are preferred.

Examples of the vinyl monomer unit having an epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl itaconate, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-p-glycidyl ether, and 3,4. −
Epoxybutene, 3,4-epoxy-3-methyl-1-
Units derived from butene, 3,4-epoxy-3-methyl-1-pentene, 5,6-epoxy-1-hexene, vinylcyclohexene monoxide, p-glycidylstyrene and the like can be mentioned. One or more kinds can be used. Among these, units derived from glycidyl acrylate and glycidyl methacrylate are preferable.

Examples of the vinyl monomer unit having a carboxylic anhydride group (—CO—O—CO—) include maleic anhydride, itaconic anhydride, citraconic anhydride, butenyl succinic anhydride, and tetrahydrophthalic anhydride. And the like. One or more of these units can be used. Among these, units derived from maleic anhydride are preferred.

The polymer block (B) may be, if necessary,
A vinyl monomer unit copolymerizable with the vinyl monomer unit having the above functional group is used in an amount of 0 to 9 with respect to all structural units.
9.9 mol%, preferably 50 to 99.9 mol%, more preferably 70 to 99.9 mol% can be contained. Examples of the vinyl monomer units that can be used in combination include styrene monomers such as styrene, p-styrenesulfonic acid, and sodium and potassium salts thereof; (meth) acrylonitriles; vinyl acetate, vinyl pivalate, and the like. Vinyl esters; (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) (Meth) acrylic acid such as 2-hydroxyethyl acrylate and its esters; (meth) acrylamide; units derived from N-vinyl-2-pyrrolidone; The above can be used. Of these, units derived from methyl acrylate, methyl methacrylate, styrene, and acrylonitrile are preferred.

The number average molecular weight of the polymer block (A) is
It is preferably from 1,000 to 100,000,
More preferably, it is 500 to 50,000. The number average molecular weight of the polymer block (B) is 1,000 to 10
0000, preferably 2,500 to 50,000.
More preferably, it is 00. Block copolymer (II
The number average molecular weight of I) is preferably from 2,000 to 200,000, and more preferably from 5,000 to 100,000. When the polymer block (A), the polymer block (B) and the block copolymer (III) having a number average molecular weight within the above range are used, the polyphenylene ether resin (I) and the polyphenylene sulfide resin are used. A thermoplastic resin composition having very excellent compatibility with (II) is obtained, and the excellent properties originally possessed by each resin are sufficiently expressed, which is preferable. In addition, the number average molecular weight referred to in the present specification is a value determined from a standard polystyrene calibration curve by gel permeation chromatography (GPC).

The method for producing the block copolymer (III) is not particularly limited. For example, a monomer component constituting the polymer block (A) [or the polymer block (B)] is converted to thio-S Radical polymerization in the presence of a compound containing a thioester group and a mercapto group in the molecule such as carboxylic acid, 2-acetylthioethylthiol, and 10-acetylthiodecanethiol, and the obtained polymer is subjected to sodium hydroxide, ammonia And a polymer having a mercapto group at one end by treatment with an alkali such as hydrochloric acid, sulfuric acid, or the like. In the presence of the polymer, a polymer block (B) [or a polymer block (A) The method for producing a block copolymer (III) by radical polymerization of a monomer component constituting the above copolymer has a desired number average molecular weight and molecular weight distribution. It preferred because the lock copolymer can be produced easily and efficiently.

The thermoplastic resin composition of the present invention is obtained by blending the block copolymer (III) with a resin mixture comprising the above polyphenylene ether resin (I) and polyphenylene sulfide resin (II). To be
The compounding ratio of the polyphenylene ether resin (I) in the resin mixture is 10 to 90 parts by weight, and 30 to 30 parts by weight.
Preferably it is 90 parts by weight. The blending ratio of the polyphenylene sulfide resin (II) is 90 to 10 parts by weight, preferably 70 to 10 parts by weight. The block copolymer (III) is blended in proportions of polyphenylene ether resin (I) and polyphenylene sulfide resin (II).
0.1 to 100 parts by weight of the resin mixture consisting of
20 parts by weight, preferably 1.0 to 10 parts by weight. When the blending ratio of the block copolymer (III) exceeds 20 parts by weight, the heat resistance of the obtained thermoplastic resin composition decreases. On the other hand, when the amount is less than 0.1 parts by weight,
Since the compatibility of the polyphenylene ether resin (I) and the polyphenylene sulfide resin (II) is not improved,
The obtained resin composition is inferior in mechanical properties and the like.

The thermoplastic resin composition of the present invention comprises the above polyphenylene ether resin (I), polyphenylene sulfide resin (II) and block copolymer (III).
Is an essential component, but may contain other components as necessary. Examples of other optional components include compounds having an action of promoting the reaction between the functional group (carboxyl group, epoxy group, carboxylic acid anhydride group) of the block copolymer (III) and the polyphenylene sulfide resin (II). Can be mentioned. By adding the compound,
A thermoplastic resin composition having more excellent mechanical properties can be obtained. In particular, even if the amount of the block copolymer (III) used is reduced, the mechanical properties of the thermoplastic resin composition can be sufficiently improved. Examples of the compound include tertiary amines such as triphenylamine and 2,4,6-tris (dimethylaminomethyl) phenol; tetrabutylammonium fluoride, triethylbenzylammonium chloride, tetramethylammonium chloride, trioctylammonium chloride. , Tributylbenzylammonium chloride,
N-laurylpyridinium chloride, tetramethylammonium bromide, tetraethylammonium bromide, -n-bromide
Ammonium compounds such as butylammonium; Phosphorous acid esters such as triphenylphosphite and triisodecylphosphite; Alkyltriphenylphosphonium halogen compounds (for example, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, etc.), Phosphonium compounds such as alkenyltriphenylphosphonium halogen compounds and tetraalkylphosphonium halogen compounds (eg, tetrabutylphosphonium bromide); tertiary phosphines such as triphenylphosphine; sodium dodecylbenzene sulfonate;
Examples thereof include sulfonic acid metal salts such as sodium 3,5-dicarbomethoxybenzenesulfonate; sulfuric acid esters such as sodium lauryl sulfate. Usually, the compounding ratio of the above compound is preferably about 0.001 to 0.1 part by weight with respect to 100 parts by weight of the polyphenylene sulfide resin (II).

The thermoplastic resin composition of the present invention contains, in addition to the above-mentioned compounds, a pigment, a nucleating agent, an antioxidant, if necessary.
Thermal deterioration inhibitor, ultraviolet absorber, anti-blocking agent,
Additives such as lubricants; fibrous fillers such as glass fiber, carbon fiber and polyamide fiber; powdery fillers such as silica, aluminum hydroxide, calcium carbonate, talc, mica, titanium oxide, carbon black, potassium titanate; It may contain another polymer or the like.

As the above-mentioned other polymer, for example, polyolefin resin such as polyethylene; polycarbonate resin, etc. can be used. In the present invention, however, it is melt flowable with respect to the polyphenylene ether resin (I). In some cases, it is effective to use a styrene resin in order to improve molding processability such as properties and impact resistance.

The above-mentioned styrene resin is a polymer of monomers containing styrene as a main component.
Other monomers copolymerizable with styrene may be used, provided that the amount is usually 50% by weight or less, preferably 40% by weight or less. Examples of other copolymerizable monomers include α
-Methylstyrene, vinyltoluene, vinylethylbenzene, vinylxylene, pt-butylstyrene, α-
Aromatic monovinyl compounds such as methyl-p-methylstyrene and vinylnaphthalene; Vinyl cyanide compounds such as acrylonitrile; Methacrylic acid esters such as methyl methacrylate; Acrylic acid esters such as methyl acrylate; Methacrylic acid, acrylic acid, fumar Unsaturated carboxylic acids such as acids; unsaturated dicarboxylic acid anhydrides such as maleic anhydride; unsaturated dicarboxylic acid imides such as phenylmaleimide; unsaturated carboxylic acid amides such as acrylamide; and the like. Or 2
More than one species can be used. As typical examples of the styrene resin, polystyrene resin, rubber-reinforced polystyrene resin, styrene-butadiene-acrylonitrile copolymer (ABS resin), methyl methacrylate-butadiene-
Examples thereof include styrene copolymer (MBS resin) and styrene-acrylonitrile copolymer (AS resin). The rubber-reinforced polystyrene resin can be industrially produced by dissolving a rubber-like polymer in a styrene monomer and polymerizing it by a method such as a bulk polymerization method or a bulk suspension polymerization method. The type of the rubber-like polymer is not particularly limited, and those conventionally used for rubber-modified styrene resins such as natural rubber; styrene-isoprene copolymer rubber, butyl rubber, ethylene-propylene copolymer rubber, etc. Or a graft copolymer rubber of these rubbers and styrene can be used. The mixing ratio of the styrene resin is preferably 25 to 400 parts by weight with respect to 100 parts by weight of the polyphenylene ether resin (I).

As a method of blending the styrene resin with the thermoplastic resin composition of the present invention, a composition with the polyphenylene ether resin (I) is prepared in advance, and the composition is treated with the polyphenylene sulfide resin (II) and A method of mixing with the block copolymer (III); any method such as a method of mixing the styrene resin with the polyphenylene ether resin (I), the polyphenylene sulfide resin (II) and the block copolymer (III) at the same time. Can be adopted.

The thermoplastic resin composition of the present invention comprises the above polyphenylene ether resin (I), polyphenylene sulfide resin (II), block copolymer (III) and, if necessary, the above-mentioned other components. Can be produced by a usual polymer blending method. For example, single screw extruder, twin screw extruder, Brabender,
Melt kneading may be performed using a melt kneader such as a kneader or a Banbury mixer, or simply dry blending may be performed. When the thermoplastic resin composition is produced by melt-kneading, the reaction between the functional group of the block copolymer (III) and the polyphenylene sulfide resin (II) proceeds, and the polyphenylene ether in the resulting thermoplastic resin composition is One of the resin (I) and the polyphenylene sulfide resin (II) is preferably dispersed in the matrix of the other resin in a finely dispersed state so that good mechanical properties are easily exhibited. Furthermore, when the compound having the function of promoting the reaction between the functional group of the block copolymer (III) and the polyphenylene sulfide resin (II) is allowed to coexist during the melt-kneading, the block is mixed during the kneading. It is preferable because the reaction between the functional group of the copolymer (III) and the polyphenylene sulfide resin (II) is further promoted, and a thermoplastic resin composition having better mechanical properties can be obtained. Melt kneading conditions are not particularly limited,
Usually, kneading may be performed at a temperature of about 250 to 300 ° C. for about 3 to 30 minutes.

The thermoplastic resin composition of the present invention can be melt-molded and heat-processed, and various molded products can be smoothly produced by any molding method such as injection molding, extrusion molding, inflation film molding, blow molding and the like. can do.

The thermoplastic resin composition of the present invention is, for example,
Power tools, general industrial parts, gears, cams and other mechanical parts, automotive interior and exterior parts, automotive electrical components, automotive engine parts and other automotive related parts, home appliances and OA
It is useful as a molding material for various applications such as housing parts for equipment or electronics-related parts.

[0037]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the following Examples and Comparative Examples, tensile strength, bending strength, flexural modulus, Izod impact strength, peelability of molded articles, heat deformation temperature, and flame retardancy were measured or evaluated by the following methods.

[Tensile Strength] The tensile strength was measured according to ASTM D638.

[Bending Strength, Flexural Modulus] ASTM D7
Measured according to 90.

[Izod Impact Strength] ASTM D25
6 (notched).

[Releasability of molded product] 10 mm × 30 mm ×
Bending a 2mm plate-shaped test piece
Nothing was observed. If the compatibility between the resins is poor, peeling occurs.

[Heat Deformation Temperature] It was measured according to ASTM D648 (load: 18.6 kg / cm ² ).

[Flame Retardancy Test] VB based on UL-94
The degree of flame retardancy (V-0 rank, V-1 rank) of each test piece was evaluated by the (Vertical Burning) method.

Reference Example 1 [Synthesis of Block Copolymer Containing Carboxyl Group] 75 kg of styrene was charged into a 90-liter polymerization tank, and the temperature was raised to 90 ° C. under a nitrogen atmosphere. After 30 minutes, 32 g of thio-S-acetic acid was added into the polymerization tank, and a radical polymerization initiator (V-65, manufactured by Wako Pure Chemical Industries, Ltd., 7 g) was immediately added.
Wt% toluene solution) at a rate of 430 ml / hour,
Further, thio-S-acetic acid (6% by weight toluene solution) was added to 7
It was added to the polymerization tank at a rate of 50 ml / hour to initiate polymerization. When the polymerization rate (polymer conversion rate) reached 40%, the polymerization was stopped and the internal temperature was cooled. By removing the solvent and the unreacted monomer of the obtained viscous liquid, a number average molecular weight of 1 having a thio-S-acetate group at a terminal is obtained.
1,000 polystyrenes were obtained. This polystyrene 3
0 kg, 30 kg of toluene and 15 kg of butanol were charged into a 90-liter reaction vessel, and heated to 70 ° C. under a nitrogen atmosphere.
10% by weight sodium hydroxide / methanol solution 13
5 ml was added, and a transesterification reaction of the thio-S-acetic acid ester group at the polystyrene end was performed. Two hours later, 30 g of acetic acid was added to the reaction vessel to complete the reaction. The solvent was distilled off from the obtained reaction solution to obtain polystyrene having a mercapto group at the terminal. 28.2 kg of methyl methacrylate, 1.8 kg of methacrylic acid, toluene 4
8 kg and 30 kg of polystyrene having a mercapto group at the end were charged into a 200-liter polymerization tank, and the inside thereof was sufficiently purged with nitrogen at 90 ° C., and then a radical polymerization initiator (V-
65, 10% by weight toluene solution manufactured by Wako Pure Chemical Industries, Ltd.)
Was added to the polymerization vessel at a rate of 54 ml / hour to initiate polymerization. When the polymerization rate (polymer conversion rate) reaches 95%, the polymerization is stopped, and a polystyrene block (A) and a methyl methacrylate-methacrylic acid copolymer (methyl methacrylate: methacrylic acid = 94: 6 (molar ratio)) block. An AB-type diblock copolymer (hereinafter, referred to as block copolymer 1) composed of (B) was obtained. The number average molecular weight of the polymer block (A) of the obtained block copolymer 1 was 11,000, the number average molecular weight of the polymer block (B) was 10,000, and the number average molecular weight of the block copolymer 1 was 21. 2,000.

Reference Example 2 [Synthesis of Block Copolymer Containing Epoxy Group] 75 kg of styrene was charged into a 90 liter polymerization tank, and the internal temperature was raised to 90 ° C. in a nitrogen atmosphere. After 30 minutes, 32 g of thio-S-acetic acid was added into the polymerization tank, and a radical polymerization initiator (V-65, manufactured by Wako Pure Chemical Industries, Ltd., 7 g) was immediately added.
Wt% toluene solution) at a rate of 430 ml / hour,
Further, thio-S-acetic acid (6% by weight toluene solution) was added to 7
It was added to the polymerization tank at a rate of 50 ml / hour to initiate polymerization. When the polymerization rate (polymer conversion rate) reached 40%, the polymerization was stopped and the internal temperature was cooled. By removing the solvent and the unreacted monomer of the obtained viscous liquid, a number average molecular weight of 1 having a thio-S-acetate group at a terminal is obtained.
1,000 polystyrenes were obtained. This polystyrene 3
0 kg, 30 kg of toluene and 15 kg of butanol were charged into a 90-liter reaction vessel, and heated to 70 ° C. under a nitrogen atmosphere.
10% by weight sodium hydroxide / methanol solution 13
5 ml was added, and a transesterification reaction of the thio-S-acetic acid ester group at the polystyrene end was performed. Two hours later, 30 g of acetic acid was added to the reaction vessel to complete the reaction. The solvent was distilled off from the obtained reaction solution to obtain polystyrene having a mercapto group at the terminal. Methyl methacrylate 29.1kg, glycidyl methacrylate 0.9K
g, 48 kg of toluene and 30 kg of polystyrene having a mercapto group at a terminal were charged into a 200-liter polymerization tank, and the inside thereof was sufficiently purged with nitrogen at 90 ° C., and then a radical polymerization initiator (V-65, manufactured by Wako Pure Chemical Industries, Ltd. (A 10% by weight toluene solution) was added to the polymerization tank at a rate of 54 ml / hour to initiate polymerization. Polymerization rate (polymer conversion rate) is 95
%, The polymerization was stopped, and a polystyrene block (A) and a methyl methacrylate-glycidyl methacrylate copolymer (methyl methacrylate: glycidyl methacrylate = 97: 3 (molar ratio)) block (B)
AB-type diblock copolymer (hereinafter, referred to as block copolymer 2). The number average molecular weight of the polymer block (A) of the obtained block copolymer 2 is 1
1,000, the number average molecular weight of the polymer block (B) is 8,000, and the number average molecular weight of the block copolymer 2 is 1
It was 9,000.

Reference Example 3 [Synthesis of Block Copolymer Having Carboxylic Anhydride Group] 45 kg of styrene was charged into a 60-liter polymerization tank, and the temperature was raised to 90 ° C. under a nitrogen atmosphere. Thirty minutes later, 19.2 g of thio-S-acetic acid was added to the polymerization tank, and a radical polymerization initiator (V-65, Wako Pure Chemical Industries, Ltd.) was immediately added.
Was added to the polymerization vessel at a rate of 260 ml / hour and thio-S-acetic acid (3% by weight toluene solution) at a rate of 900 ml / hour to initiate polymerization. When the polymerization rate (polymer conversion rate) reached 40%, the polymerization was stopped and the internal temperature was cooled. By removing the solvent and the unreacted monomer of the obtained viscous liquid, polystyrene having a number average molecular weight of 11,000 having a thio-S-acetate group at a terminal was obtained. This polystyrene 10 kg, toluene 10 kg and butanol 5
kg into a 30 liter reactor, under a nitrogen atmosphere,
At 70 ° C., 45 ml of a 10% by weight sodium hydroxide / methanol solution was added to carry out transesterification of the thio-S-acetic acid ester group at the end of polystyrene. Two hours later,
10 g of acetic acid was added to the reaction vessel to terminate the reaction. The solvent was distilled off from the obtained reaction solution to obtain polystyrene having a mercapto group at the terminal. Styrene 8.0
kg, 2.6 kg of acrylonitrile, 0.6 kg of maleic anhydride, 5.3 kg of toluene, and 3.3 kg of polystyrene having a mercapto group at the end were charged in a 50-liter polymerization tank, and the inside was sufficiently replaced with nitrogen at 90 ° C.
Radical polymerization initiator (V-65, manufactured by Wako Pure Chemical Industries, Ltd., 1
0% by weight toluene solution) at a rate of 30 ml / hour.
Furthermore, polystyrene having a mercapto group at the terminal (40
% By weight of a toluene solution) was added to the polymerization tank at a rate of 2.4 kg / hour to initiate polymerization. When the polymerization rate (polymer conversion rate) reached 65%, the polymerization was stopped, and the polystyrene block (A) and styrene-acrylonitrile-
AB type diblock copolymer (hereinafter referred to as block copolymer 3) composed of block (B) maleic anhydride terpolymer (styrene: acrylonitrile: maleic anhydride = 71: 24: 5 (molar ratio)) ). The number average molecular weight of the polymer block (A) of the obtained block copolymer 3 was 11,000, the number average molecular weight of the polymer block (B) was 10,000, and the number average molecular weight of the block copolymer 3 was 21. 2,000.

Examples 1 to 7 Poly (2,6-dimethyl-1,4-phenylene) ether [Noryl 53 manufactured by Nippon GE Plastics Co., Ltd.]
4 ”], a polyphenylene sulfide resin [“ Ryton P-6 ”manufactured by Philips Vetroleum Co., Ltd.], and the block copolymers 1 to 3 obtained in Reference Examples 1 to 3 in the proportions shown in Table 1 below. Then, the mixture was mixed using a Brabender, and then melt-extruded using a twin-screw extruder to obtain a thermoplastic resin composition. Test pieces were prepared from the obtained thermoplastic resin composition using an injection molding machine, and various physical properties were evaluated. The results are shown in Table 1 below.

Comparative Examples 1 to 3 Poly (2,6-dimethyl-1,4-phenylene) ether [Noryl 53 manufactured by Nippon GE Plastics Co., Ltd.
4 "] and a polyphenylene sulfide-based resin [" Ryton P-6 "manufactured by Philips Vetroleum Co., Ltd.] were mixed in the proportions shown in Table 1 below, and no block copolymer was blended. A thermoplastic resin composition was prepared in the same manner as above, and various properties were evaluated. The results are shown in Table 1 below.

[0049]

[Table 1]

[0050]

Industrial Applicability The thermoplastic resin composition of the present invention not only has excellent moldability, flame retardancy, heat resistance, etc., but also has mechanical properties such as tensile strength, flexural strength, flexural modulus and impact strength. It has excellent characteristics.

Claims (3)

[Claims] 1. A polyphenylene ether resin (I) 1
0 to 90 parts by weight and polyphenylene sulfide resin (I
I) 30 to 100 mol% of an aromatic vinyl-based monomer unit and 70 to 100 parts by weight of a resin mixture consisting of 90 to 10 parts by weight, and a vinyl-based monomer unit 70 copolymerizable therewith
To 0 mol% of the polymer block (A), and 0.1 to 100 mol% of a vinyl-based monomer unit having at least one functional group selected from a carboxyl group, an epoxy group and a carboxylic acid anhydride group. Block copolymer (III) composed of a polymer block (B) consisting of 99.9 to 0 mol% of a vinyl monomer unit copolymerizable with
0.1 to 20 parts by weight of a thermoplastic resin composition. 2. Constituting a block copolymer (III),
The number average molecular weight of the polymer block (A) is 1,000 to 1
The thermoplastic resin composition according to claim 1, wherein the polymer block (B) has a number average molecular weight of 1,000 to 100,000. 3. A molded article made of the thermoplastic resin composition according to claim 1.