JPH09316321A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyphenylene ether resin compsn. which has a greatly improved resistance to stress crack while retaining its excellent mechanical properties, flowability, and molded appearance. SOLUTION: This compsn. comprises 100 pts.wt. polyphenylene ether resin and 0.1-50 pts.wt. ethylene/α,β-unsatd. alkyl carboxylate copolymer which contains units derived from an α,β-unsatd. alkyl carboxylate having a 2C or higher alkyl group and has a content of α,β-unsatd. alkyl carboxylate units of 35-70wt.%.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition. More specifically, the present invention relates to a thermoplastic resin composition based on a polyphenylene ether-based resin and having significantly improved stress crack resistance.

[0002]

2. Description of the Related Art Polyphenylene ether resins have excellent properties such as heat resistance, low water absorption, low creep, dimensional stability, and dielectric properties. Widely used. However, a polyphenylene ether-based resin composition comprising a polyphenylene ether-based resin or a polyphenylene ether-based resin and a styrene-based resin is an organic solvent such as hexane under stress,
Since it has a drawback that it easily cracks when it comes into contact with kerosene, coconut oil, or grease (the stress crack resistance is not good), its use is extremely limited.

As an invention of a polyphenylene ether-based resin composition in which an attempt has been made to improve the stress crack resistance of the polyphenylene ether-based resin, JP-A-48-42047, JP-A-48-47943 and JP-A-48-47943 disclose the invention. 6
There is an invention described in Japanese Patent No. 2851.

JP-A-48-42047 discloses that in a composition comprising polyphenylene ether and rubber-modified polystyrene, the base polystyrene in the rubber-modified polystyrene has an intrinsic root viscosity of at least about 1.0 dl / g. A polyphenylene ether-based resin composition "characterized thermoplastic composition with high impact strength" is described.

JP-A-48-62851 discloses that "an elastomer block copolymer of polyphenylene ether, vinyl aromatic compound and conjugated diene, and a styrene homopolymer or random copolymer resin as an optional component are disclosed. And a polymer composition comprising: a polyphenylene ether-based resin composition.

JP-A-48-47943 discloses a polyphenylene ether-based resin composition comprising "a polymer composition containing polyphenylene ether, an acrylonitrile-diene rubber-styrene resin modified with an acrylic resin, and a polystyrene resin as an optional component". Things are listed.

However, in the polyphenylene ether-based resin compositions described in JP-A-48-42047 and JP-A-48-62851, other mechanical properties such as rigidity are significantly impaired. There is. Further, in the polyphenylene ether-based resin composition described in JP-A-48-47943, the compatibility between the polyphenylene ether-based resin and the acrylic resin-modified acrylonitrile-diene rubber-styrene resin is extremely poor, so that the acrylic resin-modified acrylonitrile is used. There is a problem that a sufficient effect cannot be obtained because the content ratio of -diene rubber-styrene resin is extremely limited.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyphenylene ether-based resin composition having significantly improved stress crack resistance while maintaining excellent properties in terms of mechanical properties, fluidity, and appearance of a molded article. To provide things.

[0009]

That is, the present invention comprises the following components (A) and (B), and (A) 100
The present invention relates to a thermoplastic resin composition in which the content of (B) per part by weight is 0.1 to 50 parts by weight. (A): Polyphenylene ether resin (B): Ethylene-α, β having an α, β-unsaturated carboxylic acid alkyl ester in which the alkyl group has 2 or more carbon atoms
-An unsaturated carboxylic acid alkyl ester-based copolymer, wherein the content of the α, β-unsaturated carboxylic acid alkyl ester in the copolymer is 35 to 70% by weight-
α, β-Unsaturated Carboxylic Acid Alkyl Ester Copolymer

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The component (A) of the present invention is a polyphenylene ether resin.

The component (A) polyphenylene ether-based resin according to the present invention is represented by the following general formula (wherein R ₁ , R ₂ , R
₃ , R ₄ and R ₅ are selected from hydrogen, a halogen atom, a hydrocarbon group or a substituted hydrocarbon group, and one of them is always a hydrogen atom. Is a polymer obtained by oxidatively polymerizing one or more of the phenolic compounds represented by the formula (1) with oxygen or an oxygen-containing gas using an oxidation coupling catalyst, and a known polyphenylene ether-based resin can be used.

[0012]

R ₁ , R ₂ , R ₃ , R _{4 according to the} above general formula
And R ₅ include, for example, hydrogen, chlorine, bromine, fluorine, iodine, methyl, ethyl, n- or isopropyl, pri-, sec- or t-butyl, chloroethyl, hydroxyethyl, phenylethyl, benzyl, Hydroxymethyl, carboxyethyl, methoxycarbonylethyl, cyanoethyl, phenyl, chlorophenyl,
Methylphenyl, dimethylphenyl, ethylphenyl,
Allyl and the like.

Specific examples of the above general formula include phenol; o-, m-, or p-cresol; 2,6-, 2,
5-, 2,4- or 3,5-dimethylphenol; 2-
Methyl-6-phenylphenol; 2,6-diphenylphenol; 2,6-diethylphenol; 2-methyl-6-ethylphenol; 2,3,5-, 2,3,6-
Or 2,4,6-trimethylphenol; 3-methyl-
6-t-butylphenol; thymol; 2-methyl-6
-Allylphenol and the like.

The component (A) according to the present invention further comprises a phenol compound other than the above-mentioned general formula, for example, bisphenol-
A, a polymer obtained by similarly oxidatively polymerizing a copolymer of a polyvalent hydroxyaromatic compound such as tetrabromobisphenol-A, resorcin, hydroquinone, and a novolak resin with a phenol compound represented by the above general formula. You may.

The oxidative coupling catalyst used in the oxidative polymerization of the phenol compound is not particularly limited, and any catalyst having a polymerization ability can be used.
The method for producing such a polyphenylene ether-based resin is described in, for example, U.S. Pat. Nos. 3,306,874, 3,306,875 and 3,257,357, and Japanese Patent Publication No.
No. 17,880, JP-A-50-51197 and JP-A-1-304119.

Specific examples of the component (A) include poly (2,
6-dimethyl-1,4-phenylene ether), poly (2,6-diethyl-1,4-phenylene ether),
Poly (2-methyl-6-ethyl-1,4-phenylene ether), poly (2-methyl-6-propyl-1,4-phenyl)
Phenylene ether), poly (2,6-dipropyl-)
1,4-phenylene ether), poly (2-ethyl-6)
-Propyl-1,4-phenylene ether), poly (2,6-dibutyl-1,4-phenylene ether),
Poly (2,6-dipropenyl-1,4-phenylene ether), poly (2,6-dilauryl-1,4-phenylene ether), poly (2,6-diphenyl-1,4-phenylene ether), poly ( 2,6-dimethoxy-1,
4-phenylene ether), poly (2,6-diethoxy-1,4-phenylene ether), poly (2-methoxy-6-ethoxy-1,4-phenylene ether), poly (2-ethyl-6-stearyloxy) -1,4-phenylene ether), poly (2-methyl-6-phenyl-)
1,4-phenylene ether), poly (2-methyl-
1,4-phenylene ether), poly (2-ethoxy-
1,4-phenylene ether), poly (2-chloro-
1,4-phenylene ether), poly (3-methyl-6)
-T-butyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether),
Poly (2,5-dibromo-1,4-phenylene ether), poly (2,6-dibenzyl-1,4-phenylene ether), and various copolymers containing plural kinds of repeating units constituting these polymers Can be combined.
2,3,6-trimethylphenol in the copolymer,
Copolymers of polysubstituted phenols such as 2,3,5,6-tetramethylphenol and 2,6-dimethylphenol are also included.

Preferred among the components (A) are poly (2,6-dimethyl-1,4-phenylene ether),
Poly (2,6-diphenyl-1,4-phenylene ether) and a large part of 2,6-dimethylphenol and a small part of 3-methyl-6-t-butylphenol or 2,3
And a copolymer with 6-trimethylphenol.

The molecular weight of the component (A) is not specifically defined because its preferred range varies depending on the purpose, but it is generally 0.1 to 0.000 expressed as the intrinsic viscosity measured in chloroform at 30 ° C. 7 dl / g, more preferably 0.2 to 0.6 dl / g.

The component (A) according to the present invention includes those obtained by modifying the above-mentioned polymer or copolymer by graft polymerization of a styrene-based monomer such as styrene or α-methylstyrene.

The component (B) of the present invention is an ethylene-α, β-unsaturated carboxylic acid alkyl ester copolymer having an α, β-unsaturated carboxylic acid alkyl ester in which the alkyl group has 2 or more carbon atoms. Therefore, α, β in the copolymer
-The content of unsaturated carboxylic acid alkyl ester is 35 to 35
The ethylene-α, β-unsaturated carboxylic acid alkyl ester copolymer is 70% by weight, and a specific example thereof is an ethylene- (meth) acrylate copolymer.

A specific example of the above α, β-unsaturated carboxylic acid alkyl ester is ethyl (meth) acrylate. Here, (meth) acrylate means acrylate and / or methacrylate. As the (meth) acrylate, those obtained from alcohols having 2 to 8 carbon atoms are preferable, and for example, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate,
2-Ethylhexyl acrylate, 2-ethylhexyl methacrylate, etc. are exemplified, and these may be used alone or in combination of two or more. In addition,
Most preferred is ethyl methacrylate.

The content of the α, β-unsaturated carboxylic acid alkyl ester in the component (B) is 35 to 70% by weight,
It is preferably 35 to 60% by weight. If the content is too small, the effect of improving the stress crack resistance is not sufficient, while if the content is too large, poor dispersion results in reduced impact resistance and poor appearance.

The content of (B) in the thermoplastic resin composition is from 0.1 to 50 parts by weight, preferably from 2 to 10 parts by weight, per 100 parts by weight of (A). If the content is too small, the effect of improving the oil resistance is not sufficient, while if the content is too large, the rigidity is lowered, causing a peeling phenomenon in the molded product.

The thermoplastic resin composition of the present invention contains (C) a styrene resin in addition to the above (A) and (B), and the content of (C) per 100 parts by weight of (A) is reduced. 19
The content of (B) may be from 0.1 to 50 parts by weight per 100 parts by weight of the total amount of (A) and (C).

The styrenic resin (C) according to the present invention is a polymer or copolymer derived from a styrenic monomer and having at least 25% by weight or more of a repeating unit represented by the following general formula. And known polymers and copolymers can be used.

[0027]

In the above general formula, R is hydrogen, carbon number 1
~ 6 alkyl or halogen; Y is hydrogen, vinyl, halogen, amino group, hydroxyl group or alkyl having 1 to 6 carbon atoms;
n is 0 or an integer of 1 to 5.

Examples of the component (C) are homopolymers such as polystyrene and polychlorostyrene; for example, ethylene-α-olefin- (non-conjugated diene) copolymer rubber having a crystallinity of less than 15%, and polybutadiene. Rubber, styrene-butadiene random copolymer rubber, styrene-butadiene block copolymer rubber, hydrogenated styrene-butadiene block copolymer rubber (hydrogenated repeating units derived from butadiene), polyisoprene rubber, Styrene-isoprene random copolymer rubber, styrene-isoprene block copolymer rubber, hydrogenated styrene-isoprene random copolymer rubber (hydrogenated repeating units derived from isoprene), urethane rubber, natural rubber, etc. Polystyrene modified with rubber in rubber modified copolymer Styrene-acrylonitrile copolymer, styrene-methyl methacrylate copolymer, styrene-maleic anhydride copolymer, styrene-methyl acrylate copolymer, etc. Examples thereof include a copolymer of a monomer and a styrene-based monomer; a mixture thereof.

The amount of (C) used is such that the content of (C) per 100 parts by weight of (A) is 1900 parts by weight or less, and the amount of (C) per 100 parts by weight of the total of (A) and (C) is The content of B) is adjusted to be 0.1 to 50 parts by weight. By using (C) within this range,
The effect that the moldability is improved can be obtained. If (C) is used excessively, heat resistance will be reduced.

The thermoplastic resin composition of the present invention contains (D) a rubbery polymer in addition to (A) and (B) or (A), (B) and (C), and A) and (C)
May be 50 parts by weight or less per 100 parts by weight of the total amount of (D).

The component (D) rubbery polymer according to the present invention refers to natural and synthetic polymers which are elastic at room temperature.
Known rubbery polymers can be used. Examples of the component (D) include an ethylene-α-olefin- (non-conjugated diene) copolymer rubber having a crystallinity of less than 15%, and a crystallinity of 15%.
% Of ethylene-α-olefin- (non-conjugated diene)
Rubber, polybutadiene rubber, styrene butadiene random copolymer rubber, styrene butadiene block copolymer rubber, hydrogenated styrene butadiene block copolymer Polymer rubber (having hydrogenated repeating units derived from butadiene), copolymer rubber obtained by graft-polymerizing a styrene monomer onto polybutadiene rubber, and styrene-based monomer obtained by styrene-butadiene random copolymer rubber Copolymer rubber obtained by graft-polymerizing a monomer, a copolymer rubber obtained by graft-polymerizing a styrene-based monomer to a styrene-butadiene block copolymer rubber,
Copolymer rubber, polyisoprene rubber, styrene-isoprene random prepared by graft-polymerizing a styrene monomer onto hydrogenated styrene-butadiene block copolymer rubber (having hydrogenated repeating units derived from butadiene) Styrene-based monomers are used for copolymer rubber, styrene-isoprene block copolymer rubber, hydrogenated styrene-isoprene random copolymer rubber (hydrogenated repeating units derived from isoprene), and polyisoprene rubber. Copolymer rubber obtained by graft polymerization,
A copolymer rubber obtained by graft-polymerizing a styrene monomer to a styrene-isoprene random copolymer rubber, a copolymer rubber obtained by graft-polymerizing a styrene monomer to a styrene-isoprene block copolymer rubber, A copolymer rubber, a polyurethane rubber, a mixture of these rubbers, obtained by graft-polymerizing a styrene-based monomer to a hydrogenated styrene-isoprene random copolymer rubber (having a repeating unit derived from isoprene hydrogenated); Is raised. Further, a modified rubber modified by reacting these rubbers with a compound having a functional group such as a carboxyl group or an epoxy group is also included in the component (D).

In a copolymer rubber obtained by graft-polymerizing the above-mentioned various styrene monomers related to the component (D),
The content of the repeating unit derived from the styrene-based monomer is preferably less than 25%, and styrene is most preferable as the styrene-based monomer.

The ethylene-α-olefin- (non-conjugated diene) copolymer rubber according to the components (C) and (D) includes ethylene-propylene copolymer rubber and ethylene-butene-1 copolymer rubber. United rubber, ethylene-propylene-non-conjugated diene copolymer rubber, ethylene-butene-1
-Non-conjugated diene copolymer rubber and the like.

Further, the above-mentioned, for example, styrene-butadiene block copolymer rubber, hydrogenated styrene-butadiene block copolymer rubber, styrene-isoprene block copolymer rubber, and hydrogenated component (C) and component (D). The number of each block in the styrene-isoprene block copolymer rubber is not particularly limited. Taking the styrene-butadiene block copolymer rubber as an example, the copolymer rubber is a styrene-butadiene block copolymer rubber. Besides, for example, styrene-butadiene-styrene block copolymer rubber and styrene-butadiene-styrene-
It may be a butadiene block copolymer rubber.

The amount of (D) used is adjusted so that the content of (D) per 100 parts by weight of the total of (A) and (C) is 50 parts by weight or less. Within this range (D)
The effect of improving the impact resistance can be obtained by using. If (D) is used excessively, the rigidity is reduced.

In the composition of the present invention, if necessary, a crystalline olefin polymer having a crystallinity of 15% or more may be added in addition to the components (A) to (D). Examples of such olefin polymers include polypropylene, high density polyethylene, low density polyethylene, linear low density polyethylene, propylene-ethylene copolymer, ethylene-butene-1 copolymer, ethylene-pentene copolymer, ethylene- Olefin polymers such as hexene copolymer and poly-4-methylpentene-1 can be mentioned. The above copolymer may be any of a random copolymer, a block copolymer, and a graft copolymer. These polymers and copolymers can be used alone or as a mixture of two or more. Of these, polypropylene, polyethylene of various densities, propylene-ethylene copolymer is preferred,
Particularly preferred are polypropylene, propylene-ethylene random copolymer and propylene-ethylene block copolymer.

[0038] The composition of the present invention may further contain other polymer compounds and auxiliaries as necessary. As other polymer compounds, for example, polyvinyl chloride, polymethyl methacrylate, polyvinyl acetate, polyvinyl pyridine, polyvinyl carbazole, polyacrylamide,
Polymers such as polyacrylonitrile, polycarbonate, polysulfone, polyethersulfone, polyethylene terephthalate, polybutylene terephthalate, polyarylene esters (for example, U-polymer of Unitika Ltd.), polyphenylene sulfide, 6-nylon,
Polyamides such as 6,6-nylon and 12-nylon,
Examples include condensation type polymer compounds such as polyacetal, and various kinds of thermosetting resins such as silicone resin, fluorine resin, polyimide, polyamide imide, phenol resin, alkyd resin, unsaturated polyester resin, and davon resin.

The composition of the present invention may contain various fillers for the purpose of strengthening or imparting functions. Examples of the filler include glass fiber, carbon fiber, polyamide fiber, metal fiber such as aluminum and stainless steel, and fiber such as metal whisker, silica, alumina, calcium carbonate, talc, mica, glass flake, clay, kaolin, magnesium sulfate, and magnesium sulfate. wollastonite, it may be an inorganic filler such as carbon black, TiO _2, ZnO and Sb ₂ O _3. Any of these can be used as a reinforcing material for the composition, but fillers such as carbon fiber, metal fiber, and carbon black reduce the surface resistivity and volume resistivity of the resin composition, so that conductivity is imparted. A resin composition can also be obtained.

When the rigidity and heat resistance of the resin composition of the present invention are to be improved, inorganic fillers such as glass fiber, potassium titanate whisker, talc, glass flake, mica, and calcium carbonate may be used as the filler. It is particularly preferred to use carbon fibers.

The resin composition of the present invention further comprises Sb ₂ O ₃ ,
Flame retardants or flame retardant assistants such as halogen compounds and phosphate esters, other lubricants, nucleating agents, plasticizers such as triphenyl phosphate and phthalate esters, stabilizers, dyes, pigments, antistatic agents, antioxidants , A weather resistance imparting agent and the like.

Examples of flame retardants include triphenyl phosphate, tricresyl phosphate, phosphate obtained from a mixture of isopropyl phenol and phenol,
Phosphates such as benzohydroquinone, resorcin or phosphates obtained from a mixture of a bifunctional phenol such as bisphenol A with other alcohols or phenols; decabromobiphenyl, pentabromotoluene, decabromodiphenyl ether , Hexabromobenzene, brominated polystyrene, brominated epoxy resins, and the like; and nitrogen-containing compounds such as melamine and melamine triisocyanurate.

Other specific examples of the stabilizer include sterically hindered phenols, organic phosphites, oxalic diazides, sterically hindered amines, and the like, and specific examples of the lubricant include polyethylene wax, paraffin, and the like. I can give it. The mixing ratio of the above-mentioned other substances can be arbitrarily selected according to the purpose. However, if a general guideline for using them is shown, the total amount of the components (A) and (B) is 100 wt. 3 parts flame retardant
0 parts by weight or less, preferably 1 to 20 parts by weight,
0 parts by weight or less, preferably 0.001 to 10 parts by weight, and the lubricant is 2 parts by weight or less.

The method for producing the polyphenylene ether-based resin composition of the present invention is not particularly limited, and various methods such as a solution blending method and a melt kneading method can be exemplified. The preferred method is the melt kneading method. As a specific method, after mixing each component with a known mixer such as a Henschel mixer, a super mixer, a ribbon blender, and a V blender, the mixture is mixed with a Banbury mixer, a plastomill, a Brabender plastograph, a uniaxial or biaxial extrusion. Examples of the method include melt kneading with a known kneader such as a kneader. The kneading temperature may be selected in the range of 150 to 400 ° C, preferably 200 to 350 ° C.

The order of mixing and kneading of the components is arbitrary.
For example, when melt-kneading using an extruder or the like, any combination of each component may be separately kneaded, and then all the combinations may be mixed and kneaded, or a plurality of components may be supplied to one extruder. A mouth (feed port) may be provided, and one or two or more components may be sequentially fed from each feed port. For example, a method in which components (A) to (D) are added all at once and melt-kneaded at the same time, components (A), (B) and (C) are previously melt-kneaded, and then component (D) is additionally added And melt-kneading the components (A), (C) and (D) in advance, and then melt-kneading by adding the component (B) additionally, and the components (B) and (D). ) Is preliminarily kneaded, and then the component (A) is additionally added, followed by melt kneading.

The thermoplastic resin composition of the present invention has remarkably improved oil resistance and can be optimally used in the fields of, for example, pump casings, hot water tanks, motor housings, etc. by utilizing its characteristics.

[0047]

The present invention will be described below in more detail with reference to examples, but the scope of the present invention is not limited by these examples. All the examples and comparative examples are shown in the table below.

The components used and their abbreviations are as follows. Component (A) polyphenylene ether-based resin PPE has an intrinsic viscosity of 0.46 as measured in chloroform at 30 ° C.
dl / g of poly (2,6-dimethyl-1,4-phenylene ether).

Component (B) ethylene-ethyl acrylate
Polymer EEA-1-ethyl acrylate content 38wt%, MFR (19
0 ° C., 2.16 kg) 25 g / 10 min EEA-2 ethyl acrylate content 25 wt%, MFR (19
0 ° C., 2.16 kg) 20 g / 10 min EEA-3 ethyl acrylate content 34.5 wt%, MFR
(190 ° C, 2.16kg) 190g / 10min

Component (C) Styrene resin PS-1 Sumibright (registered trademark) E1 manufactured by Sumitomo Chemical Co., Ltd.
83N (grade) polystyrene. The weight average molecular weight is 30 × 10 ⁴ , and the MI is 2.4 g / 10 min under the measurement conditions of 200 ° C. and 5 kg load. PS-2 Sumitomo Chemical Co., Ltd. Sumibright (registered trademark) M5
High impact polystyrene of 88 (grade). The rubber content is 9.0 wt%, the weight average molecular weight is 21.5 × 10 ⁴ ,
MI is 3.0 g / 200 ° C. under a measurement condition of 5 kg load.
10 min.

Component (D) Rubbery Polymer A hydrogenated styrene-butadiene-styrene block copolymer, Clayton (trade name) G1657 (grade) manufactured by SEBS Shell Chemical. Filler Glass fiber TP66 (grade) manufactured by Nippon Sheet Glass Co., Ltd., fiber diameter 10 μm, fiber length 3 mm. Abbreviated as GF.

Stress crack resistance (unit is time) A semicircular jig with a curvature R of 165 mm or 98 mm to which a test piece of 100 mm × 12.7 mm × 3 mm is attached is immersed in kerosene, then immersed, and then cracked on the test piece. The time until the onset of the onset was measured. The longer the time until crack generation, the better the stress crack resistance. Abbreviated as "stoke resistant".

A 2 mm thick square plate was obtained by bamboo skin peel injection molding of the molded product, the square plate was bent several times, and the following judgment was made based on the occurrence of peeling at the bent portion. ○: No peeling △: Slight peeling ×: Notable peeling

Example 1 42 parts by weight of PPE, 4 parts by weight of EEA-1, PS-1
9 parts by weight and PS-245 parts by weight were charged from the first hopper of a continuous twin-screw kneader (TEM-50 manufactured by Toshiba Machine Co., Ltd.), the cylinder temperature was set to 260 ° C., and the melt kneading was performed at a screw rotation speed of 250 rpm. Then, granulation was performed to obtain a polyphenylene ether-based resin composition. The obtained composition was injection molded at 260 ° C. to prepare a test piece, and the test piece was evaluated for physical properties and stress crack resistance against kerosene.

Examples 2 to 3 and Comparative Examples 1 to 8 The same procedure as in Example 1 was carried out except that the composition was as shown in Table 1, Table 2 or Table 3 (only GF was charged from the second hopper). . The conditions and results are shown in the same table.

The following can be seen from the results. Examples 1 to 3 satisfying the conditions of the present invention show satisfactory results in all evaluation items. On the other hand, Comparative Example 1, Comparative Example 2, Comparative Example 4 and Comparative Example 6 lacking the component (B) which is an essential component of the present invention are inferior in stress crack resistance,
Comparative Example 3, Comparative Example 5, Comparative Example 7, and Comparative Example 8 in which the component (B) was used but whose ester amount was too small were inferior in stress crack resistance and bamboo peeling releasability of the molded product.

[0057]

[Table 1]

[0058]

[Table 2] −−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Comparative Example 1 2 3 4 5 Formulation wt (A) PPE 100 42 42 42 42 (B) EEA-1 0 0 0 0 0 EEA-2 0 0 4 0 4 EEA-3 0 0 0 0 0 (C) PS1 0 9 9 4 4 PS2 0 49 45 49 45 (D) SEBS 0 0 0 5 5 Others GF 0 0 0 0 0 B / A 0 0 9.5 0 9.5 B / (A + C) × 100 0 0 4.2 0 4.4 D / (A + C) × 100 0 0 0 5.3 5.5 (B) Ester amount wt% * 1--25-25 Evaluation Stress cracking resistance R165 min 20 20 20 15 10 Bamboo peeling of molded products ○ ○ × ○ × −−−−−−−−−−−−−−− −−−−−−−−−−−−−−−−

[0059]

[Table 3]

* 1 (B) ester amount: (B) the content of the α, β-unsaturated carboxylic acid alkyl ester in the ethylene-α, β-unsaturated carboxylic acid alkyl ester copolymer, It was measured by the method.

A standard sample of an ethylene-α, β-unsaturated carboxylic acid alkyl ester copolymer having a different ester content and a known content was used with an infrared spectrophotometer at a wave number of 3480 cm ^-1 . A calibration curve for absorbance is created, and the calibration curve and the wave number 348 of the test sample are
The ester content of the test sample was determined from the absorbance at 0 cm ^-1 .

[0062]

As described above, according to the present invention, a polyphenylene ether-based resin composition having significantly improved stress crack resistance while maintaining excellent properties in terms of mechanical properties, fluidity, and appearance of a molded article. Could be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical display location C08L 21:00)

Claims (4)

[Claims] 1. It contains the following components (A) and (B),
And the content of (B) per 100 parts by weight of (A) is 0.
1 to 50 parts by weight of a thermoplastic resin composition. (A): Polyphenylene ether resin (B): Ethylene-α, β having an α, β-unsaturated carboxylic acid alkyl ester in which the alkyl group has 2 or more carbon atoms
-An unsaturated carboxylic acid alkyl ester-based copolymer, wherein the content of the α, β-unsaturated carboxylic acid alkyl ester in the copolymer is 35 to 70% by weight-
α, β-Unsaturated Carboxylic Acid Alkyl Ester Copolymer 2. The composition according to claim 1, further comprising (C) in addition to (A) and (B), wherein the content of (C) per 100 parts by weight of (A) is 1900 parts by weight or less, And (B) per 100 parts by weight of the total amount of (A) and (C)
Is a thermoplastic resin composition having a content of 0.1 to 50 parts by weight. (C): Styrene resin 3. In addition to (A) and (B) described in claim 1, or (A), (B) and (C) described in claim 2, the following (D) is contained, and (A) and Total amount of (C) 100
A thermoplastic resin composition having a content of (D) of 50 parts by weight or less per part by weight. (D): rubbery polymer 4. The thermoplastic resin composition according to claim 1, wherein the α, β-unsaturated carboxylic acid alkyl ester (B) is ethyl (meth) acrylate.