JPH07196867A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition excellent in heat resistance, moldability and impact resistance by mixing a polyarylethersulfone of a specified structure with a copolymer of an alpha,beta-unsaturated cyclic imide with an aromatic vinyl compound. CONSTITUTION:The resin composition comprises 95-5wt.% polyarylethersulfone composed of repeating units of formula I and repeating units of formula II in a molar ratio of (10-70):(30-90) and 5-95wt.% copolymer comprising repeating units of an alpha,beta-unsaturated cyclic imide and repeating units of an aromatic vinyl compound. The molecular weight of the polyarylethersulfone is desirably such that the reduced viscosity is 0.2-1.0 when measured in the 0.5g/100mol solution in N-methyl-2-pyrrolidone at 30 deg.C. Examples of the alpha,beta-unsaturated cyclic imide include maleimide or N-phenylmaleimide. Examples of the aromatic vinyl compounds include styrene and alpha-methylstyrene.

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 an excellent balance of heat resistance, moldability and impact resistance.

[0002]

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

For example, Japanese Patent Publication No. 46-37896 and Japanese Patent Publication No. 49
-27668 or JP-A-56-167752
Composition of BS resin and polyether sulfone, JP-A-56
-16552 discloses a composition with an ABS resin, polysulfone, and an organic silicon compound, and JP-A-56-16552 describes a composition with an ABS resin, polyarylene polysulfone, and a polycarbonate, and JP-A-63-305152. The publication discloses a composition with ABS resin, polysulfone, and polyetherimide. In addition, JP-A-61-667
Japanese Patent Publication 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 the rubber-like polymer in order to improve the impact resistance, and therefore it is unavoidable that the heat resistance is lowered. That is, the balance of physical properties such as heat resistance and impact resistance is not always satisfactory, and improvement is required.

[0005]

OBJECT OF THE INVENTION It is an object of the present invention to provide a thermoplastic resin composition having an excellent balance of heat resistance and impact resistance.

[0006]

[Technical Means for Solving the Problems]
A thermoplastic resin composition comprising a polyaryl ether sulfone having a specific structure and a copolymer containing a repeating unit of an α, β-unsaturated cyclic imide and a repeating unit of an aromatic vinyl compound, has a heat resistance and a molding property. It has been found that it has an excellent balance of properties and impact resistance. The present invention comprises (A) repeating units of the following formulas (I) and (II):

[0007]

[Chemical 2]

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

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

[0010]

[Chemical 3]

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

The production method is as follows:
A polycondensation reaction of a dihalogenodiphenyl sulfone compound and a dihydric phenol compound in the presence of an alkali metal compound,
Alternatively, it can be produced by using hydroquinone and 4,4′-biphenol as the dihydric phenol compound in a predetermined ratio in the polycondensation reaction of the dimetallogene diphenyl sulfone compound and the alkali metal di-salt of the dihydric phenol synthesized in advance.

In the dihydric phenol compounds hydroquinone and 4,4'-biphenol, at least one of the hydrogen atoms on the benzene ring is a suitable substituent (for example, a lower alkyl group such as a methyl group, an ethyl group or a propyl group, 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 of the repeating unit (I) to the repeating unit (II) can be adjusted by the charging ratio in the polycondensation reaction of hydroquinone and 4,4'-biphenol. In the composition of the present invention, the ratio of the repeating unit (I) to the repeating unit (II) of the polyarylethersulfone is 10 to 70:30.
~ 90 (mol%). If it 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 polyarylethersulfone is not particularly limited, but the reduced viscosity (measured at 30 ° C.) of a solution of N-methyl-2-pyrrolidone at a concentration of 0.5 g / 100 ml ( ηsp / c) is 0.2 ~
1.0 is preferable, and 0.4 to 0.6 is particularly preferable.

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
-Chlorophenyl) maleimide, aromatic maleimide such as 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 imide may be used as a mixture of two or more kinds.

As the aromatic vinyl compound, styrene,
Examples thereof include styrene and styrene derivatives such as α-methylstyrene, p-methylstyrene, p-chlorostyrene, pt-butylstyrene, and styrenesulfonic acid.

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

A copolymer containing each of the above components as a monomer is 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 composition of each component of the copolymer of the component (B) is not particularly limited, but the α, β-unsaturated cyclic imide is preferably 5 to 50 mol%. Aromatic vinyl compounds are
50 to 95 mol% is preferable.

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

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

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

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

The composition of the present invention may contain a rubber-like polymer in addition to the above components. Examples of the rubber-like polymer include polybutadiene rubber, ethylene-propylene copolymer rubber, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, styrene-
Examples thereof 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. In addition, 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 their hydrogenated products (SEB, SEB,
SEBS, SEP, SEPS) and modified functional groups thereof, or a graft copolymer obtained by grafting styrene and / or acrylonitrile or methyl methacrylate onto these rubber-like polymers, styrene-butadiene copolymer rubber and styrene-acrylonitrile. ABS resin, AAS resin, ACS resin, AES resin, MBS resin, MAS resin, etc. which consist of a blend with resin etc. or these combinations can be mentioned. Examples of the production method include known production methods such as emulsion polymerization method, suspension polymerization method, solution polymerization method, and bulk polymerization method. By adding the above rubber-like resin, physical properties such as impact resistance (notched Izod strength) of the composition are further improved.

Polyethylene, polypropylene, ethylene / vinyl acetate copolymers, butadiene / acrylate / styrene copolymers, acrylate-based elastic copolymers, polyvinyl chloride-based copolymers are also used as long as the characteristics of the composition of the present invention are not impaired. Resin, polyester resin, thermoplastic resin such as polyamide resin, thermosetting resin such as phenol resin, melamine resin, silicone resin, epoxy resin, glass fiber, carbon fiber, boron fiber, silicon carbide fiber, asbestos fiber, Reinforcing agents such as metal fibers, clay, mica, silica, graphite, glass beads, calcium carbonate, talc, etc., or antioxidants, heat stabilizers, UV inhibitors, flame retardants, pigments, antistatic agents, coloring One or more agents may be added.

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

There is no particular limitation on the method of blending the respective components of the present invention, but they can be blended by kneading using an ordinary kneader. For example, it can be obtained as pellets by melt-kneading using a single-screw extruder, a twin-screw extruder, a mixing roll, a Banbury mixer or the like. The pellets are molded into an arbitrary shape such as a film, a pipe or a tube by injection molding, blow molding, extrusion molding or the like.

[0029]

INDUSTRIAL APPLICABILITY In the present invention, a composition comprising a copolymer containing a polyaryl ether 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 high impact resistance is obtained and the decrease in heat resistance is suppressed as compared with the conventionally known composition using a sulfone 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 various automotive parts, electronic and electrical parts, mechanical parts, medical and tableware fields. It can be used as a material.

[0030]

【Example】

(Preparation method of test piece) After the composition was pelletized, the test piece was manufactured by Sumitomo Heavy Industries, Ltd. injection molding machine Nestal SG100 (mold clamping force 10
0 ton) was used to prepare a test piece. (Test method of test piece) (1) Deflection temperature under load Tested according to ASTM D648. (2) Izod impact strength (with notch) It 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 added to 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 which had been 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 completion of the reaction, in order to separate the inorganic substances from the polymerization solution, the polymerization solution was obtained by filtering at a nitrogen pressure of 1.5 kg / cm ² . Pour 300 g of polymerization solution into 2000 ml of ethanol, and add 50
The polymer was precipitated while stirring at 00 rpm, filtered and separated to obtain a polymer. 50 g of this polymer was added to ethanol 500
After washing with ml, it was dried at 90 ° C. to obtain a powder of polyarylethersulfone (component A). The reduced viscosity (ηsp / c) of the obtained polyarylethersulfone was 0.52, and the ratio of the repeating unit (I) to the repeating unit (II) was 50:50 (mol%).
Met.

As the copolymer (component B) containing the repeating unit of α, β-unsaturated cyclic imide and the repeating unit of aromatic vinyl compound, one synthesized by the following method was used. A monomer mixture consisting of 80% by weight of styrene and 20% by weight of N-phenylenemaleimide was dispersed in water at a concentration of 20%, and suspension polymerization was carried out for 5 hours at 70 ° C. with stirring 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 above component A and 30% by weight of the component B were mixed, and this mixture was melt-kneaded at 300 ° C. using a 30 mmφ twin screw extruder manufactured by Nakatani Machinery Co., Ltd. I got a thing. Each evaluation experiment was conducted using this composition.
The results are shown in Table 1.

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

Example 4 Copolymer containing 50% by weight of the polyaryl ether sulfone (component A) used in Example 1 and a repeating unit of α, β-unsaturated cyclic imide and a repeating unit of aromatic vinyl compound. (Component B) Resin was prepared in the same manner as in Example 1 except that, in addition to 35% by weight, 15% by weight of an acrylic elastic body (KCA-301 manufactured by Kureha Chemical Industry Co., Ltd.) was mixed at a kneading temperature of 300 ° C. A composition was obtained. Each evaluation experiment was conducted in the same manner as in Example 1 using this composition. Notched Izod Impact strength is 45 kgf ・ cm / cm and deflection temperature under load is 160
It was ℃.

Examples 5 to 6 Rubber graft-acrylonitrile-styrene copolymer rubber was synthesized by the following method. Ethylene-propylene-
Ethylidene norbornene copolymer rubber (EPDM) 7kg
Emulsion containing acrylonitrile 1.3kg, styrene 3.
Add 8kg, add 20g benzoyl peroxide, 60 ℃,
Polymerize for 5 hours with stirring, coagulate with a small amount of sulfuric acid, wash by filtration, dry, and 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.
was nm.

A resin composition was obtained in the same manner as in Example 1 in the proportions shown in Table 2. Using this composition, each evaluation experiment was conducted in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 1 In Example 2, the polyaryl ether sulfone of the component (A) was replaced by a polysulfone (A
Except that MOCO P-1700) was used.

[0039]

[Chemical 4]

A resin composition was obtained in the same manner as in Example 1.
Each evaluation experiment was conducted 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 ratios shown in Table 1 were used. Each evaluation experiment was conducted 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 polyaryl ether sulfone of the component (A) was replaced by a polysulfone (AM
Except that OCO P-1700) was used.

[0043]

[Chemical 5]

A resin composition was obtained in the same manner as in Example 4.
Each evaluation experiment was conducted 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]

Claims (1)

[Claims] 1. (A) consists of repeating units of the following formulas (I) and (II): The ratio of repeating units (I) to repeating units (II) is 10-70: 30-90
Copolymer containing 95 to 5% by weight of polyaryl ether sulfone having a structure of (mol%) and (B) α, β-unsaturated cyclic imide repeating unit and aromatic vinyl compound repeating unit 5 to A thermoplastic resin composition comprising 95% by weight.