JPH03422B2 - - Google Patents

Description

[Detailed description of the invention]

<Industrial Application Field> The present invention consists of a modified polyphenylene ether, a polyamide, and a block copolymer elastomer, and has high impact resistance as represented by Izot impact strength,
The present invention relates to a thermoplastic resin composition that is well-balanced and excellent in rigidity represented by flexural modulus, heat resistance represented by heat distortion temperature, and moldability. <Prior Art> Polyphenylene ether is a resin that has excellent properties such as heat resistance and rigidity, and is attracting attention as an engineering plastic, but it has poor impact resistance. Furthermore, since the resin has a high melt viscosity, high temperatures are required to mold the resin itself while melting it, which causes various undesirable problems such as discoloration and oxidative deterioration. In order to solve this problem, a resin composition of polyphenylene ether and rubber-modified polystyrene resin is disclosed in US Pat. No. 3,383,435. Furthermore, a method has been proposed in which a rubber-like elastic body is blended in order to improve the impact resistance of a resin composition of polyphenylene ether and rubber-modified polystyrene resin. For example, Japanese Patent Publication No. 57-56941 discloses a vinyl aromatic hydrocarbon block in which A is polymerized in a composition consisting of polyphenylene ether and rubber-modified polystyrene resin, and B is a vinyl aromatic hydrocarbon block in which the degree of unsaturation is initialized by hydrogenation. Hydrogenated A-B- which is a diene block whose degree of unsaturation has been reduced to less than 10%
A resin composition containing a type A block copolymer elastomer is disclosed. There are also proposals to improve the moldability and impact resistance of polyphenylene ether by blending polyolefin with it (U.S. Pat. No. 3,361,851 and Japanese Patent Publication No. 42-7069). Publication No.). Furthermore, as another proposal to improve the impact resistance of polyphenylene ether, it has been disclosed that an ethylene/propylene/polyene copolymer (so-called EPDM) is blended (U.S. Patent No.
3920770 specification). As a method to improve the impact resistance of polyamide,
A resin composition made by blending a polybutadiene-based elastomer with polyamide is disclosed in JP-A-52-105952, and a resin composition made by blending a conjugated diene-monovinyl aromatic hydrocarbon block copolymer with polyamide is disclosed. The composition is also disclosed in JP-A-48-89240. For the purpose of improving the fluidity of polyphenylene ether, a resin composition comprising polyphenylene ether and polyamide is disclosed in Japanese Patent Publication No. 45-997. In addition, for the purpose of improving the solvent resistance of polyphenylene ether, polyphenylene ether and polyamide can be obtained by adding a compound having a specific structure such as maleic anhydride and melt-kneading the mixture. A method for producing a resin composition is disclosed in Japanese Patent Publication No. 11966/1983. Further, a resin composition comprising polyphenylene ether modified with a specific compound and polyamide is also disclosed in JP-A-59-66452. In order to improve the impact resistance of a resin composition consisting of polyphenylene ether and polyamide, a partially hydrogenated polymer block A consisting of a monoalkenyl arene terminal polymer block A and a partially hydrogenated polymer block B of a conjugated diene polymer is added. A resin composition containing an A-B-A' type hydrogenated block copolymer is also disclosed in JP-A-53-132053.
It is disclosed in the publication No. In addition, JP-A-56-49753 discloses a resin composition obtained by melt-kneading polyphenylene ether, polyamide, and a specific compound such as maleic anhydride added to polyphenylene ether, polyamide, and a rubber-like substance. Disclosed. <Problems to be Solved by the Invention> However, the resin composition comprising polyphenylene ether and rubber-modified polystyrene resin described in U.S. Pat. No. 3,383,435 does not improve the moldability of polyphenylene ether. However, it cannot be said that it has sufficient impact resistance at a practical level. In the resin composition described in JP-A-57-56941, in which a hydrogenated A-B-A type block copolymer elastomer is blended with a resin composition consisting of polyphenylene ether and rubber-modified polystyrene resin, a small amount of hydrogen is generally added. Blending the added A-B-A type block copolymer elastomer has little effect on improving impact resistance, and conversely, when a large amount is blended, undesirable phenomena such as poor appearance and deterioration of melt flow characteristics due to poor dispersion of the rubber-like elastomer occur. exhibits. Resin composition consisting of polyphenylene ether and polyolefin or EPDM (U.S. Patent No.
Specification No. 3361851, Specification No. 3920770, Tokukosho
42-7069) is a polyolefin or
Because the compatibility between EPDM and polyphenylene ether is inherently poor, phase separation is likely to occur.
The effect of improving impact resistance is also not as great as expected. Although the resin composition prepared by blending a conjugated diene-monovinyl aromatic hydrocarbon block copolymer with a polyamide described in JP-A-48-89240 has improved low impact properties, rigidity, and heat resistance, Since it contains glass fiber, it has poor moldability and also impairs the appearance of the molded product, which is undesirable. The resin composition described in JP-A-52-105952, which is made by blending polyamide with a polyptadiene elastomer, has improved impact resistance, but is inferior in heat resistance. Furthermore, although the resin composition comprising polyphenylene ether and polyamide described in Japanese Patent Publication No. 45-997 has improved fluidity, it has poor impact resistance and is not preferred. A modified polymer consisting of polyphenylene ether, polyamide, and a specific compound typified by maleic anhydride produced by the method described in Japanese Patent Publication No. 60-11966 can be used when melt-kneading polyphenylene ether and polyamide. Since it is manufactured by adding a specific compound at the same time, the impact resistance has been improved to some extent, but it is still not satisfactory. Further, since polyphenylene ether and polyamide are crosslinked via a compound having a specific structure, moldability is impaired, which is not preferable. The resin composition made of modified polyphenylene ether and polyamide described in Japanese Patent Publication No. 59-66452 had insufficient impact resistance and heat resistance, and was still unsatisfactory. The resin composition described in JP-A-53-132053, which is made by blending polyphenylene ether and polyamide with a rubber-like substance, has good impact resistance because the polyphenylene ether is not modified with a compound having a specific structure. Although the performance has improved somewhat, it is not enough. Furthermore, the resin composition described in JP-A No. 56-49753, which is composed of specific compounds such as polyphenylene ether, polyamide, rubber-like substance, and maleic anhydride, is composed of polyphenylene ether, polyamide, rubber-like substance, etc. Because a specific compound is added at the same time as the material is melt-kneaded, the impact resistance has improved considerably, but it is still not satisfactory, and the heat resistance is not as high as expected. That is, a resin with high impact resistance, high rigidity, high heat resistance, and excellent moldability has not yet been obtained, and there is currently a desire to develop a resin that has all of these properties. As a result of extensive research aimed at developing a resin with high impact strength, flexural modulus, and heat resistance, as well as excellent moldability, the present inventors discovered that the carboxyl group and/or carboxylic acid anhydride structure has been modified as a substituent. It has been discovered that the above object can be achieved by blending polyphenylene ether, polyamide and block copolymer elastomer in a specific proportion, and the present invention has been achieved. <Means for solving the problems> That is, the present invention provides the following: (A) General formula

[Formula] (In the formula, Q ₁ , Q ₂ , Q ₃ and Q ₄ are each independently hydrogen, halogen,
a polyphenylene ether selected from the group consisting of hydrocarbon, halohydrocarbon, hydrocarbonoxy, and halohydrocarbonoxy, where n represents the total number of monomer units and is an integer of 20 or more; 0.1 to 20 parts by weight of a 1,2-substituted olefin compound having a carboxyl group or carboxylic acid anhydride structure based on 100 parts by weight of polyphenylene ether;
Polyphenylene ethers 5 to 90 having carboxyl groups and/or carboxylic acid anhydride structures as part of substituents obtained by reaction in the presence of 0.1 to 30 parts by weight of a radical generator per 100 parts by weight
% by weight, (B) polyamide 5-90% by weight and (C) A-
B-A' type block copolymer elastomer (where A,
A' is a polymerized vinyl aromatic hydrocarbon block of the same or different kind, and B is a polymerized conjugated diene block) and/or in the block copolymer elastomer, the intermediate polymer block part B is hydrogenated. Hydrogenation A-B-
The object of the present invention is to provide a thermoplastic resin composition containing 5 to 60% by weight of an A' type block copolymer elastomer (A, A', and B are defined as above). The thermoplastic resin composition of the present invention comprises (A) a modified product of polyphenylene ether, (B) polyamide, and (C) A
It is obtained by mixing a -B-A' type block copolymer elastomer and/or a hydrogenated A-B-A' type block copolymer elastomer. The polyphenylene ether used to prepare component (A) constituting the resin composition of the present invention is preferably a homopolymer or copolymer containing one or more units represented by the above general formula. The method for producing polyphenylene ether is not particularly limited, but for example, US Pat. No. 3,306,874 and US Pat.
It can be produced by reaction of phenols according to procedures such as those described in 3257357 and 3257358. These phenols include 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-dibutylphenol,
2,6-dilaurylphenol, 2,6-diprobylphenol, 2,6-diphenylphenol, 2-methyl-6-ethylphenol, 2-methyl-6-cyclohexylphenol, 2-methyl-6-tolylphenol , 2-methyl-6-methoxyphenol, 2-methyl-6-butylphenol, 2,6-dimethoxyphenol, 2,
3,6-trimethylphenol, 2,3,5,6
-tetramethylphenol and 2,6-diethoxyphenol, but are not limited thereto. Each of these may be reacted alone to form a corresponding homopolymer or with another phenol to form a corresponding copolymer having different units encompassed by the above formula. In particular, 2,
6-dimethylphenol and the corresponding polymers, namely poly(2,6-dimethyl-1,4-phenol) ether, as well as 2,6-dimethylphenol and other phenols, such as 2,3,
Use in combination with 6-trimethylphenol, 2-methyl-6-butylphenol, etc. and copolymers corresponding thereto, such as poly(2,6-dimethyl-co-2-methyl-6-butyl-1,4-phenylene) ether Examples include. In addition, 1,2 having a carboxyl group or carboxylic acid anhydride structure used in the preparation of component (A)
- Preferred specific examples of substituted olefin compounds include maleic anhydride, hymicic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride,
Examples include aconitic anhydride, 5-norbornene 2-methyl-2-carboxylic acid, and phthalic acid.
The amount of the 1,2-substituted olefin compound having a carboxyl group or carboxylic acid anhydride structure is 0.1 to 100 parts by weight of polyphenylene ether.
20 parts by weight, preferably in the range of 0.3 to 10 parts by weight. If the amount is less than 0.1 part by weight, no balanced improvement in impact strength, bending strength and heat resistance will be observed in the resin composition comprising the modified product, polyamide and block copolymer elastomer. In addition, the radical generator used in the preparation of component (A) includes known organic peroxides and diazo compounds, and preferred specific examples include benzoyl peroxide, dicumyl peroxide, di-tert
-butyl peroxide, tert-butylcumyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, azobisisobutyronitrile and the like. The amount of the radical generator used is in the range of 0.1 to 30 parts by weight, preferably 1 to 20 parts by weight, per 100 parts by weight of the 1,2-substituted olefin compound. If the amount is less than 0.1 part by weight, no improvement in performance, particularly in heat resistance and impact resistance, will be observed in the resin composition comprising the resulting modified product, polyamide, and block copolymer elastomer. The following methods can be used to prepare component (A). (a) A radical generator and a 1,2-substituted olefin compound having a carboxyl group or carboxylic anhydride structure are added to a solution containing polyphenylene ether, and the mixture is heated at a temperature of 60°C to 150°C for several tens of minutes to several hours. , how to stir. (b) 220°C to 370°C in a substantially solvent-free system;
A method of melting each component for 20 seconds to 30 minutes, preferably 40 seconds to 5 minutes. Method (a) is preferably adopted when existing reaction equipment and purification equipment are available, but method (b) can be modified using light equipment such as a general-purpose twin-screw extruder. It has the advantage of being able to be changed in a short time because it does not require a desolvation step or a polymer purification step. Polyamides (B) used in the present invention include polyamides obtained by ring-opening polymerization of lactams such as ε-caprolactam and ω-dodecalactam;
-aminocaproic acid, 11-aminoundecanoic acid,
Polyamides derived from amino acids such as 12-aminododecanoic acid, ethylenediamine, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine,
2,2,4-/2,4,4-trimethylhexamethylenediamine, 1,3- and 1,4-bis(aminomethyl)cyclohexane, bis(4,
aliphatic, alicyclic, such as 4′-aminocyclohexyl)methane, meta- and para-xylylene diamine,
Aromatic diamines and adipic acid, speric acid, sebacic acid, dodecanedioic acid, 1,3- and 1,4-
Aliphatic and alicyclic acids such as cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid, dimer acid,
Examples include polyamides derived from aromatic dicarboxylic acids, copolyamides thereof, and mixed polyamides. Among these, polycaproamide (nylon 6), polyundecamide (nylon 11), polydodecanamide (nylon 12), polyhexamethylene adivamide (nylon 66) and copolyamides containing these as main components are usually used. Useful. As a method for polymerizing polyamide, generally known melt polymerization, solid phase polymerization, or a combination thereof can be employed. The degree of polymerization of polyamide is not particularly limited, and the relative viscosity (polymer 1
(g was dissolved in 100ml of 98% concentrated sulfuric acid and measured at 25℃)
Any polyamide within the range of 2.0 to 5.0 can be selected depending on the purpose. The block copolymer elastomer used as component (C) in the present invention is an A-B-A' type block copolymer elastomer consisting of a vinyl aromatic hydrocarbon and a conjugated diene, and has terminal blocks A and A' may be the same or different, and is a thermoplastic homopolymer or copolymer derived from a vinyl aromatic hydrocarbon whose aromatic moiety may be monocyclic or polycyclic.
Examples of such vinyl aromatic hydrocarbons include styrene, α-methylstyrene, vinyltoluene,
Examples include vinylxylene, ethylvinylxylene, vinylnaphthalene and mixtures thereof. Intermediate polymer block B consists of a conjugated diene hydrocarbon, such as 1,3-butadiene, 2,
3-dimethylbutadiene, isoprene, 1,3-
Polymers derived from pentadiene and mixtures thereof, and the like. In addition, hydrogenation A-
The B-A' type block copolymer elastomer refers to the above-mentioned A
-B-A' type block copolymer elastomer in which the intermediate polymer block portion B is hydrogenated, and may be hydrogenated in any proportion. The block copolymer elastomer can be produced by a generally known method. For example, it can be manufactured by the method shown in US Pat. No. 3,251,905, US Pat. No. 3,231,635, and the like.
In addition, the block copolymer elastomer is
A hydrogenated block copolymer elastomer can be produced by hydrogenation according to the method disclosed in No. 3431323. In the thermoplastic resin composition of the present invention, the blending ratio of the modified polyphenylene ether (A), the polyamide (B), and the block copolymer elastomer is 5 to 90%.
% by weight, preferably 15-80% by weight, particularly preferably 20-70% by weight, 5-90% by weight of (B), preferably
10 to 80% by weight, particularly preferably 15 to 70% by weight and (C) 5 to 60% by weight, preferably 8 to 50% by weight,
Particularly preferred is 10 to 40% by weight. If (A) is less than 5% by weight, heat resistance and rigidity will be poor, and if (A) is more than 90% by weight, impact resistance will be poor and moldability will be impaired, which is not preferable. If (B) is less than 5% by weight, moldability is poor, and if (B) is more than 90% by weight, rigidity and heat resistance are undesirable. If (C) is less than 5% by weight, impact resistance will be poor, and if (C) is more than 60% by weight, rigidity and heat resistance will be poor and moldability will also be impaired, which is not preferable. There are no particular limitations on the method for producing the thermoplastic resin composition of the present invention, and generally known methods can be employed. That is, a modified polyphenylene ether (A), a polyamide (B), and a block copolymer elastomer (C) are prepared in the form of pellets, powder, pieces, etc.
Various methods are used, such as uniformly mixing using a high-speed stirrer, etc., and then melt-kneading using a single-screw or multi-screw extruder with sufficient kneading capacity, or melt-kneading using a Banbury mixer or rubber roll machine. can do. In addition, modified polyphenylene ether (A), polyamide (B), polyamide
(B) and the block copolymer elastomer (C), the modified polyphenylene ether (A) and the block copolymer elastomer (C), etc. are pre-kneaded in advance, and then adjusted to a predetermined blending ratio. A method of kneading is also possible. The thermoplastic resin composition of the present invention comprises polyphenylene ether modified product (A), polyamide (B), block copolymer elastomer (C), and optionally polystyrene (PS), styrene/acrylonitrile. Polymer (SAN), polymethyl methacrylate (PMMA), styrene/methyl methacrylate/acrylonitrile copolymer, α-methylstyrene/
Acrylonitrile copolymer, α-methylstyrene/styrene/acrylonitrile copolymer, α-
Vinyl polymers such as methylstyrene/methyl methacrylate/acrylonitrile copolymer, p-methylstyrene/acrylonitrile copolymer, styrene/N-phenylmaleimide copolymer, styrene/maleic anhydride copolymer, acrylonitrile- Butadiene-styrene terpolymer (ABS)
Resin, methacrylic acid resin-budadiene-styrene terpolymer (MBS) resin, AES resin, AAS resin, polycarbonate, polybutylene terephthalate, polyethylene terephthalate, etc., by appropriately mixing thermoplastic resins, polyethylene, polypropylene, ethylene/propylene, etc. copolymer, ethylene/butene-1 copolymer, ethylene/propylene/dicyclopentadiene copolymer, ethylene/
Properly mix polyolefin rubbers such as propylene/5-ethylidene 2-norporene copolymer, ethylene/propylene/1,4-hexadiene copolymer, ethylene/vinyl acetate copolymer, and ethylene/butyl acrylate copolymer. By doing so, it is also possible to adjust the physical properties and characteristics to more desirable values. Depending on the purpose, reinforcing materials and fillers such as pigments, dyes, glass fibers, metal fibers, metal flakes, and carbon fibers, heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, lubricants, plasticizers, and electrostatic charges are also added. Inhibitors, flame retardants, etc. can be added. The resin composition of the present invention is useful as an engineering plastic, and can be particularly used as an automobile outer panel material such as wheel caps and bodies, and has other properties such as impact resistance, rigidity, and heat resistance. It can be used for various molded products that require properties such as durability or chemical resistance. <Examples> Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. Izotsu impact strength is
ASTM D256−56, Method A, heat distortion temperature is
ASTM D648−56, flexural modulus is ASTM D790
-61. Izot impact strength and flexural modulus were measured in an absolutely dry state. Reference Example 1 (Production of modified product (A) of polyphenylene ether) A-1: Polyphenylene ether powder was mixed with 5 parts by weight of maleic anhydride and the maleic anhydride based on 100 parts by weight of the polyphenylene ether. The acid is charged into an extruder along with 10 parts by weight of 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, and the generated gas is degassed from the exhaust port attached to the extruder. While extrusion temperature
Extrusion was carried out at 320°C to produce a modified polyphenylene ether (A-1). After collecting 10 g of the obtained pellets and grinding them into fine powder using a grinder,
The mixture was heated under reflux for 48 hours using a Soxhlet extractor using 100 ml of methanol. Then 8 at 90℃
A sample was obtained by drying under reduced pressure for an hour. The existence of a −CO ₂ − structure derived from the reaction with maleic anhydride in this sample was detected using the Fourier integrated infrared absorption spectrum.
This was confirmed by analyzing the absorption peak between 1600 and 1800 cm ^-1 . A-2: A modified product of polyphenylene ether (A-
2) was manufactured. 10 g of the obtained pellets were collected and purified in the same manner as in the case of A-1 using a Soxhlet extractor, and the absorption peak of the infrared absorption spectrum was analyzed in the same manner as in the case of A-1. The presence of a -CO ₂ - structure derived from the reaction was confirmed. A-3: Pipio was prepared in the same manner as in (A-1) except that 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3 was used in an amount of 2 parts by weight based on maleic anhydride. A modified product (A-3) was produced. The obtained pellet was purified in the same manner as in the case of A-1, and the presence of a -CO ₂ - structure derived from the reaction with maleic anhydride was confirmed in the same manner as in the case of A-1. A-4: (A-1) except that 0.7 parts by weight of 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3 was used based on maleic anhydride.
A modified polyphenylene ether (A-4) was produced in the same manner as above. The obtained pellets are A
Purification was performed in the same manner as in the case of A-1, and the presence of a _-CO2- structure derived from the reaction with maleic anhydride was confirmed in the same manner as in the case of A-1. Reference Example 2 (Production of polyamide (B)) The following nylon 6, nylon 66 and nylon 12 were produced by a melt polymerization method. Nylon 6: Nylon 6 (B-1) having a relative viscosity of 2.75 was polymerized from ε-caprolactam using concentrated sulfuric acid. Nylon 66: Nylon with relative viscosity 2.60 from equimolar salt of hexamethylene diamine and adipic acid to concentrated sulfuric acid
66 (B-2) was polymerized. Nylon 12: Nylon 12 (B-3) having a relative viscosity of 2.35 was polymerized from 12-aminododecanoic acid using concentrated sulfuric acid. Examples Modified polyphenylene ethers (A-1, A-2) prepared in Reference Examples and polyamides (B-1 to
3) And as a block copolymer elastomer, unsaturated polystyrene-polybutadiene-polystyrene block copolymer "Cariflex" TR-1101 manufactured by Shell Chemical Company is used.
(C-1) and/or Shell Chemical
Hydrogenated polystyrene-polybutadiene-polystyrene block copolymer “Kraton” G1652 (C-2) manufactured by Co., Ltd. was mixed at the compounding ratio shown in Table 1, and melt-kneaded using a 30 mm diameter twin-screw extruder. After that, it was pelletized. The extrusion temperature is
It was carried out at 280℃. Next, the pellets were dried in vacuum, and then injection molded to form test pieces for measuring physical properties. During injection molding, the cylinder temperature was set at 280°C. The mold temperature was set at 80°C. The measurement results are shown in Table 1. Comparative Example Modified polyphenylene ether (A), polyamide (B) and block copolymer elastomer (C) produced in Reference Example, polyphenylene ether (hereinafter referred to as PPO) used as the raw material polymer in Reference Example 1. ) were mixed at the blending ratio shown in Table 1, and the physical properties were measured in the same manner as in the examples. The measurement results are shown in Table 1. The following is clear from the results of Examples and Comparative Examples. All of the resin compositions of the present invention (Experiments Nos. 1 to 14) had high Izot impact strength, high thermal deformation temperature, and high flexural modulus, and had excellent moldability. On the other hand, resin compositions (Experiment Nos. 15 and 16) consisting only of a modified polyphenylene ether (A) and a block copolymer elastomer (C) that do not contain polyamide had poor moldability. Ta. The resin compositions (Experiment Nos. 17 and 18) consisting only of polyamide (B) containing no modified polyphenylene ether and block copolymer elastomer (C) had low heat distortion temperatures. Resin compositions containing only the modified polyphenylene ether (A) and polyamide (B) that did not contain the block copolymer elastomer (Experiment Nos. 19 to 21) had low Izot impact strength. Resin compositions containing more than 60% by weight of block copolymer elastomer (C) (Experiment Nos. 22 and 23) have drawbacks such as low heat distortion temperature, low flexural modulus, and poor moldability. Was. When using polyphenylene ether that has not been modified with a compound with a specific structure (Experiment No. 24)
had low Izot impact strength. When a compound with a specific structure was melted and kneaded together with each component (Experiment No. 25), balanced improvements in Izot impact strength and heat distortion temperature were not achieved. When unmodified polyphenylene ether and polyamide (B-2) were pre-kneaded with a compound having a specific structure and then melt-kneaded with block copolymer elastomer (C-1) (Experiment No. 26), Izot impact was observed. Although the strength was improved, it was still insufficient and was not practical. In addition, after pre-kneading unmodified polyphenylene ether and block copolymer elastomer (C-1) with a compound having a specific structure, polyamide (B-2) is produced.
When melt-kneaded with (Experiment No. 27), the Izot impact strength was low.

【table】

[Table] <Effects of the invention> As explained above, the resin composition of the present invention has the following properties:
It has excellent impact resistance as represented by Izot impact strength, rigidity as represented by flexural modulus, and heat resistance as represented by heat distortion temperature, and has good moldability.

Claims (1)

[Claims] 1 (A) General formula [Formula] (wherein Q ₁ , Q ₂ , Q ₃ and Q ₄ each independently represent hydrogen, halogen, hydrocarbon, halohydrocarbon, hydrocarbon oxy and halohydrocarbonoxy, where n represents the total number of monomer units and is an integer of 20 or more), 0.1% per 100 parts by weight of the polyphenylene ether. ~20 parts by weight of a 1,2-substituted olefin compound having a carboxyl group or carboxylic acid anhydride structure is added in the presence of 0.1 to 30 parts by weight of a radical generator based on 100 parts by weight of the 1,2-substituted olefin compound. Polyphenylene ethers 5 to 90 having carboxyl groups and/or carboxylic acid anhydride structures obtained by reaction as part of substituents
% by weight, (B) polyamide 5-90% by weight and (C) A-
B-A' type block copolymer elastomer (where A,
A' is a polymerized vinyl aromatic hydrocarbon block of the same or different kind, and B is a polymerized conjugated diene block) and/or in the block copolymer elastomer, the intermediate polymer block part B is hydrogenated. Hydrogenation A-B-
A thermoplastic resin composition comprising 5 to 60% by weight of an A' type block copolymer elastomer (A, A', and B are defined as above).