JP2949699B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition having a good balance of heat resistance, moldability and impact resistance.

[0002]

2. Description of the Related Art Sulfone polymers such as polysulfone and polyethersulfone are known as engineering plastics having excellent heat resistance.
However, it is known that the impact resistance is not always large, and that the molding processability is insufficient, such as requiring a high temperature of 300 ° C. or more during the molding process. As an improved method, acrylonitrile-butadiene-styrene resin (hereinafter referred to as A
It is known to blend a rubber-grafted styrene copolymer such as BS resin).

For example, Japanese Patent Publication No. 46-37896, Japanese Patent Publication No. 49-37896
A-27668 or JP-A-56-167752 discloses A
Composition of BS resin and polyether sulfone, JP-A-56
JP-A-16552 discloses a composition with an ABS resin, polysulfone, and an organosilicon compound. JP-A-56-16552 discloses a composition with an ABS resin, polyarylene polysulfone, and a polycarbonate, and JP-A-63-305152. The publication discloses a composition with an ABS resin, polysulfone, and polyetherimide, and the like. Also, JP-A-61-667
No. 50 discloses a composition of a copolymer having a repeating unit of a vinyl aromatic monomer and a maleimide monomer and a polyether sulfone resin.

However, in these compositions, it is necessary to add a large amount of a rubbery polymer in order to improve the impact resistance, so that it is inevitable that the heat resistance is reduced. That is, the balance of physical properties such as heat resistance and impact resistance is not always satisfactory, and improvement is required.

[0005]

An object of the present invention is to provide a thermoplastic resin composition having an excellent balance between heat resistance and impact resistance.

[0006]

[Technical means for solving the problems]
A thermoplastic resin composition comprising a copolymer containing a polyarylether sulfone having a specific structure, a repeating unit of an α, β-unsaturated cyclic imide and a repeating unit of an aromatic vinyl compound is heat-resistant and molded. It was found that the balance between the properties and the impact resistance was excellent. The present invention comprises (A) a repeating unit of the following formulas (I) and (II),

[0007]

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The ratio of the repeating unit (I) to the repeating unit (II) is 10 to
It contains 95 to 5% by weight of a polyarylether sulfone having a structure of 70:30 to 90 (mol%) and (B) a repeating unit of an α, β-unsaturated cyclic imide and a repeating unit of an aromatic vinyl compound. The present invention relates to a thermoplastic resin composition comprising 5 to 95% by weight of a copolymer.

The component (A) of the composition of the present invention has the following formula:
Consisting of repeating units (I) and (II),

[0010]

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The ratio of the repeating unit (I) to the repeating unit (II) is 10 to
It is a polyarylether sulfone having a structure of 70:30 to 90 (mol%).

[0012] The production method is as follows:
In the presence of an alkali metal compound, a polycondensation reaction between a dihalogenodiphenyl sulfone compound and a dihydric phenol compound,
Alternatively, it can be produced by using hydroquinone and 4,4′-biphenol as a dihydric phenol compound at a predetermined ratio in a polycondensation reaction between a previously synthesized alkali metal disalt of dihydric phenol and a dihalogenodiphenyl sulfone compound.

In the dihydric phenol compounds hydroquinone and 4,4'-biphenol, at least one of the hydrogens on the benzene ring is substituted with a suitable substituent (for example, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, etc.). Alternatively, those substituted with a substituent such as a lower alkoxy group such as a methoxy group and an ethoxy group may be used.

The ratio between the repeating unit (I) and the repeating unit (II) can be adjusted by the charging ratio in the polycondensation reaction between hydroquinone and 4,4'-biphenol, respectively. In the composition of the present invention, the ratio of the repeating unit (I) to the repeating unit (II) of the polyarylethersulfone is from 10 to 70:30.
9090 (mol%). If the ratio is out of the above range, the balance of the physical properties of the composition is lost, which is not preferable.

In the composition of the present invention, the molecular weight of the polyaryl ether sulfone is not particularly limited, but the reduced viscosity (at 30 ° C.) of a 0.5 g / 100 ml solution of N-methyl-2-pyrrolidone as a solvent is measured. ηsp / c) is 0.2 ~
1.0 is preferable, and 0.4 to 0.6 is particularly preferably used.

The component (B) of the composition of the present invention is a copolymer containing a repeating unit of an α, β-unsaturated cyclic imide and a repeating unit of an aromatic vinyl compound. α, β
-As the unsaturated cyclic imide, maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, Nt-butylmaleimide, alkyl-substituted maleimide such as N-lauroylmaleimide, N-phenylmaleimide,
N- (tolyl) maleimide, N- (2,6-dimethylphenyl)
Maleimide, N- (p-chlorophenyl) maleimide, N- (o
Aromatic maleimides such as -chlorophenyl) maleimide and N- (p-bromophenyl) maleimide; and N-cyclohexylmaleimide. Among these, maleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like can be preferably used. The above α, β-unsaturated cyclic imides can be used as a mixture of two or more kinds.

As the aromatic vinyl compound, styrene,
Styrene and styrene derivatives such as α-methylstyrene, p-methylstyrene, p-chlorostyrene, pt-butylstyrene, styrenesulfonic acid and the like can be mentioned.

In addition to the above components, a vinyl cyanide compound may be copolymerized. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. Further, α, β-unsaturated acid anhydrides such as acrylic acid, methacrylic acid, maleic anhydride, and itaconic anhydride, and their methyl-, propyl-,
Esters or diesters such as n-butyl-, phenyl- and cyclohexyl- may be copolymerized.

Examples of the copolymer containing each of the above components as a monomer include N-phenylmaleimide-acrylonitrile-
Styrene copolymer, N-phenylmaleimide-acrylonitrile-α-methylstyrene copolymer, N-phenylmaleimide-styrene copolymer, N-phenylmaleimide-α
-Methylstyrene copolymer and the like can be preferably used.

The component composition of the copolymer of component (B) is not particularly limited, but the α, β-unsaturated cyclic imide is preferably 5 to 50 mol%. The aromatic vinyl compound is
50-95 mol% is preferred.

The molecular weight of the copolymer of component (B) is not particularly limited, but is preferably 10,000 to 200,000, particularly preferably
30,000 to 150,000 are preferred.

The mixing ratio of the component (A) to the component (B) in the composition of the present invention is such that the component (A) is 5 to 95% by weight,
(B) The component is 95 to 5% by weight. Preferably, component (A) is 20-90% by weight and component (B) is 80-10% by weight.

The mixing ratio is related to the balance of properties such as heat resistance, moldability and mechanical properties. If the ratio is out of the above range, the balance of these characteristics will be lost.

That is, when the proportion of the component (A) exceeds 95% by weight, the effect of improving the moldability is small, and when it is less than 5% by weight, the heat resistance decreases.

The composition of the present invention may contain a rubbery polymer in addition to the above components. Examples of the rubbery polymer include polybutadiene rubber, ethylene-propylene copolymer rubber, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, and styrene-
Examples include butadiene copolymer rubber, acid-modified rubber such as maleic anhydride and itaconic anhydride, and glycidyl group-modified rubber such as glycidyl methacrylate and glycidyl acrylate. Also, acrylonitrile-butadiene copolymer rubber, chlorinated polyethylene, acrylic rubber, styrene-butadiene block copolymer rubber (S
B, SBS), styrene isoprene-based block copolymer rubber (SI, SIS) and hydrogenated products thereof (SEB,
SEBS, SEP, SEPS) and their modified functional groups, or graft copolymers obtained by grafting styrene and / or acrylonitrile or methyl methacrylate to these rubbery polymers, styrene-butadiene copolymer rubber and styrene-acrylonitrile Examples thereof include an ABS resin, an AAS resin, an ACS resin, an AES resin, an MBS resin, and a MAS resin, which are a blend with a resin or the like, or a combination thereof. Examples of the production method include known production methods such as an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, and a bulk polymerization method. By adding the rubber-like resin, physical properties such as impact resistance (notched Izod strength) of the composition are further improved.

As long as the properties of the composition of the present invention are not impaired, polyethylene, polypropylene, ethylene / vinyl acetate copolymer, butadiene / acrylate / styrene copolymer, acrylate-based elastic copolymer, polyvinyl chloride-based Thermoplastic resins such as resins, polyester resins, polyamide resins, etc., thermosetting resins such as phenolic resins, melamine resins, silicone resins, epoxy resins, glass fibers, carbon fibers, boron fibers, silicon carbide fibers, asbestos fibers, Reinforcing agents such as metal fibers, fillers such as clay, mica, silica, graphite, glass beads, calcium carbonate, and talc; or antioxidants, heat stabilizers, ultraviolet inhibitors, flame retardants, pigments, antistatic agents, coloring One or more agents may be added.

Polyarylether sulfone and α, β-
In order to improve the dispersibility of a copolymer containing a repeating unit of an unsaturated cyclic imide and a repeating unit of an aromatic vinyl compound, a compatibilizer may be newly added.

The method of blending the components of the present invention is not particularly limited, but can be blended by kneading using a usual kneader. For example, pellets can be obtained by melt-kneading using a single-screw extruder, a twin-screw extruder, a mixing roll, a Banbury mixer, or the like. The pellets are formed into an arbitrary shape such as a film, a pipe, and a tube by injection molding, blow molding, extrusion molding, or the like.

[0029]

According to the present invention, a composition comprising a copolymer comprising a polyarylether sulfone having a specific structural unit, a repeating unit of an α, β-unsaturated cyclic imide and a repeating unit of an aromatic vinyl compound is In addition, the moldability is improved, and a higher impact resistance is obtained and a decrease in heat resistance is suppressed as compared with a composition using a conventionally known sulfone-based polymer. That is, the composition of the present invention is a thermoplastic resin composition having an excellent balance of physical properties such as moldability, heat resistance and impact resistance, and is used in various fields of automobiles, electronic and electrical parts, mechanical parts, medical and tableware fields. It can be used as a material.

[0030]

【Example】

(Method of preparing test piece) The test piece was prepared by pelletizing the composition, and then injection molding machine Nestal SG100 (mold clamping force 10) manufactured by Sumitomo Heavy Industries, Ltd.
(0ton). (Test method of test piece) (1) Deflection temperature under load The test was performed according to ASTM D648. (2) Izod impact strength (with notch) This was performed according to ASTM D256.

Example 1 73.3 g (0.255 mol) of 4,4'-dichlorodiphenyl sulfone,
Hydroquinone 13.7 g (0.124 mol) and 4,4'-biphenol 23.2 g (0.124 mol) were dissolved in azeotropic dehydration toluene 30 ml and N-methyl-2-pyrrolidone 300 ml under a nitrogen atmosphere, and then dissolved in nitrogen. 37.9 g of potassium carbonate heat-treated at 70 ° C. for 30 minutes was stirred and reacted at 180 ° C. for 8 hours in a nitrogen atmosphere to obtain a polymerization solution. After the completion of the reaction, the mixture was filtered at a nitrogen pressure of 1.5 kg / cm ² to separate the inorganic substance from the polymerization solution, thereby obtaining a polymerization solution. Pour 300 g of the polymerization solution into 2000 ml of ethanol,
The polymer was precipitated while stirring at 00 rpm, filtered and separated to obtain a polymer. 50 g of this polymer is mixed with 500 ethanol
After washing with ml, it was dried at 90 ° C. to obtain polyarylethersulfone (component A) powder. The reduced viscosity (ηsp / c) of the obtained polyarylether sulfone is 0.52, and the ratio of the repeating unit (I) to the repeating unit (II) is 50:50 (mol%).
Met.

As the copolymer (component B) containing a repeating unit of an α, β-unsaturated cyclic imide and a repeating unit of an aromatic vinyl compound, a copolymer synthesized by the following method was used. A monomer mixture consisting of 80% by weight of styrene and 20% by weight of N-phenylene maleimide was dispersed in water at a concentration of 20%, and suspension polymerization was carried out at 70 ° C. for 5 hours while stirring at 70 ° C. using benzoyl peroxide as an initiator. After filtration, washing and drying, a powdery unsaturated imide copolymer was obtained. The weight average molecular weight of the obtained copolymer was 120,000.

70% by weight of the component A and 30% by weight of the component B were mixed, and the mixture was melt-kneaded at 300 ° C. using a 30 mmφ twin-screw extruder manufactured by Nakatani Machinery Co., Ltd. I got something. Each evaluation experiment was performed using this composition.
The results are shown in Table 1.

Examples 2 and 3 In Example 1, the mixing ratios of the components A and B are shown in Table 1.
A resin composition was obtained in the same manner as in Example 1, except for the following. Each evaluation experiment was performed in the same manner as in Example 1 using this composition. The results are shown in Table 1.

Example 4 A copolymer containing 50% by weight of the polyaryl ether sulfone (component A) used in Example 1, a repeating unit of an α, β-unsaturated cyclic imide and a repeating unit of an aromatic vinyl compound (Component B) Resin was prepared in the same manner as in Example 1 except that 35% by weight of an acrylic elastomer (KCA-301 manufactured by Kureha Chemical Industry Co., Ltd.) was mixed at a kneading temperature of 300 ° C. in addition to 35% by weight. A composition was obtained. Each evaluation experiment was performed in the same manner as in Example 1 using this composition. Notched Izod impact strength is 45kgf ・ cm / cm and deflection temperature under load is 160
° C.

Examples 5 to 6 A rubber graft-acrylonitrile-styrene copolymer rubber was synthesized by the following method. Ethylene-propylene-
Ethylidene norbornene copolymer rubber (EPDM) 7kg
1.3 kg of acrylonitrile and 3.
8 kg, 20 g of benzoyl peroxide, 60 ° C,
The mixture was polymerized under stirring for 5 hours, coagulated with a small amount of sulfuric acid, washed by filtration, dried and dried to give EPDM graft-acrylonitrile-
A styrene copolymer rubber was obtained. The rubber content of the obtained rubber copolymer was 70% by weight, and the average particle diameter of the rubber was 300%.
nm.

A resin composition was obtained in the same manner as in Example 1 at the ratios shown in Table 2. Each evaluation experiment was performed in the same manner as in Example 1 using this composition. The results are shown in Table 2.

Comparative Example 1 In Example 2, a polysulfone (A) having a structure represented by the following formula was used instead of the polyaryl ether sulfone of the component (A).
MOCO P-1700)

[0039]

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A resin composition was obtained in the same manner as in Example 1.
Each evaluation experiment was performed in the same manner as in Example 1 using this composition. The results are shown in Table 3.

Comparative Examples 2 and 3 A resin composition was obtained in the same manner as in Example 1 except that the mixing ratio was as shown in Table 1. Each evaluation experiment was performed in the same manner as in Comparative Example 1 using this composition. The results are shown in Table 3.

Comparative Example 4 In Example 4, the polyarylether sulfone of the component (A) was replaced with a polysulfone (AM
OCO P-1700)

[0043]

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A resin composition was obtained in the same manner as in Example 4.
Each evaluation experiment was performed in the same manner as in Example 4 using this composition. The results are shown in Table 3.

[0045]

[Table 1]

[0046]

[Table 2]

[0047]

[Table 3]

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-61-66750 (JP, A) JP-A-2-281031 (JP, A) JP-A-1-313563 (JP, A) JP-A-57-167 109850 (JP, A) JP-A-7-18172 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08L 1/00-101/14

Claims (1)

(57) [Claims] (A) It comprises a repeating unit of the following formulas (I) and (II): The ratio of the repeating unit (I) to the repeating unit (II) is 10 to 70:30 to 90
(Mol%) A copolymer containing 95 to 5% by weight of a polyaryl ether sulfone having a structure of (A) and (B) a repeating unit of an α, β-unsaturated cyclic imide and a repeating unit of an aromatic vinyl compound A thermoplastic resin composition comprising 95% by weight.