JPH0598147A - Modified polyphenylene ether-based resin composition - Google Patents

Abstract

PURPOSE:To provide the title composition excellent in molding processability, impact resistance and thermal stability, suitable for e.g. large-size molding, comprising each specific modified polyphenylene ether-based resin, impact- resistant styrene-based resin, modified block copolymer resin and styrenebased resin at specified proportion. CONSTITUTION:The objective composition comprising (A) 10-90 pts.wt. of a polyphenylene ether-based resin modified with an unsaturated carboxylic acid like maleic acid or its derivative, (B) 90-10 pts.wt. of an impact-resistant styrene- based resin containing high-cis-conjugated diene rubber >=50% in 1,4-cis bond and <=10% in 1,2-vinyl bond, (C) 0-80 pts.wt. of a styrene-based resin, and (D) 0-20 pts.wt. of a modified block copolymer resin made up of (1) styrene-based polymer block modified with an unsaturated carboxylic acid such as maleic acid or its derivative and (2) olefin elastomer block.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyphenylene ether resin composition having excellent impact resistance and thermal stability, and excellent secondary processability such as moldability and coating adhesion. More specifically, a modified polyphenylene ether-based resin modified with an unsaturated carboxylic acid or a derivative thereof is used as the polyphenylene ether-based resin, which has 50% or more of 1,4-cis bonds and has 1,2-vinyl bonds of 10 or less.
The present invention relates to obtaining a polyphenylene ether-based resin composition excellent in the above-mentioned properties and particularly suitable for large-scale molding applications by reinforcing with a high-impact styrene-based resin containing a high cis conjugated diene-based rubber of not more than%.

[0002]

2. Description of the Related Art Polyphenylene ether resin has heat resistance,
It is a resin that has excellent properties such as electrical characteristics, acid resistance, alkali resistance, and low specific gravity and low water absorption, but on the other hand, its low fluidity makes it difficult to perform melt molding and has low impact strength. Therefore, it also has the drawback of being slightly brittle.
In order to remedy these drawbacks at the same time, a technique of blending high impact polystyrene containing a polybutadiene component has been developed and disclosed in US Pat. No. 3,383,435. However, due to the chemical instability of the 1,2-vinyl bond, changes in physical properties due to oxidative deterioration are large,
It was very difficult to avoid deterioration of physical properties due to melt molding, heat exposure or light exposure. On the other hand, a technique of reinforcing with a hydrogenated styrene-butadiene block copolymer containing almost no double bond is disclosed in, for example, Japanese Patent Laid-Open No.
Although disclosed in JP-A-71742, even though this technology has excellent thermal stability, since rubber particles of the impact-resistant styrene resin do not contain dispersed particles of the styrene polymer, the rubber efficiency is low and the resistance is high. It was necessary to add a large amount of rubber component in order to improve the impact resistance. Moreover, since the affinity between the hydrogenated styrene-butadiene block copolymer and the polyphenylene ether resin is not always sufficient,
Peeling often occurred in the molded product. In addition, the higher the hydrogenation rate of the 1,4-butadiene component in the butadiene block, the higher the glass transition point of the rubber component, so that sufficient low temperature impact resistance cannot be obtained by such a technique alone. Further, recently, demands for secondary processability such as enlargement of molded products and coating adhesion have been increasing, and conventional polyphenylene ether-based resin compositions have insufficient secondary processability, particularly coating adhesion.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyphenylene ether resin with molding processability and impact resistance by a melt processing step in which the above problems are solved or by heating such as heat exposure. The purpose of the present invention is to obtain a polyphenylene ether-based resin composition which does not cause deterioration in physical properties and has an excellent balance of impact resistance, coating adhesion and the like as compared with conventional resin compositions, and which is particularly suitable for large-scale molding.

[0004]

As a result of intensive studies, the present inventors have found that when a polyphenylene ether resin is reinforced with an impact-resistant styrene resin containing a conjugated diene rubber, the polyphenylene ether resin is unsaturated as a polyphenylene ether resin. By using a modified polyphenylene ether resin modified with a carboxylic acid or a derivative thereof, it was found that excellent moldability and coating adhesion can be achieved, and the bonding amount of 1,2-vinyl in the conjugated diene rubber component is It was found that oxidative deterioration is promoted when the amount increases, resulting in deterioration of physical properties.
It was found that there is an appropriate 1,4-cis bond amount and 1,2-vinyl bond amount for maintaining the physical property balance. Further, it has been found that the effect is further improved by adding a modified block copolymer resin composed of a styrene polymer block and an olefin elastomer block modified with an unsaturated carboxylic acid or a derivative thereof as required. The present invention has been completed.

That is, the present invention comprises (A) 10 to 90 parts by weight of a modified polyphenylene ether resin modified with an unsaturated carboxylic acid or a derivative thereof, and (B) 1,4-
90 to 10 parts by weight of a high-cis conjugated diene rubber having a cis bond content of 50% or more and a 1,2-vinyl bond content of 10% or less, and (C) a styrene resin content of 0 to 80. (A) component of 0 to 20 parts by weight of a modified block copolymer resin comprising a styrene-based polymer block modified with an unsaturated carboxylic acid or a derivative thereof and an olefin-based elastomer block.
It is intended to provide a polyphenylene ether resin composition comprising component (B), component (C) and component (D), which is excellent in molding processability, thermal stability, impact resistance and coating adhesion.

The modified polyphenylene ether resin which is the component (A) of the composition of the present invention is a modified polyphenylene ether resin obtained by modifying the following polyphenylene ether resin with an unsaturated carboxylic acid or a derivative thereof. The polyphenylene ether resin used in the present invention is represented by the general formulas (1) and (2)

[0007]

[Chemical 1]

[0008]

[Chemical 2]

(Wherein R1, R2, R3, R4, R5
R6 is a monovalent residue such as an alkyl group having 1 to 4 carbon atoms, an aryl group, halogen, and hydrogen, and R5 and R6 are not hydrogen at the same time) as a repeating unit, and the constitutional unit is represented by the general formula (1) or ( A homopolymer or copolymer of 2) can be used. A typical example of a homopolymer of a polyphenylene ether resin is poly (2,6-dimethyl-
1,4-phenylene ether, poly (2-methyl-6-
Ethyl 1,4-phenylene) ether, poly (2,6-)
Diethyl-1,4-phenylene) ether, poly (2-
Ethyl-6-n-propyl-1,4-phenylene) ether, poly (2,6-di-n-propyl-1,4-phenylene) ether, poly (2-methyl-6-n-butyl-1,) 4-phenylene) ether, poly (2-ethyl-)
6-isopropyl-1,4-phenylene) ether, poly (2-methyl-6-chloroethyl-1,4-phenylene) ether, poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether, poly Homopolymers such as (2-methyl-6-chloroethyl-1,4-phenylene) ether are mentioned.

The polyphenylene ether copolymer is 2,
Copolymer of 6-dimethylphenol and 2,3,6-trimethylphenol or copolymer of o-cresol or 2,3,6-trimethylphenol and o-
It includes a polyphenylene ether copolymer mainly composed of a polyphenylene ether structure such as a copolymer with cresol.

The high cis conjugated diene rubber used in the present invention contains at least 50% by weight of 1,4-cis bonds,
The 1,2-vinyl bond needs to be 10% by weight or less. This rubber can be prepared in a known manner, for example, by the following heterogeneous catalysts: chromium compounds adsorbed on an inorganic support, or organometallic compounds (eg trialkylaluminium) and transition metal compounds (eg halogenides, especially titanium chloride, titanium iodide). Alternatively, butadiene is produced by stereoregular polymerization in an inert hydrocarbon solution using a catalyst containing a reaction product with a lithium halogenide). In the preferred polybutadiene, the 1,4-cis bond content is greater than 85% by weight of the polybutadiene, and the particularly preferred polybutadiene is the 1,4-cis bond content greater than 95% by weight.

Examples of the styrene resin used in the present invention include styrene compounds, compounds copolymerizable with styrene compounds, and rubbery polymers. The styrene compound is represented by the general formula (3)

[0013]

[Chemical 3]

(Wherein R represents hydrogen, lower alkyl or halogen, Z is selected from the group consisting of vinyl, hydrogen, halogen and lower alkyl, and p is an integer of 0 to 5) Means Specific examples of these include styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert-butylstyrene and ethylstyrene. Further, as the compound copolymerizable with the styrene compound, methacrylic acid esters; methyl methacrylate, ethyl methacrylate, etc., unsaturated nitrile compounds; acrylonitrile, methacrylonitrile, etc.,
Examples thereof include acid anhydrides such as maleic anhydride, which are used together with styrene compounds. Examples of the rubbery polymer include conjugated diene rubber and ethylene-propylene copolymer rubber.

In the present invention, the content of the high-impact styrene resin containing the high cis conjugated diene rubber is 90 to 10.
It is preferably selected from the range of parts by weight. Content is 9
When it exceeds 0 parts by weight, the necessary amount of polyphenylene ether resin cannot be added, and when it is less than 10 parts by weight, the high cis conjugated diene rubber cannot be sufficiently contained, resulting in impact resistance and environmental cracking resistance. It is not preferable because the property cannot be improved sufficiently.

In the present invention, the styrenic resin is used to control the heat distortion temperature and the molding processability, and if the purpose is achieved by the high impact styrenic resin containing the high cis conjugated diene rubber, it is not necessary to add it. However, if necessary, up to 80 parts by weight can be added. If it exceeds 80 parts by weight, the impact-resistant styrene-based resin containing the polyphenylene ether-based resin and the high cis conjugated diene rubber cannot be added in the required amount, which is not preferable.

The method for producing the impact resistant styrene resin of the present invention is not limited, and any of bulk polymerization, solution polymerization, emulsion polymerization and suspension polymerization well known to those skilled in the art may be used. .. The modified block copolymer resin, which is the component (D) of the composition of the present invention, is a modified block copolymer resin obtained by modifying the block copolymer with an unsaturated carboxylic acid or a derivative thereof.

The block copolymer as the raw material of the component (D) referred to in the present invention is a block copolymer comprising at least one styrene polymer block and at least one olefin elastomer block. The styrene-based polymer block referred to in the present invention is specifically represented by the general formula (3)

[0019]

[Chemical 4]

(Wherein R represents hydrogen, lower alkyl or halogen, Z is selected from the group consisting of vinyl, hydrogen, halogen and lower alkyl, and p is an integer of 0 to 5) Is a polymer or copolymer block derived from The olefin elastomer block referred to in the present invention includes monoolefins such as ethylene, propylene, 1-butene and isobutylene, conjugated diolefins such as butadiene, isoprene and 1,3-pentadiene, 1,4-hexadiene and norbornene derivatives. A polymer block having a form in which one or more olefin compounds selected from non-conjugated diolefins are polymerized or copolymerized, and the unsaturation degree of the block is 20% or less. Therefore, when the above diolefins are used as the constituent monomers of the olefin elastomer block, the degree of unsaturation of the block portion is 2
Measures to reduce the degree of unsaturation, such as hydrogenation, must be taken to the extent that it does not exceed 0%. Further, a styrene compound may be randomly copolymerized with the olefin elastomer block. The method for obtaining the modified compound of the component (A) and the component (D) is not limited, but the most useful method is to melt the original polymer and the unsaturated carboxylic acid or its derivative and, if necessary, an organic peroxide. It is a method of kneading. It is also useful to separately prepare the component (A) and the component (D), but it is also a useful means to carry out the modification treatment simultaneously in the coexistence of the polyphenylene ether resin and the block copolymer. Furthermore, in order to control the amount of modification, an unmodified original polymer may be added to the final composition within a range that does not impair the effects of the present invention.

Examples of unsaturated carboxylic acids or their derivatives used in the present invention include maleic acid, fumaric acid, itaconic acid, halogenated maleic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, endo-cis. -Bicyclo [2,2,1] -5-heptene-2,3-dicarboxylic acid and acid anhydrides, esters, amides, imides, etc. of these dicarboxylic acids, acrylic acid, methacrylic acid, etc., and esters of these monocarboxylic acids, Examples thereof include amide.
These can be used not only as one type but also as a mixture of two or more types. Of these, unsaturated dicarboxylic acids or derivatives thereof are preferable, and maleic anhydride is particularly preferable.

The radical initiator used in the present invention is an organic or inorganic radical generator usually used as a polymerization catalyst for vinyl compounds. Of these, organic peroxides are preferable. Specific examples include tertiary butyl hydroperoxide, cumene hydroperoxide,
Ditertiary butyl peroxide, dicumyl peroxide,
2,5-dimethyl-2,5-di (tertiary butyl peroxy) hexane, isobutyl peroxide, benzoyl peroxide, diisopropyl peroxy carbonate,
Examples thereof include tertiary butyl peroxybenzoate, α, α′-azobisisobutyl nitrile, tertiary butyl peroxylaurate and the like.

The amount of the molecular unit containing a carboxylic acid group or its derivative group contained in the modified polyphenylene ether resin, that is, the addition amount of the unsaturated carboxylic acid or its derivative is the whole modified polyphenylene ether resin used in the present invention. The average value is 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of the polyphenylene ether resin. When the molecular unit containing the carboxylic acid group or its derivative group is less than 0.05 parts by weight, almost no improvement effect is recognized as compared with the unmodified polyphenylene ether, and even if it exceeds 10 parts by weight, it is The improvement effect is not so remarkable.

The amount of the molecular unit containing the carboxylic acid group or its derivative group contained in the modified block copolymer, that is, the addition amount of the unsaturated carboxylic acid or its derivative is the whole modified block copolymer used in the present invention. As an average value of 0.05 per 100 parts by weight of the block copolymer
10 to 10 parts by weight, preferably 0.2 to 5 parts by weight. When the molecular unit containing a carboxylic acid group or its derivative group is less than 0.05 parts by weight, almost no improvement effect is recognized as compared with the unmodified block copolymer, and even if it exceeds 10 parts by weight, The improvement effect is not remarkable as compared with the case. When the amount of the molecular unit containing a carboxylic acid group or its derivative group exceeds 0.05 parts by weight, an unmodified block copolymer can be used in combination, and the amount that can be used in combination is a carboxylic acid group or its derivative. With respect to the total of the modified and unmodified block copolymer, the amount of the molecular unit containing a group is
It is preferably 0.05 part by weight or more, and the amount of the unmodified block copolymer does not exceed the amount of the modified block copolymer.

In the present invention, the content of the modified polyphenylene ether resin as the component (A) is preferably in the range of 10 to 90 parts by weight. When the content is less than 10 parts by weight,
The modified polyphenylene ether resin is not preferable because the improvement effect is not sufficiently exhibited, and when it exceeds 90 parts by weight, it is not preferable because the moldability or impact resistant styrene resin cannot be added.

The component (C) is mainly used for controlling the processability of the composition and the heat distortion temperature. When the amount of the component exceeds 80 parts by weight, the properties of the polyphenylene ether resin are significantly impaired, which is not preferable. The component (D) is useful for further improving impact resistance and oil resistance. However, if the amount of the component exceeds 20 parts by weight, the rigidity is extremely lowered, which is not preferable.

Other additives to the composition of the present invention, such as:
Plasticizers, stabilizers, UV absorbers, flame retardants, colorants, mold release agents and fibrous reinforcing agents such as glass fibers and carbon fibers, and fillers such as glass beads, calcium carbonate and talc may be added. it can. As the stabilizer, one or a combination of phosphite esters, hindered phenols, alkanolamines, acid amides, dithiocarbamic acid metal salts, inorganic sulfides and metal oxides can be used. ..

As the flame retardant, aromatic phosphate ester,
Red phosphorus, aromatic halogen compounds, antimony trioxide, etc. are particularly effective. Any method may be used as a method of mixing the respective components constituting the present invention. For example, an extruder, a heating roll, a Banbury mixer, a kneader or the like can be used.

[0029]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples. Hereinafter,% and part represent weight% and part by weight, respectively. In addition,
The impact-resistant styrene resin used in the following examples and comparative examples was prepared by the manufacturing method described below. Table 2 shows the impact-resistant styrene resins used in Examples and Comparative Examples, and the conjugated diene rubber and the high cis conjugated diene rubber used in the preparation thereof.

Production Example 1 Production of Impact Resistant Styrenic Resin {Component (B), Corresponding to Table 1} The impact resistant styrene resin used in the examples was produced by the bulk polymerization method. A typical example will be described below. 94 parts of 1,4-cis bond, 3% of 1,2-vinyl bond, 3% of 1,4-trans bond and 10 parts of high cis polybutadiene having a 5% styrene solution viscosity of 65 centipoise, 90 parts of styrene and ethylbenzene. It is dissolved in 8 parts and 0.05 parts of benzoyl peroxide and 0.0 parts with respect to styrene.
Add 1 part of α-methylstyrene dimer and add 4 parts at 80 ° C.
Polymerization was carried out with stirring at 110 ° C. for 4 hours and 150 ° C. for 4 hours. Further, heat treatment was performed at about 230 ° C. for 30 minutes, and then unreacted styrene and ethylbenzene were vacuum removed to obtain an impact-resistant styrene-based resin. The content of polybutadiene in the obtained impact-resistant styrene-based resin was 11%, and the average particle diameter of partially hydrogenated polybutadiene in the state of containing dispersed particles of polystyrene was 2.7 μm.

Production Example 2; Preparation of modified polyphenylene ether resin {component (A)}, intrinsic viscosity 0.50 (measured in chloroform at 30 ° C.)
Of poly (2,6-dimethyl-1,4-phenylene) ether (PPE) of 100 parts by weight of polystyrene 50
Parts, maleic anhydride 2 parts, and perbutyl D 0.5 parts uniformly mixed, and then, using an extruder, under a nitrogen atmosphere at 300 ° C.
The mixture was melt-kneaded in and maleated to obtain a modified polyphenylene ether resin mixture. The amount of maleic anhydride added to 100 parts of the polyphenylene ether resin determined by titration with sodium methylate was 0.8 parts.

In the examples, the amount of maleic anhydride added to the components in the composition was measured as follows. The composition was dissolved in dichloromethane at 38 ° C and then filtered, and then the solution portion was allowed to stand at -5 ° C for 24 hours to precipitate a modified polyphenylene ether resin, which was filtered to separate the resin. did. Next, the filtrate was added dropwise to methanol, polystyrene was reprecipitated and filtered, and this was separated. The amount of maleic anhydride added to each component was measured by titration with sodium methylate.

No addition of maleic anhydride to polystyrene was observed. Production Example 3; Preparation of modified block copolymer resin {(D) component}, 2 parts of maleic anhydride, perbutyl D (to 100 parts of a block copolymer consisting of a styrene polymer block and an olefin elastomer block) After uniformly mixing 0.5 parts of Nippon Oil & Fats Co., Ltd., 260 using an extruder
The mixture was melt-kneaded at 0 ° C. to carry out a maleation reaction to obtain a modified block copolymer mixture. The addition amount of maleic anhydride to the block copolymer of the modified block copolymer resin determined by titration with sodium methylate is 1.0 to
It was 1.2 parts.

Production Example 4; Preparation of Simultaneous Modification of Polyphenylene Ether and Block Copolymer (Components (A) and (D) by Simultaneous Modification), Intrinsic Viscosity 0.50 (measured in chloroform at 30 ° C.)
To 50 parts of poly (2,6-dimethyl-1,4-phenylene) ether (PPE), 17 parts of a block copolymer consisting of a styrene polymer block and an olefin elastomer block, 33 parts of polystyrene, maleic anhydride After uniformly mixing 0.5 parts of acid and 0.25 part of perbutyl D, the mixture was melt-kneaded at 300 ° C. in a nitrogen atmosphere using an extruder to carry out a maleation reaction to obtain a modified polyphenylene ether resin mixture. Polyphenylene ether resin 1 determined by titration with sodium methylate
The amount of maleic anhydride added to 00 parts was 0.2 part.

In the examples, the amount of maleic anhydride added to the components in the composition was measured as follows. The composition was dissolved in dichloromethane at 38 ° C. and then filtered, and then the solution portion was left at −5 ° C. for 24 hours to precipitate a modified polyphenylene ether resin, which was filtered to separate the resin. .. Next, the filtrate was added dropwise to methanol to reprecipitate polystyrene, which was then filtered and separated.
The amount of maleic anhydride added to each component was measured by titration with sodium methylate.

No addition of maleic anhydride to polystyrene was observed. The amount of maleic anhydride added to the block copolymer of the modified block copolymer resin was 0.8 to 1.2 parts. Next, a method for measuring and evaluating physical properties of the resin composition will be described. (1) Melting index According to JIS K 7210 Temperature: 250 ° C., Load: 10 Kg An injection molding machine (manufactured by Toshiba Machine Co., IS80C, cylinder temperature 280 ° C. or 290 ° C.) is used to prepare a test piece,
The following (2) to (5) were measured.

(2) Heat distortion temperature ASTM D648, load: 18.6 Kg / cm ² (3) Izod impact strength ASTM D256, notched temperature: 23 ° C. (4) Molding stability Injection molding temperature 280 ° C. (or 290) 310 ° C (or 3 ° C) against Izod impact strength of the molded product
After being retained in the cylinder at 20 ° C. for 10 minutes (or 15 minutes), it was judged from the retention rate of the Izod impact strength of the molded product.

Injection molding machine (manufactured by Toshiba Machine Co., IS8
75 × 75 × 3mm at 0C, cylinder temperature 290 ℃)
A test piece was prepared and the following (7) to (8) were measured. (5) Coating adhesion After coating with a commercially available urethane-based paint, conduct a cross-cut test,
The following ranks were given according to the number of peeled squares in all squares (100 pieces).

◎: Peeling number is 0 ◯: Peeling number is 1 to 10 Δ: Peeling number is 11 to 20 ×: Peeling number is 21 to 100

[0040]

Example 1 35 parts of the modified polyphenylene ether resin prepared in Production Example 2, No. 1 in Table 1. 54 parts of high impact polystyrene (hereinafter abbreviated as HIPS) of No. 1, 11 parts of the modified block copolymer resin prepared in Production Example 3 (addition amount of maleic anhydride 1.0 part) and Sumilizer BHT (Hinder manufactured by Sumitomo Chemical Co., Ltd. 1 part of dephenol) was melt-kneaded at a temperature of 280 ° C. using an extruder to obtain a resin composition.
Table 2 shows the results of physical property tests of the resin composition.

[0041]

Example 2 7 parts of modified polyphenylene ether resin prepared in Production Example 2 and poly (2,6-dimethyl-1,2) with an intrinsic viscosity of 0.50 (measured in chloroform at 30 ° C.)
4-phenylene) ether (hereinafter abbreviated as PPE) 2
No. 8 of Table 1, No. Impact-resistant polystyrene of 1 (hereinafter H
Abbreviated as IPS) 54 parts, modified block copolymer resin prepared in Production Example 3 (addition amount of maleic anhydride 1.0 part)
11 parts and Sumilyzer BHT (Sumitomo Chemical's hindered phenol) 1 part were melt-kneaded at a temperature of 280 ° C. using an extruder to obtain a resin composition. Table 2 shows the results of physical property tests of the resin composition.

[0042]

Example 3 Simultaneous modification of the polyphenylene ether and the block copolymer prepared in Production Example 4 (46 parts), N in Table 1
o. 54 parts of high impact polystyrene (hereinafter abbreviated as HIPS) 1 and 1 part of Sumilizer BHT (hindered phenol manufactured by Sumitomo Chemical Co., Ltd.) at 280 ° C. using an extruder.
The resin composition was obtained by melt-kneading at the temperature of. Table 2 shows the results of physical property tests of the resin composition.

[0043]

Comparative Example 1 Intrinsic viscosity 0.50 (in chloroform, 30
Poly (2,6-dimethyl-1,4-phenylene) ether (hereinafter abbreviated as PPE) (measured at C) was used in Example 1.
The same operation as in Example 1 was carried out except that the modified polyphenylene ether resin was used instead of the modified polyphenylene ether resin. The results are shown in Table 2.

[0044]

Comparative Example 2 No. 1 in Table 1 Table 1 instead of HIPS 1
No. Comparative Example 1 was repeated except that HIPS of No. 2 was used to obtain a resin composition. The results are shown in Table 2.

[0045]

Example 4 45 parts of the modified polyphenylene ether resin prepared in Production Example 2, No. 1 in Table 1. 55 parts of HIPS 1 and 1 part of Sumilizer BHT (hindered phenol manufactured by Sumitomo Chemical Co., Ltd.) were melt-kneaded at a temperature of 280 ° C. using an extruder to obtain a resin composition. Table 3 shows the results of physical property tests of the resin composition.

[0046]

Example 5 9 parts of the modified polyphenylene ether resin prepared in Production Example 2 and poly (2,6-dimethyl-1,2) with an intrinsic viscosity of 0.50 (measured in chloroform at 30 ° C.)
4-phenylene) ether (hereinafter abbreviated as PPE) 3
No. 6 of Table 1, No. 6 of Table 1. 55 parts of HIPS 1 and 1 part of Sumilizer BHT (hindered phenol manufactured by Sumitomo Chemical Co., Ltd.) were melt-kneaded at a temperature of 280 ° C. using an extruder to obtain a resin composition. Table 3 shows the results of physical property tests of the resin composition.

[0047]

Comparative Example 3 A resin composition was prepared by repeating Example 3 except that PPE having an intrinsic viscosity of 0.50 (measured in chloroform at 30 ° C.) was used in place of the modified polyphenylene ether resin used in Example 3. Got Table 3 shows the results of physical property tests of the resin composition.

[0048]

Comparative Example 4 No. 1 in Table 1 Table 1 instead of HIPS 1
No. Comparative Example 3 was repeated except that HIPS of 2 was used to obtain a resin composition. The results are shown in Table 3.

[0049]

[Table 1]

[0050]

[Table 2]

[0051]

[Table 3]

[0052]

EFFECTS OF THE INVENTION The composition of the present invention does not deteriorate in physical properties due to heating in a melt processing step or heat exposure, and has an excellent balance of impact resistance, coating adhesion and the like as compared with conventional resin compositions. It is industrially useful and suitable for molding.

Claims (1)

[Claims] 1. (A) 10 to 90 parts by weight of a modified polyphenylene ether resin modified with an unsaturated carboxylic acid or a derivative thereof, (B) having 50% or more of 1,4-cis bond, and Two
-Impact-resistant styrene resin 90 to 10 parts by weight containing a high cis conjugated diene rubber having a vinyl bond of 10% or less, (C) styrene resin 0 to 80 parts by weight, (D) unsaturated carboxylic acid or its derivative Block copolymer resin comprising a styrene-based polymer block and an olefin-based elastomer block modified by
To 20 parts by weight of the component (A), the component (B), the component (C), and the component (D) having excellent moldability, thermal stability, impact resistance, and coating adhesion. object.