JPH09302217A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition excellent in mechanical properties including tensile strength, flexural strength, modulus in flexure, and impact strength, heat resistance, moldability, etc., 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. polycarbonate 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 from 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 polycarbonate resin and a block copolymer having a specific functional group, and a molded article comprising the thermoplastic resin composition. . The thermoplastic resin composition of the present invention has excellent moldability, heat resistance, mechanical properties, and the like, and can be suitably used as a molding material for industrial materials, industrial materials, household goods, and the like.

[0002]

2. Description of the Related Art Polyphenylene ether resins are resins that have recently been attracting attention as engineering plastics because of their excellent heat resistance, mechanical properties and electrical properties, but they have the drawback of being inferior in impact resistance. For this reason, generally used is an impact-resistant polystyrene resin having good compatibility or a compound in which a polystyrene-based thermoplastic elastomer is mixed with a polyphenylene ether-based resin. However, these resin compositions are inferior in heat resistance, gasoline resistance, etc., because they have the drawbacks of the polystyrene-based resin to be blended, and are significantly limited in their applications.

On the other hand, since the polycarbonate resin is excellent in toughness and heat resistance, the above-mentioned drawbacks can be expected to be improved by blending the polycarbonate resin with the polyphenylene ether resin, but in reality, the polyphenylene ether is actually used. The compatibility between the base resin and the polycarbonate resin is remarkably poor, and the phases are immediately separated by simply melt-kneading, so that the expected effect cannot be obtained.

Japanese Patent Laid-Open No. 1-252660 discloses that a graft copolymer of ethylene-glycidyl methacrylate and a vinyl polymer is blended in a resin mixture of a polyphenylene ether resin and a polycarbonate resin to improve heat resistance. It is described that a resin composition having improved moldability and mechanical properties can be obtained. Further, JP-A-7-
Japanese Patent Publication No. 179741 describes that a graft copolymer composed of a polycarbonate-based resin segment and a vinyl-based resin segment is added to a resin mixture of a polyphenylene ether-based resin and a polycarbonate-based resin.

[Problems to be Solved by the Invention]

However, even when the graft copolymers described in JP-A-1-252660 and JP-A-7-179741 are used, the polyphenylene ether resin and the polycarbonate resin are not sufficiently compatibilized. Therefore, it is desired to have more excellent properties such as mechanical properties, heat resistance and molding processability. Further, in the above-mentioned graft copolymer, since peroxide is used in the production, the peroxide remaining in the graft copolymer is decomposed in the production of the intended resin composition, resulting in deterioration of the resin or It has the disadvantage of causing crosslinking.

The object of the present invention is to provide a thermoplastic resin composition having excellent mechanical properties such as tensile strength, bending strength, flexural modulus, impact strength, heat resistance and moldability, and the thermoplastic resin composition. It is to provide a molded article made of.

[0007]

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. It was found that, by blending the coalesce in a resin mixture consisting of a polyphenylene ether-based resin and a polycarbonate-based resin in a specific amount, the compatibility of both resins is remarkably improved and the characteristics of both resins are sufficiently expressed. The present invention has been completed.

That is, the present invention provides a resin mixture 1 comprising 10 to 90 parts by weight of a polyphenylene ether resin (I) and 90 to 10 parts by weight of a polycarbonate resin (II).
Aromatic vinyl-based monomer unit 30 to 30 parts by weight
Polymer block (A) consisting of 100 mol% and 70 to 0 mol% of a vinyl monomer unit copolymerizable therewith, and at least one functional group selected from a carboxyl group, an epoxy group and a carboxylic acid anhydride group. Block copolymer composed of a polymer block (B) consisting of 0.1 to 100 mol% of a vinyl-based monomer unit having 9 and 99.9 to 0 mol% of a vinyl-based monomer unit copolymerizable therewith. The present invention relates to a thermoplastic resin composition containing 0.1 to 20 parts by weight of the compound (III). Further, the present invention relates to a molded article comprising the above-mentioned thermoplastic resin composition.

[0009]

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 polycarbonate resin (II) used in the present invention can be obtained, for example, by subjecting a diol compound and a carbonic acid diester compound to a polycondensation reaction by a transesterification method according to a conventional method.

The diol compound is not particularly limited,
Various known compounds such as aromatic diols, alicyclic diols, and aliphatic diols can be used. Examples of the aromatic diol include bis (4-hydroxyphenyl) methane and 1,1-bis (4-hydroxyphenyl)
Ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane ,
2,2-bis (4-hydroxy-1-methylphenylpropane), 1,1-bis (4-hydroxy-t-methylphenyl) propane, 2,2-bis (4-hydroxy-
Bis (hydroxyaryl) alkanes such as 3-bromophenyl) propane; bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclopentane and 1,1- (4-hydroxyphenyl) cyclohexane Dihydroxyaryl ethers such as 4,4-dihydroxydiphenyl ether and 4,4-dihydroxy-3,3-dimethylphenyl ether; 4,4-dihydroxydiphenyl sulfide;
Dihydroxydiaryl sulfides such as 4,4-dihydroxy-3,3-dimethylphenyl sulfide;
4,4-dihydroxydiphenylsulfoxide, 4,4
Dihydroxydiarylsulfoxides such as -dihydroxy-3,3-dimethyldiphenylsulfoxide;
Examples thereof include dihydroxydiarylsulfones such as 4,4-dihydroxy-3,3-dimethyldiphenylsulfone. Examples of the alicyclic diol include cyclohexane dimethanol, cyclohexane diol, and the like. Further, examples of the aliphatic diol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, and 3-methyl-1,5.
-Pentanediol, 1,6-hexanediol, 1,
Examples thereof include 8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol. Of these, aromatic diols are preferably used, and 2,2-bis (4
More preferably, (-hydroxyphenyl) propane is used.

The carbonic acid diester compound is not particularly limited and known compounds can be used. For example, diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl carbonate ) Carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate and the like. Among these, it is preferable to use diphenyl carbonate.

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. Of these, one type or two or more types 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 itaconic acid ester, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-p-glycidyl ether, 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 acid anhydride group (-CO-O-CO-) include maleic anhydride, itaconic anhydride, citraconic anhydride, butenyl succinic anhydride, and tetrahydrophthalic anhydride. And the like, and one or more of these can be used. Among these, units derived from maleic anhydride are preferred.

The polymer block (B) is, 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 polycarbonate resin ( A thermoplastic resin composition having extremely excellent compatibility with II) is obtained, and the excellent effects originally possessed by each resin are sufficiently exhibited, which is preferable. In addition, the number average molecular weight as referred to in the present specification refers to gel permeation chromatography (G
It is a value obtained from a standard polystyrene calibration curve by the PC) method.

The method for producing the block copolymer (III) is not particularly limited, but, for example, the monomer component constituting the polymer block (A) [or the polymer block (B)] is replaced with 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 resulting polymer is sodium hydroxide, ammonia. Etc. or an acid such as hydrochloric acid or sulfuric acid to obtain a polymer having a mercapto group at one end, and in the presence of the polymer, the polymer block (B) [or the polymer block (A) A method for producing a block copolymer (III) by radically polymerizing a monomer component constituting the compound has a desired number average molecular weight and molecular weight distribution. Preferred can be obtained lock copolymer (III) 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 polycarbonate resin (II). . The compounding ratio of the polyphenylene ether resin (I) in the resin mixture is 10 to 90 parts by weight, preferably 30 to 90 parts by weight. The blending ratio of the polycarbonate-based resin (II) is 90 to 10 parts by weight, preferably 70 to 10 parts by weight. The mixing ratio of the block copolymer (III) is 0.1 to 20 parts by weight based on 100 parts by weight of the resin mixture composed of the polyphenylene ether resin (I) and the polycarbonate resin (II). 0-1
It is preferably 0 parts by weight. Block copolymer (II
If the blending ratio of I) exceeds 20 parts by weight, the heat resistance of the resulting thermoplastic resin composition will decrease. On the other hand, 0.
When the amount is less than 1 part by weight, the compatibility between the polyphenylene ether resin (I) and the polycarbonate resin (II) is not improved, so that the mechanical properties of the obtained resin composition are deteriorated.

The thermoplastic resin composition of the present invention contains the above-mentioned polyphenylene ether resin (I), polycarbonate resin (II) and block copolymer (III) as essential components, but if necessary, other You may contain the component. Examples of other optional components include block copolymers (II
Examples thereof include compounds having the action of promoting the reaction between the functional group (carboxyl group, epoxy group, carboxylic acid anhydride group) possessed by I) and the polycarbonate resin (II). 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.
As the compound, for example, triphenylamine, 2,
Tertiary amines such as 4,6-tris (dimethylaminomethyl) phenol; tetrabutylammonium fluoride, triethylbenzylammonium chloride, tetramethylammonium chloride, trioctylammonium chloride, tributylbenzylammonium chloride, N-laurylpyridinium chloride, odor Ammonium compounds such as tetramethylammonium bromide, tetraethylammonium bromide, and n-butylammonium bromide; triphenyl phosphite;
A phosphite such as triisodecyl phosphite;
Alkyltriphenylphosphonium halogen compounds (eg, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, etc.), alkenyltriphenylphosphonium halogen compounds, tetraalkylphosphonium halogen compounds (eg, tetrabutylphosphonium bromide, etc.) Phosphonium compounds; tertiary phosphines such as triphenylphosphine; metal sulfonates such as sodium dodecylbenzenesulfonate and sodium 3,5-dicarbomethoxybenzenesulfonate; and sulfates such as sodium lauryl sulfate. Usually, the compounding ratio of the above compound is preferably about 0.001 to 0.1 part by weight based on 100 parts by weight of the polycarbonate 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 other polymer, for example, polyolefin resin such as polyethylene; polyester resin such as polyethylene terephthalate or polyamide resin can be used. In the present invention, polyphenylene ether resin ( For I), it may be effective to use a styrene resin in order to improve molding processability such as melt fluidity.

The above-mentioned styrene-based 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 polycarbonate resin (II) and the block. Copolymer (II
Method of mixing with I); Styrene resin is polyphenylene ether resin (I), polycarbonate resin (II)
And any method such as a method of simultaneously mixing with the block copolymer (III) can be adopted.

The thermoplastic resin composition of the present invention comprises the above-mentioned polyphenylene ether resin (I), polycarbonate resin (II), block copolymer (III) and, if necessary, the above-mentioned other components. It can be used and produced by conventional polymer blending techniques. For example, melt kneading may be performed using a melt kneader such as a single screw extruder, a twin screw extruder, a Brabender, a kneader, a Banbury mixer, or simply dry blending. When the thermoplastic resin composition is produced by melt-kneading, the reaction between the functional group of the block copolymer (III) and the polycarbonate resin (II) proceeds, and in the obtained thermoplastic resin composition, the polyphenylene ether resin is used. One of the resin (I) and the polycarbonate-based resin (II) is preferably in a state of being finely dispersed in the matrix of the other resin and easily exhibiting good mechanical properties. Further, when the compound having the function of promoting the reaction between the functional group of the block copolymer (III) and the polycarbonate resin (II) is allowed to coexist during the melt kneading, the block copolymer is kneaded during the kneading. It is preferable because the reaction between the functional group of the polymer (III) and the polycarbonate resin (II) is further promoted, and a thermoplastic resin composition having better mechanical properties can be obtained. The melt-kneading conditions are not particularly limited, but it is usually good to carry out kneading 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 articles 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.

[0032]

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, flexural modulus, bending strength, Izod impact strength, heat deformation temperature, and peelability of molded products were measured or evaluated by the following methods.

[Tensile Strength] 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 Distortion Temperature] The heat distortion temperature was measured according to ASTM D648 (load: 18.6 kg / cm ² ).

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 temperature was raised to 90 ° C. under 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 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.

Reference Example 4 [Production method of graft copolymer] 3.4 kg of sodium hydroxide was dissolved in 4.2 kg of water,
While maintaining at 20 ° C, 2,2-bis (4-hydroxyphenyl) propane 6.6Kg, hydrosulfite 8
g was dissolved. To this, 28 liters of methylene chloride was added and stirred, 260 g of p-tert-butylphenol was added, and then 3.3 kg of phosgene was blown in for 60 minutes. After the completion of blowing phosgene, the reaction solution was emulsified by vigorous stirring, 8 g of triethylamine was added, and stirring was continued for about 1 hour to polymerize. The polymerization liquid was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and then 35 liters of isopropanol was added to precipitate a polymer. The precipitate was filtered and then vacuum dried to obtain a white powder of polycarbonate resin. As a result of measuring the viscosity of the polycarbonate resin, the viscosity average molecular weight was 16,000. 1700 g of this polycarbonate resin was put into a 5 liter autoclave, 2.5 kg of water and 2.5 g of polyvinyl alcohol as a suspending agent were added. Separately, benzoyl peroxide 1.5 as a radical initiator
g, 6 g of t-butylperoxymethacryloyloxyethyl carbonate as a radically polymerizable organic peroxide,
Dissolved in styrene. Then, this solution was put into the autoclave and stirred. Next, the polycarbonate resin was impregnated with styrene containing a radical polymerization initiator and a radically polymerizable organic peroxide by keeping the internal temperature of the autoclave at 60 to 65 ° C. and stirring for 2 hours. Then, the temperature was raised to 80 to 85 ° C. and maintained for 7 hours to complete the polymerization, followed by washing with water and drying to obtain a graft precursor. The number average degree of polymerization of styrene in the graft precursor was 900. Next, this graft precursor was extruded with a Labo Plastomill uniaxial extruder (manufactured by Toyo Seiki Seisakusho, Ltd.) at 250 ° C. to carry out a grafting reaction to obtain a graft copolymer composed of a polycarbonate segment and a styrene segment.

Examples 1 to 7 Poly (2,6-dimethyl-1,4-phenylene) ether [Noryl 73 manufactured by Nippon GE Plastics Co., Ltd.]
1 "], a polycarbonate resin [" Lexan 1X1 "manufactured by Nippon GE Plastics Co., Ltd.] and Reference Examples 1 to 1
After the block copolymers 1 to 3 obtained in Example 3 were blended in the proportions shown in Table 1 below and mixed using a Brabender,
A thermoplastic resin composition was obtained by melt extrusion using a twin-screw extruder. 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 Example 1 Poly (2,6-dimethyl-1,4-phenylene) ether [Noryl 73 manufactured by Nippon GE Plastics Co., Ltd.]
1 ”], and a polycarbonate resin [“ Lexane 1X1 ”manufactured by Japan GE Plastics Co., Ltd.] in the proportions shown in Table 1 below, in the same manner as in Examples 1 to 7 Was prepared and various physical properties were evaluated.
The results are shown in Table 1 below.

Comparative Examples 2 to 4 Thermoplastic resin compositions were prepared in the same manner as in Examples 1 to 7 except that the graft copolymer obtained in Reference Example 4 was used instead of the block copolymer. , Various physical properties were evaluated. The results are shown in Table 1 below.

[0045]

[Table 1]

[0046]

The thermoplastic resin composition of the present invention is excellent in mechanical properties such as tensile strength, flexural strength, flexural modulus and impact strength, heat resistance, moldability and the like.

Claims (3)

[Claims] 1. A polyphenylene ether resin (I) 1
0-90 parts by weight and polycarbonate resin (II) 90-
A polymer comprising 30 to 100 mol% of an aromatic vinyl monomer unit and 70 to 0 mol% of a vinyl monomer unit copolymerizable with the aromatic vinyl monomer unit to 100 parts by weight of a resin mixture consisting of 10 parts by weight. A vinyl-based monomer unit having a block (A) and at least one functional group selected from a carboxyl group, an epoxy group, and a carboxylic acid anhydride group.
A block copolymer (III) composed of a polymer block (B) composed of 1 to 100 mol% and 99.9 to 0 mol% of a vinyl monomer unit copolymerizable therewith is added in an amount of 0.1%.
A thermoplastic resin composition containing 1 to 20 parts by weight. 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.