JP3449638B2 - Impact resistant 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 resin composition which has excellent impact resistance, rigidity, heat resistance and chemical resistance and which can be used in the electric / electronic field, the automobile field and various other industrial material fields.

[0002]

2. Description of the Related Art Polyphenylene ether has a mechanical property, an electrical property, a heat resistance, a low temperature property, a low water absorption property and excellent dimensional stability, but has a drawback that it is inferior in moldability and impact resistance. By blending with high-impact polystyrene, these problems are improved, and it is widely used as a resin composition for, for example, electric / electronic parts, office equipment housings, automobile parts, precision parts, and various industrial parts. However, the classical polyphenylene ether resin composition (disclosed in U.S. Pat. No. 3,383,435) consisting of this polyphenylene ether and high-impact polystyrene is not sufficient although the impact resistance is improved.

For this reason, for example, US Pat.
No. 56 and U.S. Pat. No. 4,322,507 propose to improve impact resistance by blending a polyphenylene ether resin with a hydrogenated product of a vinyl aromatic compound-conjugated diene compound block copolymer. Has been done. In addition, Japanese Patent Publication No. 62-54346
Japanese Patent Laid-Open Publication No. Sho 62-62 proposes to improve the impact resistance and chemical resistance by blending a polyphenylene ether resin with an ethylene-ethyl acrylate copolymer.
-47221 and JP-A-58-5356, a polyphenylene ether-based resin is prepared by adding a hydrogenated product of a vinyl aromatic compound-conjugated diene compound block copolymer and an ethylene-unsaturated carboxylic acid ester copolymer. Proposals have been made to compound it to improve impact and chemical resistance.

[0004]

However, the prior art disclosed herein provides a resin composition having improved chemical resistance and is superior in heat resistance as compared with the classical polyphenylene ether resin composition. Although giving a resin composition, especially in a composition containing a large amount of an ethylene-unsaturated carboxylic acid ester copolymer, the compatibility between the polyphenylene ether resin and the ethylene-ethyl acrylate copolymer is insufficient and the layer peeling phenomenon occurs. The current situation is that

[0005]

In view of the above situation, the present inventors have decided to hydrogenate a vinyl aromatic compound-conjugated diene compound block copolymer having a vinyl aromatic compound bonding amount within a specific range. By blending the product at a specific ratio with an ethylene-ethyl acrylate copolymer, the miscibility of the polyphenylene ether resin and the ethylene-unsaturated carboxylic acid ester copolymer is improved, and the impact resistance, rigidity, and
It has been found that a resin composition having excellent heat resistance and chemical resistance can be obtained.

That is, according to the present invention, 70 to 99% by weight of a polyphenylene ether resin comprising (a) a polyphenylene ether and (b) a styrene resin, and (c) a bound vinyl aromatic compound amount of 45 to 80% by weight. 0.5 to 15% by weight of a hydrogenated product of the vinyl aromatic compound-conjugated diene compound block copolymer, and 0.5 to 15% by weight of (d) an ethylene-unsaturated carboxylic acid ester copolymer. It is a resin composition characterized by the above.

The present invention will be described in detail below. The polyphenylene ether (hereinafter simply referred to as PPE) used as the component (a) in the present invention is represented by the following general formulas (1) and (2).

[0008]

[Chemical 1]

[0009]

[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 or hydrogen, and R5 and R6 are not hydrogen at the same time. ), And a reduced viscosity (0.5 g / deciliter, chloroform solution, 30
C. measurement) in the range of 0.15 to 0.80 deciliter / g, preferably in the range of 0.20 to 0.70 deciliter / g, more preferably in the range of 0.30 to 0.60 deciliter / g. It is a polymer and / or a copolymer.

Representative examples of homopolymers of polyphenylene ether include poly (2,6-dimethyl-1,4-phenylene ether and 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
Examples thereof include homopolymers such as -phenylene) ether and poly (2-methyl-6-chloroethyl-1,4-phenylene) ether.

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.

In addition to the above-mentioned PPE, the PPE used in the present invention can be radical-generated with the PPE and α, β-unsaturated carboxylic acid or its derivative, styrene or its derivative, unsaturated carboxylic acid or its derivative. 8 in melted state, solution state, slurry state in the presence or absence of agent
It may be a known modified PPE obtained by reacting at a temperature of 0 to 350 ° C.
It may be a mixture of PE and the modified PPE in any ratio.

The styrene resin used as the component (b) in the present invention is a polymer obtained by polymerizing a styrene compound or a compound copolymerizable with the styrene compound in the presence or absence of a rubbery polymer. Is. The styrene compound is represented by the general formula (3)

[0015]

[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 a compound. Specific examples thereof include styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert-butylstyrene, ethylstyrene and the like. The compounds copolymerizable with the styrene compound include methacrylic acid esters such as methyl methacrylate and ethyl methacrylate; unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile;
Examples thereof include acid anhydrides such as maleic anhydride, which are used together with styrene compounds. The amount of the copolymerizable compound used is 30% by weight based on the total amount of the styrene compound.
It is preferably 15% by weight or less.

Examples of the rubbery polymer include a conjugated diene rubber, a copolymer of a conjugated diene and an aromatic vinyl compound, an ethylene-propylene copolymer rubber and the like. Specifically, polybutadiene and styrene-butadiene copolymer are particularly preferable. Moreover, when using an unsaturated rubbery polymer, it is preferable to use a partially hydrogenated rubber.

Polystyrene and rubber-modified polystyrene are particularly preferable as the styrene resin.
The method for producing the styrene resin used in the present invention is not particularly limited, and any of bulk polymerization, solution polymerization, emulsion polymerization and suspension polymerization well known to those skilled in the art may be used.

Next, the hydrogenated product of the vinyl aromatic compound-conjugated diene compound (hereinafter abbreviated as hydrogenated block copolymer) used as the component (c) in the present invention is at least one vinyl aromatic compound. A hydrogenated block copolymer obtained by hydrogenating a block copolymer composed of a polymer block A mainly composed of and a polymer block B mainly composed of at least one conjugated diene compound, for example, A-
B, A-B-A, A-B-A-B, (A-B-) ₄ -S
It is a hydrogenated product of a vinyl aromatic compound-conjugated diene compound block copolymer having a structure of i, A-B-A-B-A, or the like. The hydrogenated block copolymer of the component (c) is
The vinyl aromatic compound bonded with the block copolymer before hydrogenation is 45 to 80% by weight, preferably 50 to 50% by weight.
It contains 70% by weight. When the binding amount of the vinyl aromatic compound is 45% by weight or less or 80% by weight or more,
Delamination occurs and impact resistance is poor.

Further, the polymer block A mainly containing these vinyl aromatic compounds and the polymer block B mainly containing these conjugated diene compounds are the conjugated diene compound or vinyl aromatic compound in the molecular chain of each polymer block. The distribution of the compound may be random, tapered (in which the monomer component increases or decreases along the molecular chain), partially block-shaped, or any combination thereof. When there are two or more polymer blocks mainly composed of the merged block and the conjugated diene compound, the polymer blocks may have the same structure or different structures.

The vinyl aromatic compound constituting the block copolymer is, for example, one or more of styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, diphenylethylene and the like. It can be selected, and styrene is particularly preferable. Examples of the conjugated diene compound include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3.
One or more selected from butadiene and the like, and among them, butadiene, isoprene and combinations thereof are preferable. The polymer block mainly composed of the conjugated diene compound can have a microstructure in the block arbitrarily selected. For example, in the polymer block mainly composed of butadiene, the 1,2-vinyl bond has 2 to 60%. %, Preferably 8-40%.

The number average molecular weight of the block copolymer having the above structure is 5,000 to 1,000,000,
It is preferably in the range of 10,000 to 800,000, more preferably 30,000 to 500,000, and has a molecular weight distribution [weight average molecular weight (Mw) measured by gel permeation chromatography and number average molecular weight (M
The ratio of n)] is 10 or less. Further, the molecular structure of this block copolymer may be linear, branched, radial, or any combination thereof.

Thus, the block copolymer of the present invention is
Hydrogenated block copolymer obtained by hydrogenating an aliphatic double bond of a polymer block B mainly composed of a conjugated diene compound of a block copolymer (hydrogenated product of vinyl aromatic compound-conjugated diene compound block copolymer) ), And the hydrogenation rate of such aliphatic double bonds is at least 50% or more, preferably 80% or more, more preferably 95% or more.

The hydrogenated block copolymer of the above-mentioned component (c) may be obtained by any production method as long as it has the above-mentioned structure.
Examples of known manufacturing methods include, for example, JP-A-47-1.
No. 1486, No. 49-66743, No. 50-75651, No. 54-126255.
JP-A-56-10542, JP-A-56-
62847, JP-A-56-100840,
British Patent No. 1130770 and US Patent No. 3281
383 and 3639517, as well as British Patent No. 1020720 and US Patent No. 333.
3024 and 4501857.

Further, the hydrogenated block copolymer of the component (c) used in the present invention includes, in addition to the above-mentioned hydrogenated block copolymer, the hydrogenated block copolymer and an α, β-unsaturated carboxylic acid. Or a derivative thereof in the presence or absence of a radical generator in a molten state, a solution state, or a slurry state at 80 to 3
Even a known modified (copolymerized with 0.01 to 10% by weight of the α, β-unsaturated carboxylic acid or its derivative) hydrogenated block copolymer obtained by reaction at a temperature of 50 ° C. Of course, a mixture of the above-mentioned hydrogenated block copolymer and the modified hydrogenated block copolymer may be used in any ratio.

Next, specific examples of the unsaturated carboxylic acid ester of the ethylene-unsaturated carboxylic acid ester copolymer used as the component (d) in the present invention include ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, Ethyl methacrylate,
Butyl methacrylate and 2-ethylhexyl methacrylate are mentioned. Preferably ethyl acrylate,
Butyl acrylate and methyl methacrylate, and more preferably ethyl acrylate. Further, the copolymer may be copolymerized with another copolymerizable third component such as unsaturated carboxylic acid. The content of the bound unsaturated carboxylic acid ester in the copolymer is 2 to
It is in the range of 50% by weight, preferably in the range of 5 to 35% by weight. Further, the melt flow rate of the copolymer is AST
Measured at 190 ° C. according to the method of MD-1238,
The range of 0.5 to 250 g / 10 minutes is preferable.

In the present invention, the preferable weight ratio of (a) polyphenylene ether to (b) styrene resin is 9
/ 1 to 1/9, and more preferably 6/4 to 2/8
Is. The blending amounts of the hydrogenated block copolymer of the component (c) and the ethylene-unsaturated carboxylic acid ester copolymer of the component (d) in the present invention are (a), (b), (c) and (d). The amount is 0.5 to 15% by weight, preferably 1 to 10% by weight, based on the total amount of the components. When the total amount of the components (c) and (d) is 1% by weight or less, the impact resistance is not improved, and when it is 30% by weight or more, the rigidity and the heat resistance are largely decreased, which is not preferable.

The preferred weight ratio of the hydrogenated block copolymer as the component (c) and the ethylene-unsaturated carboxylic acid ester copolymer as the component (d) is 1/1 to 1/3.
When only the hydrogenated block copolymer of the component (c) is blended alone without blending the ethylene-unsaturated carboxylic acid ester copolymer of the component (d), and when the hydrogenated block copolymer of the component (c) is blended When only the ethylene-unsaturated carboxylic acid ester copolymer of the component (d) is blended alone without blending, the effect of improving the impact resistance is small, or conversely, the impact resistance is decreased. To be By using the specific hydrogenated block copolymer used as the component (c) and the ethylene-unsaturated carboxylic acid ester copolymer of the component (d) in a specific ratio, remarkable impact resistance and rigidity can be obtained. It is surprising that the decline can be suppressed.

The expression of this synergistic effect is presumed to be due to the following reasons. That is, when the hydrogenated block copolymer of the component (c) is used alone, the miscibility of the hydrogenated block copolymer with the polyphenylene ether-based resin is very good, and therefore the hydrogenated block copolymer is used. Is not finely dispersed, so there is no effect of improving impact resistance, and ethylene-
When the unsaturated carboxylic acid ester copolymer is used alone, it is difficult to finely disperse the copolymer due to poor miscibility of the copolymer and the polyphenylene ether resin, and the adhesiveness of the interface is Since the peeling phenomenon was observed in the molded product due to insufficientness and the impact resistance was lowered, when these were used together, the hydrogenated block copolymer of the component (c) and the polyphenylene ether resin (d) It is considered that this is because the compound functions as an admixture with the ethylene-unsaturated carboxylic acid ester copolymer as the component) and has a fine dispersion suitable for exhibiting good adhesiveness at the interface and exhibiting impact resistance. The dispersed form of the hydrogenated block copolymer of the component (c) and the ethylene-unsaturated carboxylic acid ester copolymer of the component (d) can be observed by a transmission electron microscope.

A flame retardant resin composition can be obtained by adding a flame retardant for imparting self-extinguishing property to the composition of the present invention. As such flame retardants, elemental phosphorus, phosphorus-containing compounds, nitrogen-containing compounds, halogen-containing compounds, antimony compounds and the like can be used alone or in combination.
Among them, a phosphoric acid ester compound is preferably used, and specific examples thereof include triphenyl phosphate, trixylenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, bisphenol A-bis (diphenyl). Phosphate), bisphenol A-bis (dicresyl phosphate),
Examples thereof include hydroxyphenyl diphenyl phosphate, and particularly preferred are bisphenol A-bis (diphenyl phosphate) and bisphenol A-bis (dicresyl phosphate). The blending amount of the flame retardant is appropriately selected depending on the required flame retardant performance and the composition of the components, but in general, the components (a), (b),
1 to 100 parts by weight of the total amount of (c) and (d)
It is in the range of 35 parts by weight, preferably 2 to 25 parts by weight.

In the present invention, in addition to the above components, if necessary, other additional components such as the above-mentioned non-hydrogenated block copolymer of the component (c) can be used as long as the characteristics and effects of the present invention are not impaired. Polymers, antioxidants, flame retardants (organic phosphate compounds, inorganic phosphorus compounds, halogen flame retardants, etc.), plasticizers (oil, low molecular weight polyethylene, epoxidized soybean oil, polyethylene glycol, fatty acid esters, etc.) ), Flame retardant aids, weather (light) resistance improvers, lubricants, inorganic or organic fillers and reinforcements (glass fiber, carbon fiber, whiskers, mica, talc, carbon black,
Titanium oxide, calcium carbonate, potassium titanate, wollastonite, conductive metal fibers, conductive carbon black, etc.), various colorants, release agents and the like can be added.

The polymer composition of the present invention can be produced by various methods using the above components. For example, a heat-melting and kneading method using a single-screw extruder, a twin-screw extruder, a roll, a kneader, a Brabender plastograph, a Banbury mixer and the like can be mentioned. Among them, the melt-kneading method using a twin-screw extruder is most preferable. The melt-kneading temperature at this time is not particularly limited, but is usually 150 to 3
It can be arbitrarily selected from 50 ° C.

The resin composition of the present invention thus obtained can be used to obtain molded articles of various parts by various conventionally known molding methods such as injection molding, extrusion molding and blow molding. Examples of these various parts include automobile parts, and specifically, bumpers, fenders,
Suitable for exterior parts such as door panels, various moldings, emblems, engine hoods, wheel caps, roofs, spoilers, various aero parts, and interior parts such as instrument panels, console boxes, trims, etc. Further, it can be suitably used as an interior / exterior component of electric equipment, and is specifically suitable for various computer and its peripheral equipment, other office automation equipment, cabinets such as televisions, videos, various disc players, and parts such as refrigerators. There is.

[0034]

EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The physical properties were evaluated by the following methods and conditions using injection-molded test pieces. (1) Drop weight impact strength 50 mm on a test piece support with a hole of 38 mm diameter
A flat test piece having a thickness of × 90 mm × 2.5 mm was placed, the weight was dropped under the following conditions, and the total absorbed energy at the time of breakage was measured by a weight drop graphic impact tester manufactured by Toyo Seiki Co., Ltd.

-Height of falling weight: 1 m-Diameter of tip of falling weight: 13 mm-Load of falling weight: 6.5 Kg (2) Bending strength and flexural modulus Measured based on ASTM D790. (3) Heat distortion temperature Based on ASTM D648, load 18.6 Kg / cm
Measured at ² . (4) Presence or absence of layer delamination A tensile test piece having a thickness of 1/8 inch (based on ASTM D638) was repeatedly bent to confirm the presence or absence of layer delamination on the fracture surface.

The following components were used as the components in the examples and comparative examples. (A-1): Poly-2,6-dimethyl-1,4-phenylene ether having a reduced viscosity of 0.42 deciliter / g measured at 30 ° C. in chloroform. (A-2): Poly 2,6-dimethyl-1,4-phenylene ether having a reduced viscosity of 0.53 deciliter / g measured at 30 ° C. in chloroform. (B-1): Partially hydrogenated conjugated diene rubber-modified impact-resistant polystyrene resin prepared by the method of Production Examples 1 and 2. (B-2): 9% polybutadiene having about 98% cis-1,4 bonds, a rubber particle size of 1.5 μm, and a reduced viscosity of 0.53 deciliter measured in toluene of free polystyrene at 30 ° C. / G rubber-modified impact-resistant polystyrene resin. (C-1): polystyrene-hydrogenated polybutadiene-polystyrene-hydrogenated polybutadiene structure, bound styrene amount 62%, number average molecular weight 8
8,000, the hydrogenation rate of the polybutadiene part is 99.9
% Hydrogenated block copolymer. (C-2): Polystyrene-hydrogenated polybutadiene-polystyrene structure, bound styrene amount 51
%, The number average molecular weight is 117,000, and the hydrogenation rate of the polybutadiene part is 99.9%. (C-3): Polystyrene-hydrogenated polybutadiene-polystyrene-hydrogenated polybutadiene structure, bound styrene amount 31%, number average molecular weight 9
1,000, the hydrogenation rate of the polybutadiene part is 99.8
% Hydrogenated block copolymer. (C-4): Polystyrene-hydrogenated polybutadiene-polystyrene-hydrogenated polybutadiene structure, bound styrene content 30%, number average molecular weight 17
10,000, the hydrogenation rate of the polybutadiene part is 99.9
% Hydrogenated block copolymer. (D-1): An ethylene-ethyl acrylate copolymer containing 25% by weight of ethyl acrylate and having a melt flow rate of 20 g / 10 min. (D-2): Contains 9% by weight of ethyl acrylate,
An ethylene-ethyl acrylate copolymer having a melt flow rate of 5 g / 10 min. (D-3): ethylene containing 25% by weight of ethyl acrylate and having a melt flow rate of 275 g / 10 min-
Ethyl acrylate copolymer. (D-4): Ethylene-ethyl acrylate copolymer containing 20% by weight of methyl methacrylate and having a melt flow rate of 12 g / 10 min.

Partial hydrogenation used in Examples and Comparative Examples
Impact-resistant polystyrene resin modified with conjugated diene rubber (b-
1) was prepared by the manufacturing method described below.
It [Production Example 1] Production of partially hydrogenated conjugated diene rubber The partially hydrogenated conjugated diene rubbers used in the examples are described below.
It was manufactured by the method. An agitator with an internal volume of 10 liters, a jar
Using an autoclave with a ket as a reactor,
Diene / n-hexane mixture (butadiene concentration 20%)
At 20 liters / hour, n-butyllithium / n-
Xanthane solution (concentration 5%) is introduced at 70 ml / hour.
Then, carry out continuous polymerization of butadiene at a polymerization temperature of 110 ° C.
did. Deactivate the obtained active polymer with methanol,
For a stirrer with a volume of 10 liters and a reactor with a jacket
Transfer 8 liters of polymer solution and hydrogenate at 60 ℃.
As a medium, di-p-tolyl-bis (1-cyclopentadiene)
Nyl) titanium / cyclohexane solution (concentration 1.2
Limol / liter) 250 ml and n-butyl
Lithium solution (concentration 6 mmol / l) 50 milliliters
With a bottle at 0 ° C, 2.0 kg / cm²Mixed under hydrogen pressure
Added, hydrogen partial pressure 3.0 kg / cm ²At 60
Let react for minutes. The partially hydrogenated polymer solution obtained was protected against oxidation.
2,6-di-t-butylhydroxytoluene as a stopping agent
0.5 parts per polymer was added to remove the solvent. Me
Partially hydrogenated polyb obtained by sampling after deactivation of tanol
The analytical values of Tadiene are shown in Table 1.

[0038]

[Table 1]

Production Example 2 Production of Impact-Resistant Polystyrene Resin The impact-resistant styrenic resin used in the examples was produced by the bulk polymerization method. 10 parts of partially hydrogenated polybutadiene in Table 1 was dissolved in 90 parts of styrene and 8 parts of ethylbenzene, and 0.05 part of benzoyl peroxide and 0.10 part of α-methylstyrene dimer were added to styrene. ,
Polymerization was carried out under stirring at 80 ° C. for 4 hours, 110 ° C. for 4 hours, and 150 ° C. for 4 hours. Further, heat treatment was carried out at around 230 ° C. for 30 minutes, and then unreacted styrene and ethylbenzene were removed in vacuum to obtain a high impact polystyrene resin. The content of partially hydrogenated polybutadiene in the obtained impact-resistant polystyrene-based resin was 11%, and the average particle diameter of partially hydrogenated polybutadiene in the state of containing dispersed polystyrene particles was 1.3 μm. Also, 3 in toluene
The reduced viscosity of free polystyrene measured at 0 ° C. was 0.65 deciliter / g.

[0040]

[Examples 1 to 5 and Comparative Examples 1 to 3] Each component was supplied to a twin-screw extruder having a screw diameter of 25 mm in which the maximum temperature of a heating cylinder was set to 300 ° C. and melt-kneaded. , A composition pellet was obtained. The pellets were supplied to an in-line screw type injection molding machine in which the maximum temperature of the heating cylinder was set to 240 ° C., and a physical property test piece was injection molded under the condition of a mold temperature of 60 ° C. A physical property test was conducted using these test pieces, and the results shown in Table 2 were obtained.

[0041]

[Table 2]

[0042]

[Examples 6 to 9 and Comparative Examples 4 to 6] Each component having the composition shown in Table 3 was supplied to a twin-screw extruder having a screw diameter of 25 mm in which the maximum temperature of the heating cylinder was set to 300 ° C, and melt-kneaded. , A composition pellet was obtained. The pellets were supplied to an in-line screw type injection molding machine in which the maximum temperature of the heating cylinder was set to 240 ° C., and a physical property test piece was injection molded under the condition of a mold temperature of 60 ° C. A physical property test was conducted using these test pieces, and the results shown in Table 3 were obtained.

[0043]

[Table 3]

[0044]

[Examples 10 to 11 and Comparative Example 7] Each component was blended with the composition shown in Table 4 and supplied to a twin-screw extruder with a screw diameter of 25 mm in which the maximum temperature of the heating cylinder was set to 320 ° C. A product pellet was obtained. The pellets were supplied to an in-line screw type injection molding machine in which the maximum temperature of the heating cylinder was set to 290 ° C., and a physical property test piece was injection-molded under the condition of a mold temperature of 80 ° C. A physical property test was conducted using these test pieces, and the results shown in Table 4 were obtained.

[0045]

[Table 4]

[0046]

[Examples 13 to 14, Comparative Examples 8 to 9 and Reference Example] Each component having the composition shown in Table 5 was supplied to a twin-screw extruder having a screw diameter of 25 mm in which the maximum temperature of the heating cylinder was set to 300 ° C. Melt kneading was performed to obtain a composition pellet. The pellets were supplied to an in-line screw type injection molding machine in which the maximum temperature of the heating cylinder was set to 240 ° C., and a physical property test piece was injection molded under the condition of a mold temperature of 60 ° C. A physical property test was conducted using these test pieces, and the results shown in Table 5 were obtained.

[0047]

[Table 5]

[0048]

As described above, the present invention provides a polyphenylene ether resin containing a vinyl aromatic compound-conjugated diene compound block copolymer and an ethylene-unsaturated carboxylic acid ester copolymer. By blending the vinyl aromatic compound-conjugated diene compound block copolymer hydrogenated product and the ethylene-unsaturated carboxylic acid ester copolymer in a specific range in a specific combination ratio, a polyphenylene ether Provided is a resin composition having improved miscibility between a base resin and an ethylene-unsaturated carboxylic acid ester copolymer and having no delamination phenomenon of a molded article and having excellent impact resistance, rigidity, heat resistance and chemical resistance. .

Front page continued (51) Int.Cl. ⁷ identification code FI C08L 23:08) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 71/12 C08K 5/521-5/523 C08L 25 / 04-25/14 C08L 53/02 C08L 23/08

Claims (2)

(57) [Claims] 1. (a) polyphenylene ether and (b)
Polyphenylene ether resin consisting of styrene resin 70 to 99% by weight, (c) Hydrogenated product of vinyl aromatic compound-conjugated diene compound block copolymer having 45 to 80% by weight of bound vinyl aromatic compound 0 .5～15 wt%, (d) ethylene - Ri Na by blending 0.5 to 15 wt% unsaturated carboxylic acid ester copolymer, and (c) /
Resin composition weight ratio and wherein the 1 / 1-1 / 3 der Rukoto of (d). Wherein components (a), 100 parts by weight of the total amount of (b), (c) and (d), bi as a flame retardant
Sphenol A-bis (diphenyl phosphate)
Or bisphenol A-bis (dicresylphosphine)
1 to 35 parts by weight of a phosphoric acid ester compound as a main component .