JPH101605A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition excellent in moldability and processability, flame retardance, heat resistance, etc., as well as mechanical characteristics such as tensile strength, flexural strength, flexural modulus and impact strength and a molding comprising the thermoplastic resin composition. SOLUTION: This resin composition is obtained by blending 100 pts.wt. resin mixture comprising 10-90 pts.wt. polyketone resin (I) and 90-10 pts.wt. polyphenylene sulfide resin (II) with 0.1-20 pts.wt. block copolymer (III) composed of a polymer block (A) comprising 30-100mol% aromatic vinyl-based monomer unit and 70-0mol% vinyl-based monomer unit compolymerizable therewith and a polymer block (B) comprising 0.1-100mol% vinyl-based monomer having at least one kind of functional group selected from carboxylic groups, epoxy groups and carboxylic acid anhydride groups and 99.9-0mol% vinyl-based monomer unit copolymerizable therewith. This molding is obtained from the resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polyketone resin,
The present invention relates to a thermoplastic resin composition comprising a polyphenylene sulfide 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 is excellent in moldability, flame retardancy, 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 Polyketone resins are excellent in mechanical properties, water resistance, paintability, printability, and abrasion resistance, and are about to be used for food containers and automobile interior and exterior parts. However, polyketone resins have drawbacks such as inferior impact resistance, heat resistance, and flame retardancy, and therefore, in fact, are severely restricted in use. As a method for remedying this drawback, there is known a method of blending a polyketone resin with a polystyrene-based thermoplastic elastomer (see JP-A-2-38452).

[0003]

However, the mere blending of a polyketone resin with a polyketone thermoplastic elastomer improves the impact resistance, but is inferior in heat resistance, gasoline resistance and weather resistance. Only those having the disadvantages of plastic elastomers are 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 The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a polymer block (A) containing an aromatic vinyl monomer unit in an amount of 30 mol% or more, A block copolymer comprising 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 anhydride group. By blending the coalesced resin in a specific amount in a resin mixture composed of a polyketone resin and a polyphenylene sulfide resin, it was found that the compatibility of both resins was remarkably improved and the properties possessed by both resins were sufficiently exhibited. Completed the invention.

That is, the present invention provides the following general formula (1)
Polyketone resin (I) 10 comprising a structural unit represented by
90 parts by weight and polyphenylene sulfide resin (II) 9
Per 100 parts by weight of the resin mixture consisting of 0 to 10 parts by weight, 30 to 100 mol% of an aromatic vinyl monomer unit and 70 to 0 mol% of a vinyl monomer unit copolymerizable therewith. Polymer block (A), 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 anhydride group, and vinyl copolymerizable therewith The present invention relates to a thermoplastic resin composition comprising 0.1 to 20 parts by weight of a block copolymer (III) composed of a polymer block (B) comprising 99.9 to 0 mol% of a monomer unit. Further, the present invention relates to a molded article comprising the above-mentioned thermoplastic resin composition.

[0007]

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Wherein A represents a unit derived from an olefin.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The polyketone resin used in the present invention comprises a structural unit represented by the general formula (1), wherein a unit derived from carbon monoxide and a unit derived from olefin alternate. Is a linear alternating copolymer.

Examples of the olefin include ethylene,
Examples thereof include propylene, butene, isobutene, pentene, hexene, heptene, octene, nonene, and dodecene, and one or more of these can be used. Among these, it is preferable to use ethylene and propylene, and particularly preferable to use ethylene. Further, in addition to the above monomers, if necessary, styrene, methyl acrylate, methyl methacrylate, vinyl acetate, undecenoic acid, undecenol, 6-chlorohexene, N-vinylpyrrolidone, diethyl ester of sulfonylphosphonic acid, etc. They can be used together.

The polyketone resin is, for example, palladium,
In the presence of a catalyst composition formed from a cobalt or nickel compound, a non-hydrohalic acid anion having a pKa of 6 or less, preferably 2 or less, and phosphorus, arsenic or antimony, carbon monoxide and an olefin are converted. Obtained by contact.

In the polyketone resin used in the present invention, m
Solution viscosity measured in cresol at 60 ° C. (hereinafter LV
N) is 0.5 to 10.0 dl / g.
Is preferably within the range. When the LVN is less than 0.5, the mechanical strength of the obtained resin composition becomes insufficient.

The polyphenylene sulfide resin (II) used in the present invention contains a structural unit represented by the following general formula (2) in an amount of at least 70 mol%, more preferably at least 90 mol%, based on all structural units. Within the range that does not impair the crystallinity of the resin, stretch orientation, etc.
At a ratio of 30 mol% or less based on all structural units), and may contain structural units represented by the following general formulas (3) to (9).

[0014]

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[0015]

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[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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Wherein R represents an alkyl group, a nitro group, an alkoxyl group, a carboxyl group, or a metal salt of 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, and includes, for example, an AB-type diblock copolymer, an ABA-type triblock copolymer,
BAB type triblock copolymers can be mentioned. Of these, AB-type diblock copolymers are preferred.

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,
Units derived from alkyl-substituted styrenes such as p-tert-butylstyrene and 3,4-dimethylstyrene; halogen-substituted styrenes such as chlorostyrene; and hydroxystyrenes such as p-hydroxystyrene. Species or two or more can be used. 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. Of these, units derived from glycidyl acrylate and glycidyl methacrylate are preferred.

Examples of the vinyl monomer unit having a carboxylic anhydride group (—CO—O—CO—) include, for example, maleic anhydride, itaconic anhydride, citraconic anhydride, butenyl succinic anhydride, and tetrahydrophthalic anhydride. And the like. One or more of these units can be used. Of 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 number average molecular weight of the polymer block (A), the polymer block (B) and the block copolymer (III) is within the above range, the polyketone resin (I) and the polyphenylene sulfide resin (II) A thermoplastic resin composition having extremely excellent compatibility with is obtained,
It is preferable because the excellent properties inherent in each resin are sufficiently exhibited. Incidentally, the number average molecular weight referred to in the present specification,
It 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, the 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 prepared by adding a block copolymer (II) to a resin mixture comprising the above-mentioned polyketone resin (I) and polyphenylene sulfide resin (II).
It can be obtained by blending I). The mixing ratio of the polyketone resin (I) in the resin mixture is from 10 to 90 parts by weight, and preferably from 30 to 90 parts by weight. The compounding ratio of the polyphenylene sulfide 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 2 parts by weight based on 100 parts by weight of the resin mixture composed of the polyketone resin (I) and the polyphenylene sulfide resin (II).
0 parts by weight, and 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 part by weight, the compatibility between the polyketone resin (I) and the polyphenylene sulfide resin (II) is not improved, so that the mechanical properties of the obtained thermoplastic resin composition are inferior.

The thermoplastic resin composition of the present invention comprises the above-mentioned polyketone resin (I), polyphenylene sulfide resin (II) and block copolymer (III) as essential components. It may be contained. Examples of other optional components include compounds having a function of accelerating the reaction between the functional group (carboxyl group, epoxy group, carboxylic 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.
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 compound is preferably about 0.001 to 0.1 part by weight based on 100 parts by weight of the polyphenylene sulfide resin (II).

The thermoplastic resin composition of the present invention may further comprise, if necessary, a pigment, a nucleating agent, an antioxidant,
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.

The thermoplastic resin composition of the present invention uses the above-mentioned polyketone resin (I), polyphenylene sulfide resin (II), block copolymer (III) and, if necessary, other components described above. Thus, it can be produced by a usual polymer blending technique. 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, or a Banbury mixer, or may be simply dry-blended. 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 resulting thermoplastic resin composition contains a polyketone resin ( One of the polyphenylene sulfide resin (I) and the polyphenylene sulfide resin (II) is in a state of being finely dispersed in a matrix of the other resin, and is preferable because good mechanical properties are easily exhibited. Further, when the compound having the function of accelerating 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 copolymer is mixed during the kneading. It is preferable because the reaction between the functional group of the polymer (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, but are usually about 250 to 300 ° C. for about 3 hours.
It is good to knead for about 30 minutes.

The thermoplastic resin composition of the present invention can be melt-molded or heat-processed, and various molded articles can be smoothly produced by any molding method such as injection molding, extrusion molding, blown 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.

[0039]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is 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] Measured according to ASTM D638.

[Bending strength and flexural modulus] ASTM D7
Measured according to 90.

[Izod impact strength] ASTM D25
6 (notched).

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

[Heat deformation temperature] Measured according to ASTM D648 (load 18.6 kg / cm ² ).

[Flame retardancy test] VB conforming to 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 end of the polystyrene was performed. Two hours later, 30 g of acetic acid was added to the reaction vessel to complete the reaction. By distilling off the solvent from the obtained reaction solution, polystyrene having a mercapto group at a terminal was obtained. 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 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 end of the polystyrene was performed. Two hours later, 30 g of acetic acid was added to the reaction vessel to complete the reaction. By distilling off the solvent from the obtained reaction solution, polystyrene having a mercapto group at a terminal was obtained. 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. 30 minutes later, 19.2 g of thio-S-acetic acid was added to the polymerization tank, and immediately a radical polymerization initiator (V-65, Wako Pure Chemical Industries, Ltd.)
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. By distilling off the solvent from the obtained reaction solution, polystyrene having a mercapto group at a terminal was obtained. 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 into a 50-liter polymerization tank, and the inside was sufficiently purged 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 [Synthesis of Polyketone Resin] Carbon monoxide, ethylene and propylene were dissolved in methanol in palladium acetate, trifluoroacetic acid and 1,3
By contacting with -bis [bis (2-methoxyphenyl) phosphino] propane, a polyketone resin of a linear alternating copolymer was produced. The melting point of this polyketone resin is 2
At 20 ° C, the LVN was 1.78 dl / g (measured in m-cresol at 60 ° C).

Examples 1 to 7 The polyketone resin obtained in Reference Example 4 was replaced by a polyphenylene sulfide resin (“Ryton P-6” manufactured by Philips Veterolium Co.) and the block copolymer obtained in Reference Examples 1 to 3. 1-3 are blended in the ratio shown in Table 1 below,
After mixing using a Brabender, the mixture was 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 Example 1 Test pieces were prepared from the polyketone resin obtained in Reference Example 4 using an injection molding machine, and various physical properties were evaluated in the same manner as in Examples 1 to 7. The results are shown in Table 1 below.

Comparative Examples 2 and 3 The polyketone resin obtained in Reference Example 4 was blended with a polyphenylene sulfide resin (“Ryton P-6” manufactured by Philips Veterolium Co., Ltd.) at the ratio shown in Table 1 below. Examples 1-7 except that no polymer was blended
In the same manner as in the above, a thermoplastic resin composition was prepared and various physical properties were evaluated. The results are shown in Table 1 below.

[0053]

[Table 1]

[0054]

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. 100 parts by weight of a resin mixture comprising 10 to 90 parts by weight of a polyketone resin (I) having a structural unit represented by the following general formula (1) and 90 to 10 parts by weight of a polyphenylene sulfide resin (II). On the other hand, a polymer block (A) comprising 30 to 100 mol% of an aromatic vinyl monomer unit and 70 to 0 mol% of a vinyl monomer unit copolymerizable therewith, and a carboxyl group, an epoxy group and 0.1 to 100 mol% of a vinyl monomer unit having at least one functional group selected from carboxylic anhydride groups
And 99.9 vinyl monomer units copolymerizable therewith
A thermoplastic resin composition comprising 0.1 to 20 parts by weight of a block copolymer (III) composed of a polymer block (B) of from 0 to 0 mol%. Embedded image (In the formula, A represents a unit derived from an olefin.) 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 number average molecular weight of the polymer block (B) is 1,000 to 100,000. 3. A molded article comprising the thermoplastic resin composition according to claim 1.