JP2022001624A - Polyphenylene ether-based resin composition - Google Patents

Abstract

[Problem] The present invention aims to provide a polyphenylene ether resin composition that has an excellent balance between molding flowability and heat resistance, significantly suppresses the occurrence of silver streaks on the surface of the molded article during molding, and can provide a molded article that can be used as a thin-walled molded article with high appearance without painting. [Solution] A polyphenylene ether resin composition that contains polyphenylene ether (A), a styrene-based resin (B), a block copolymer (C) containing a styrene block and a hydrogenated conjugated diene compound block, and a terpene-phenol resin (D) having a softening point (measured by ring and ball method) of 155°C or higher, characterized in that the content of component (A) is 35 to 75 parts by mass, the content of component (B) is 5 to 50 parts by mass, the content of component (C) is 1 to 20 parts by mass, and the content of component (D) is 0.5 to 15 parts by mass relative to 100 parts by mass of the total amount of components (A), (B), (C), and (D). [Selected Figure] None

Description

The present invention relates to a polyphenylene ether-based resin composition.

Polyphenylene ether resin (PPE) has various properties such as excellent mechanical properties, electrical properties, acid / alkali resistance, and heat resistance, as well as low specific gravity, low water absorption, and good dimensional stability. Because of its possession, it is widely used as a material for home appliances, OA equipment, office machines, information equipment, automobiles, and the like. In recent years, in parts used for such applications, there are increasing demands for resin materials that are thinner, lighter, and can be used without painting and have a high appearance.

Patent Document 1 relates to a resin composition having improved molding fluidity even when an inorganic filler is added by blending a specific amount of a terpene phenolic resin or a chromane inden resin with a polyphenylene ether-based resin reinforced with an inorganic filler. The technology is disclosed.
Further, Patent Document 2 discloses a method of improving the adhesiveness with a polyurethane foam by blending a specific amount of a terpene phenol resin with a polyphenylene ether-based resin composition.
Patent Document 3 states that the molding fluidity and the gloss value of a molded product are improved by blending a specific amount of a hydrocarbon resin such as a petroleum resin having a specific softening point with a poly (arylene ether) resin. Is described.

Japanese Unexamined Patent Publication No. 59-126460 Japanese Unexamined Patent Publication No. 2-199164 International Publication No. 2012/115664

However, since the conventional molded product made of polyphenylene ether resin does not have sufficient molding fluidity, when a thin-walled, particularly large-area molded product is injection-molded, it is molded under high-temperature molding conditions exceeding 300 ° C. In some cases, silver streaks (silver, silver streaks), which are considered to be derived from decomposition products of resin components and additive components, are generated on the surface of the molded product during molding, and the appearance of the molded product is often deteriorated.

The techniques described in Patent Documents 1 to 3 described above can certainly obtain a resin composition capable of improving molding fluidity and improving the gloss of a molded product, but on the other hand, under harsh molding conditions, during molding. Silver streak may occur and deteriorate the surface appearance of the molded product, which is not always sufficient to obtain a high-appearance molded product that can be used without painting.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to obtain a molded product that has an excellent balance between molding fluidity and heat resistance, significantly suppresses the generation of silver streaks on the surface of the molded product during molding, and can be used as a thin-walled molded product having a high appearance without painting. It is an object of the present invention to provide a polyphenylene ether-based resin composition capable of producing a polyphenylene ether-based resin composition.

In order to solve the above problems, the present inventors have an object of developing a polyphenylene ether-based resin composition which has an excellent balance between molding fluidity and heat resistance and can be molded into a thin-walled molded product having a high appearance without coating. As a result of diligent studies, the polyphenylene ether resin contains a polystyrene resin, a specific elastomer component, and a terpenephenol resin having a specific softening point in a specific amount ratio, thereby causing an appearance defect due to silver streak on the surface of the molded product. The present invention has been completed by clarifying that a thin-walled molded product having a good molded appearance can be stably produced for a long period of time by improving the molding fluidity without generating the molded product.

That is, the present invention is as follows.
[1]
A block copolymer (C) containing a polyphenylene ether (A), a styrene resin (B), a styrene block and a hydrogenated conjugated diene compound block, and a softening point (measured by the ring ball method) at 155 ° C. Including the above-mentioned terpene-phenol resin (D)
The content of the component (A) is 35 to 75 parts by mass with respect to the total amount of the components (A), (B), (C), and (D) of 100 parts by mass, and the content of the component (B) is contained. The polyphenylene ether system is characterized in that the amount is 5 to 50 parts by mass, the content of the component (C) is 1 to 20 parts by mass, and the content of the component (D) is 0.5 to 15 parts by mass. Resin composition.
[2]
The heat stabilizer (E) having a melting point of 200 ° C. or higher is contained in an amount of 0.05 to 3 parts by mass with respect to 100 parts by mass of the total amount of the components (A), (B), (C) and (D). , [1] The polyphenylene ether-based resin composition.
[3]
In [1] or [2], the component (C) contains a copolymer (C—a) of a styrene block having a bound styrene content of 55% by mass or more and a hydrogenated conjugated diene compound block. The polyphenylene ether-based resin composition according to the above.
[4]
Further, it contains a polyolefin resin (F), and the mass ratio ((C-a) / (F)) of the component (C-a) to the component (F) is within the range of 9/1 to 6/4. The polyphenylene ether-based resin composition according to [3].
[5]
Any of [1] to [4], wherein the total content of the components (A), (B), (C), and (D) is 90% by mass or more of the total content of the polyphenylene ether-based resin composition. The polyphenylene ether-based resin composition according to.
[6]
When the polyamide resin and / or the polyolefin resin (F) is contained, the total content of the polyamide resin and the polyolefin resin (F) in the polyphenylene ether resin composition is 8% by mass or less. , [1] to [5]. The polyphenylene ether-based resin composition according to any one of [1] to [5].

According to the present invention, the molding has an excellent balance between molding fluidity and heat resistance, and the generation of silver streaks is remarkably suppressed during molding, so that the molding can be used as a thin-walled molded product having a high appearance without painting. It is possible to provide a polyphenylene ether-based resin composition from which an article can be obtained.

Hereinafter, a mode for carrying out the present invention (hereinafter, referred to as “the present embodiment”) will be described in detail. The present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof.

<< Polyphenylene ether-based resin composition >>
The polyphenylene ether-based resin composition of the present embodiment (hereinafter, also simply referred to as “resin composition”) is a polyphenylene ether (A), a styrene-based resin (B), a styrene block, and a conjugated diene compound hydrogenated. A block copolymer (C) containing a block (hydrogenated conjugated diene compound block) and a terpene-phenol resin (D) having a softening point (measured by the ring-ball method) at 155 ° C. or higher are contained in the above (A). , (B), (C), and (D) have a total content of 100 parts by mass, the content of the component (A) is 35 to 75 parts by mass, and the content of the component (B) is 5 to 5. The content of the component (C) is 50 parts by mass, the content of the component (C) is 1 to 20 parts by mass, and the content of the component (D) is 0.5 to 15 parts by mass.
The present inventors have the above-mentioned resin composition having an excellent balance between molding fluidity and heat resistance, and the generation of silver streaks is remarkably suppressed during molding, so that the resin composition is unpainted and has a high appearance. We have found that it is a polyphenylene ether-based resin composition that can be used as a molded product, and it is sufficiently suitable for home appliance OA equipment parts such as projectors and various lighting fixtures, and decorative molded parts used for electrical and electronic equipment, automobile applications, etc. Found to be applicable.
Hereinafter, each component of the above resin composition will be described in detail.

・・・（１）〔ａ〕

・・・（１）〔ｂ〕
上記式（１）〔ａ〕、〔ｂ〕中、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５及びＲ_６は、それぞれ独立して、炭素数１〜４のアルキル基、炭素数６〜１２のアリール基、並びにハロゲン原子及び水素原子からなる群から選ばれる一価の残基であることが好ましい。
但し、かかる場合、Ｒ_５及びＲ_６が同時に水素である場合を除く。
また、前記アルキル基のより好ましい炭素数は１〜３であり、前記アリール基のより好ましい炭素数は６〜８であり、前記一価の残基の中でもより好ましくは水素である。
尚、上記（１）の〔ａ〕及び〔ｂ〕における繰り返し単位の数については、ポリフェニレンエーテル（Ａ）の分子量分布により様々であるため、特に制限されることはない。 <Polyphenylene ether (A)>
The polyphenylene ether (A) is preferably a homopolymer or a copolymer having a repeating structural unit consisting of [a] and / or [b] of the following general formula (1).

... (1) [a]

... (1) [b]
In the above formulas (1) [a] and [b], R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are independently alkyl groups having 1 to 4 carbon atoms and 6 carbon atoms, respectively. It is preferably a monovalent residue selected from the group consisting of an aryl group of ~ 12 and a halogen atom and a hydrogen atom.
However, in such a case, the case where R ₅ and R ₆ are hydrogen at the same time is excluded.
Further, the alkyl group has a more preferable carbon number of 1 to 3, the aryl group has a more preferable carbon number of 6 to 8, and hydrogen is more preferable among the monovalent residues.
The number of repeating units in [a] and [b] of (1) above is not particularly limited because it varies depending on the molecular weight distribution of the polyphenylene ether (A).

The homopolymer of the polyphenylene ether is not limited to the following, and is, for example, a poly (2,6-dimethyl-1,4-phenylene) ether, a 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 and poly (2-methyl-6-chloroethyl-1,4-phenylene) ether, etc. Can be mentioned.

The polyphenylene ether copolymer is not limited to the following, but is, for example, a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, and 2,6-dimethylphenol and o-cresol. Examples thereof include those having a polyphenylene ether structure as a main component, such as a copolymer of 2,3,6-trimethylphenol and o-cresol.

Among the polyphenylene ethers, it is preferable to use poly (2,6-dimethyl-1,4-phenylene) ether.

The above-mentioned polyphenylene ether (A) may be used alone or in combination of two or more.

Further, the polyphenylene ether (A) may contain various phenylene ether units other than the formulas (1) [a] and [b] as a partial structure.
The phenylene ether unit is not limited to the following, and is, for example, 2- (dialkylaminomethyl) -6-methylphenylene ether described in JP-A No. 01-297428 and JP-A-63-301222. Examples thereof include 2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene ether unit.

Further, the polyphenylene ether (A) may contain a structural unit other than the phenylene ether unit in the main chain.
Examples of such a structural unit include a unit derived from diphenoquinone. However, the structural unit other than the phenylene ether unit contained in the main chain is preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 5 with the polyphenylene ether (A) as 100% by mass. It is less than mass%.

Further, the polyphenylene ether (A) is one selected from the group consisting of a part or all of the polyphenylene ether, a carboxylic acid, an acid anhydride, an acid amide, an imide, an amine, an orthoester, a hydroxy, and an ammonium carboxylate salt. It may be a functionalized polyphenylene ether by reacting (modifying) with a functionalizing agent containing the above.

The reduced viscosity of the polyphenylene ether (A) used in the present embodiment is preferably in the range of 0.25 to 0.60 dL / g, more preferably 0.30 to 0.55 dL / g, and even more preferably. It is in the range of 0.35 to 0.50 dL / g. From the viewpoint of sufficient mechanical properties, 0.25 dL / g or more is preferable, and from the viewpoint of molding processability and brightness feeling of the molded product, 0.55 dL / g or less is preferable.
The reduced viscosity in this embodiment is a value obtained by measuring with a chloroform solvent, a concentration of 0.50 g / dL, and a Ubbelohde viscometer at 30 ° C.

The ratio (Mw / Mn value) of the polyphenylene ether (A) used in the present embodiment to the weight average molecular weight Mw (in the form of polymerized powder) before heat processing by extrusion or the like and the number average molecular weight Mn is preferably 1. It is 2 to 3.0, more preferably 1.5 to 2.5, and even more preferably 1.8 to 2.3. The Mw / Mn value is preferably 1.2 or more from the viewpoint of molding processability of the resin composition, and is preferably 3.0 or less from the viewpoint of maintaining the mechanical properties of the resin composition, particularly the tensile strength.
The weight average molecular weight Mw and the number average molecular weight Mn are obtained from polystyrene-equivalent molecular weights measured by GPC (gel permeation chromatography).

In the polyphenylene ether-based resin composition of the present embodiment, the content of the polyphenylene ether (A) is 100 mass by mass, which is the total amount of the components (A), (B), (C), and (D) in the resin composition. It is contained in the range of 35 to 75 parts by mass. The content is preferably 40 to 75 parts by mass, more preferably 50 to 70 parts by mass, and further preferably 55 to 70 parts by mass. From the viewpoint of sufficient heat resistance, it is important to contain 35 parts by mass or more, and from the viewpoint of maintaining the appearance of molding during molding, it is important to contain 75 parts by mass or less.

<Styrene resin (B)>
In the resin composition of the present embodiment, the styrene resin (B) can be blended mainly for the purpose of improving the molding fluidity.
In the present embodiment, the styrene-based resin (B) is a homopolymer of a styrene-based compound, or a copolymer of a styrene-based compound and a compound copolymerizable with the styrene-based compound (excluding the conjugated diene compound). To say. This component (B) does not include those included in the category of the component (C) described later.
Specific examples of the styrene-based resin (B) include styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert-butylstyrene, ethylstyrene and the like.

Examples of the compound that can be copolymerized with the styrene compound include methacrylic esters such as methyl methacrylate and ethyl methacrylate; unsaturated nitrile compounds such as acrylonitrile and methacryl nitrile; and acid anhydrides such as maleic anhydride. Be done.

The styrene-based resin (B) can be obtained by polymerizing a styrene-based compound or a compound copolymerizable with the styrene-based compound and the styrene-based compound in the presence or absence of a rubbery polymer.
Here, examples of the rubbery polymer include conjugated diene-based rubbers, copolymers of conjugated diene and aromatic vinyl compounds, hydrogenated products thereof, ethylene-propylene copolymerized rubbers, and the like.

In the present embodiment, the styrene resin (B) is preferably polystyrene or high-impact polystyrene reinforced with a rubbery polymer, and more preferably polystyrene.

The content of the styrene-based resin (B) in the resin composition of the present embodiment is 100 parts by mass in total of the components (A), (B), (C), and (D) in the resin composition. It is contained in the range of 5 to 50 parts by mass. It is preferably in the range of 10 to 40 parts by mass, more preferably in the range of 15 to 30 parts by mass, and particularly preferably in the range of 15 to 25 parts by mass. From the viewpoint of imparting sufficient molding fluidity, it is important to contain 5 parts by mass or more, and from the viewpoint of maintaining sufficient heat resistance, it is important to contain 50 parts by mass or less.

<Block copolymer (C) containing a styrene block and a hydrogenated conjugated diene compound block>
The resin composition of the present embodiment containing the above-mentioned polyphenylene ether (A) and styrene resin (B) contains a styrene block and a hydrogenated conjugated diene compound block from the viewpoint of improving impact resistance. Containing copolymer (C) (hereinafter, may be referred to as "block copolymer of styrene block and hydrogenated conjugated diene compound block" or "styrene block-hydrogenated conjugated diene compound block copolymer"). do.

From the viewpoint of thermal stability, the conjugated diene compound block preferably has a hydrogenation rate of 50% or more, more preferably 80% or more, still more preferably 95% or more.

Examples of the conjugated diene compound block include, but are not limited to, polybutadiene, polyisoprene, poly (ethylene / butylene), poly (ethylene / propylene), vinyl-polyisoprene and the like. The conjugated diene compound block may be used alone or in combination of two or more.

The mode of arrangement of the repeating units constituting the block copolymer may be a linear type or a radial type.
Further, the block structure composed of the polystyrene block and the rubber intermediate block may be any of type 2, type 3 and type 4. Above all, from the viewpoint that the desired effect can be sufficiently exerted in the present embodiment, a three-type linear type block copolymer (SEBS) having a polystyrene-poly (ethylene-butylene) -polystyrene structure is preferable. Is.
The conjugated diene compound block may contain butadiene units in a range not exceeding 30% by mass from the viewpoint of imparting impact resistance.

From the viewpoint of improving impact resistance, the component (C) preferably has a weight average molecular weight Mw in the range of 40,000 to 300,000, more preferably 50,000 to 280,000, and even more preferably. Is 80,000 to 250,000. From the viewpoint of imparting sufficient impact resistance, it is preferably 40,000 or more, and from the viewpoint of fluidity, appearance retention, and miscibility of the molded product, it is preferably 300,000 or less.

The amount of bound styrene of the styrene block-hydrogenated conjugated diene compound block copolymer is preferably in the range of 20 to 80% by mass, more preferably 50 to 70% by mass, and further preferably 55 to 75% by mass. Is. From the viewpoint of miscibility, the amount of bound styrene is preferably 20% by mass or more, and preferably 80% or less from the viewpoint of imparting impact resistance.

The component (C) more preferably contains an oil-expanded styrene block-hydrogenated conjugated diene compound block copolymer from the viewpoint of improving miscibility with the resin and improving molding fluidity.
Specifically, it is preferable to contain 5 to 100 parts by mass of the oil component with respect to 100 parts by mass of the styrene block-hydrogenated conjugated diene compound block copolymer (C). The content of the oil component is more preferably 10 to 75 parts by mass, still more preferably 20 to 50 parts by mass.
From the viewpoint of dispersibility of the component (C) with respect to the resin component, the content of the oil component with respect to 100 parts by mass of the styrene block-hydrogenated conjugated diene compound block copolymer (C) is preferably 5 parts by mass or more. From the viewpoint of heat resistance and prevention of oil bleeding on the surface of the molded body, it is preferably 100 parts by mass or less.
Here, examples of the oil component include paraffin-based, naphthen-based, and aroma-based process oils, mineral oils such as liquid paraffin, and castor oil, which are generally used as softeners for rubber. These oil components may be used alone or in combination of two or more. Further, it may be contained in the copolymer in advance at the time of producing the styrene block-hydrogenated conjugated diene compound block copolymer, or the styrene block-hydrogenated conjugated diene compound block copolymer may be extruded. It may be added and contained at the time of melt-kneading by a machine or the like.

When a high molecular weight type (Mw: 200,000 to 300,000) styrene block-hydrogenated conjugated diene compound block copolymer is used as the component (C), the miscibility in the resin composition is not sufficient by itself. , There is a risk of layer peeling on the molded product. Therefore, a styrene block-hydrogenated conjugated diene compound block copolymer of a medium molecular weight type (Mw: 50,000 to 150,000) and a bound styrene content of 55 to 80% by mass, or an oil-expanded styrene block-water. It is preferable to use a conjugated diene compound block copolymer in combination.
Medium molecular weight type and / or oil-extended type styrene block-hydrogenated conjugated diene compound block copolymer having a bound styrene content of 55 to 80% by mass, and high molecular weight type styrene block-hydrogenated conjugated diene compound block co-weight. Mass ratio with coalescence (medium molecular weight type and / or oiled type styrene block-hydrogenated conjugated diene compound block copolymer / high molecular weight type styrene block-hydrogenated conjugated diene with 50-80% by mass of bonded styrene) The compound block copolymer) is preferably in the range of 9/1 to 3/7, more preferably in the range of 7/3 to 5/5.

From the viewpoint of improving impact resistance, the component (C) preferably contains a block copolymer (C-a) of a styrene block having a bound styrene content of 55% by mass or more and a hydrogenated conjugated diene compound block. Further, the resin composition of the present embodiment may contain the polyolefin-based resin (F) described later as an elastomer component other than the component (C) in addition to the component (C-a).

The content of the component (C) in the resin composition of the present embodiment is 1 to 1 in 100 parts by mass of the total amount of the components (A), (B), (C), and (D) in the resin composition. It is within the range of 20 parts by mass. It is preferably in the range of 3 to 20 parts by mass, more preferably 5 to 15 parts by mass. The content of the component (C) is 1 part by mass or more from the viewpoint of obtaining impact resistance, and 20 parts by mass or less from the viewpoint of heat resistance and rigidity retention.

<Terpene / phenolic resin (D)>
The resin composition of the present embodiment containing the above-mentioned polyphenylene ether (A) and styrene resin (B) improves molding fluidity without deteriorating the heat resistance, mechanical strength, impact resistance, etc. of the molded product. It contains terpene-phenol resin (D) from the viewpoint of making it.

The terpene-phenol resin (D) contained in the resin composition of the present embodiment suppresses the generation of silver streak on the surface of the molded product during high-temperature molding, and maintains heat resistance, mechanical strength, impact resistance, and the like. From the viewpoint, it is a terpene-phenol resin having a softening point (measured by the ring-and-ball method) of 155 ° C. or higher.

The terpene-phenol resin is a copolymer of terpenes and phenols, and is known by itself.
The terpenes are hydrocarbons represented by (C ₅ H ₆ ) _n or oxygen-containing compounds derived from them, for example, monoterpenes (when n = 2, myrcene, osimene, pinen, limonene, citroneol, borneol, etc. Mentors, shownows, etc.), sesquiterpenes (n = 3, curcumen, etc.), diterpenes (n = 4, kanhorene, hinokiol, etc.), tetraterpenes (n = 8, carotinoids, etc.), Examples include polyterpenes (natural rubber). Preferred terpenes are monoterpenes, and particularly preferably pinene, limonene and the like.
Phenols are compounds having at least one hydroxyl group on an aromatic ring such as a benzene ring or a naphthalene ring, and may have a substituent (for example, a halogen atom, an alkyl group, etc.) on the aromatic ring. Examples of the phenols include phenol, cresol, xylenol, naphthol, catechol, resilcin, hydroquinone, pyrogallol and the like. Preferred phenols are phenols.
A preferable terpene / phenol resin is a polymer of monoterpenes and phenol, and more preferably a polymer of monoterpenes such as α-pinene and limonene and phenol.

The softening point of the terpene / phenol resin used in the resin composition of the present embodiment is 155 ° C. or higher from the viewpoint of suppressing silver streak of the molded product and maintaining heat resistance, mechanical strength, impact resistance and the like. It is preferably 155 to 180 ° C, more preferably 160 to 170 ° C.
In the present disclosure, the softening point refers to a value measured based on the softening point measuring method (ring ball method) specified in JIS K5902 and JIS K2207.
Regarding the softening point measurement method (ring ball method), specifically, the sample is melted as quickly as possible at a low temperature, and bubbles cannot be formed in the ring (annular mold) placed on a flat metal plate. Carefully fill. After cooling, use a slightly heated knife to cut off the raised part from the plane including the upper end of the ring. Next, a support (ring stand) is placed in a glass container (heating bath) having a diameter of 85 mm or more and a height of 127 mm or more, and glycerin is poured until the depth becomes 90 mm or more. Next, the steel ball (diameter 9.5 mm, weight 3.5 g) and the ring filled with the sample are immersed in glycerin so as not to come into contact with each other, and the temperature of the glycerin is maintained at 20 ° C. ± 5 ° C. for 15 minutes. Next, a steel ball is placed in the center of the surface of the sample in the ring and placed in place on the support. Next, the distance from the upper end of the ring to the glycerin surface is kept at 50 mm, a thermometer is placed, the position of the center of the mercury bulb of the thermometer is set to the same height as the center of the ring, and the container is heated. The flame of the Bunsen burner used for heating is placed between the center and the edge of the bottom of the container to equalize the heating. The rate at which the bath temperature rises after reaching 40 ° C. after the start of heating is 5.0 ± 0.5 ° C. per minute. The temperature at which the sample gradually softens, flows down from the ring, and finally comes into contact with the bottom plate of the container is read, and this is used as the softening point. The softening point is measured on two or more samples at the same time, and the average value is adopted.

The content of the terpene / phenol resin (D) in the resin composition of the present embodiment is 100 parts by mass in total of the components (A), (B), (C) and (D) in the resin composition. It is in the range of 0.5 to 15 parts by mass. It is preferably in the range of 1 to 15 parts by mass, more preferably 3 to 13 parts by mass.
From the viewpoint of improving the molding fluidity of the resin composition, it is essential to contain 0.5 parts by mass or more, and from the viewpoint of maintaining sufficient mechanical properties and thermal stability of the resin composition, it is essential to contain 15 parts by mass or less. be.

<Heat stabilizer (E)>
In the resin composition of the present embodiment, the heat stabilizer (E) having a melting point of 200 ° C. or higher is added to 100 parts by mass of the total amount of the components (A), (B), (C) and (D). It is preferably contained in an amount of 0.05 to 3 parts by mass.
The resin composition of the present embodiment containing the above-mentioned polyphenylene ether (A) and styrene resin (B) may contain a heat stabilizer (E) mainly from the viewpoint of improving thermal stability during molding. Preferably, the heat stabilizer (E) has a melting point of 200 ° C. or higher, particularly from the viewpoint of suppressing the generation of silver streak on the surface of the molded product during high-temperature molding.

Examples of the heat stabilizer (E) having a melting point of 200 ° C. or higher include a hindered phenol-based heat stabilizer and a phosphorus-based heat stabilizer.
Specific examples of the hindered phenolic heat stabilizer include 3,3', 3'', 5,5', 5''-hexa-tert-butyl-a, a'', a''-(. Mesitylene-2,4,6-triyl) tri-p-cresol, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2, 4,6 (1H, 3H, 5H) -trion and the like can be mentioned.
Specific examples of the phosphorus-based heat stabilizer include 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro. [5,5] Undecane, bis (2,4-dicumylphenyl) pentaerythritol diphosphite and the like can be mentioned.

It is important that the heat stabilizer (E) used in the present embodiment is a heat stabilizer having a melting point of 200 ° C. or higher from the viewpoint of improving the appearance of the molded product (suppressing the generation of silver streak). The melting point of the component (E) is preferably in the range of 200 to 280 ° C, more preferably in the range of 210 to 270 ° C, and even more preferably in the range of 220 to 260 ° C.
In the present embodiment, the melting point of the component (E) can be measured by, for example, a melting point measuring device (model: B-545, manufactured by Shibata Scientific Technology Co., Ltd.).

The content of the heat stabilizer (E) having a melting point of 200 ° C. or higher in the resin composition of the present embodiment is (A) in the resin composition from the viewpoint of improving the appearance of the molded product (suppressing the generation of silver streaks). , (B), (C), and (D) are preferably selected from the range of 0.05 to 3 parts by mass with respect to 100 parts by mass of the total amount of the components. It is more preferably in the range of 0.1 to 2 parts by mass, and further preferably in the range of 0.5 to 1 part by mass.

<Polyolefin resin (F)>
The resin composition of the present embodiment may contain a polyolefin-based resin (F). The polyolefin resin (F) is not limited to the following, but is, for example, an ethylene-α-olefin copolymer such as polyethylene, polypropylene, an ethylene-propylene copolymer, an ethylene-octene copolymer, or ethylene. Examples thereof include ethylene-alkyl acrylate copolymers such as methyl acrylate, ethyl ethylene-ethyl acrylate, ethylene-methyl methacrylate, and ethylene-ethyl methacrylate.

When the ethylene-based copolymer is used as the polyolefin-based resin, the mass ratio of the ethylene component and the component copolymerizable with ethylene in the ethylene-based copolymer (ethylene component / component copolymerizable with ethylene). Is preferably in the range of 60/40 to 95/5, more preferably 65/35 to 65, from the viewpoint of improving compatibility with the styrene block-conjugated diene compound block copolymer, heat resistance, mechanical properties and the like. It is 90/10, more preferably in the range of 70/30 to 85/15.

When the polyolefin-based resin (F) is blended alone in the resin composition of the present embodiment, the miscibility in the resin composition is not sufficient and the molded product may be layered. It is preferable to use in combination with a styrene block-hydrogenated conjugated diene compound block copolymer (C-a) having a bonded styrene content of 55% by mass or more.

The content of the polyolefin resin (F) is preferably small from the viewpoint of maintaining physical properties, and the mass ratio of the component (C-a) to the component (F) ((C-a) / (F)). ) Is preferably in the range of 9/1 to 6/4, and more preferably in the range of 8/2 to 7/3.

<Other additives>
The resin composition of the present embodiment has other components such as an antioxidant, a lubricant, a mold release agent, a colorant, etc., as long as the heat resistance, mechanical properties, surface appearance, etc. of the resin composition are not significantly deteriorated. It is possible to further contain additives.
When the above-mentioned other additives are contained, they are preferably contained in the range of 0.001 to 3% by mass, more preferably 0.01 to 2% by mass, based on 100% by mass of the resin composition. %, More preferably in the range of 0.05 to 1% by mass. From the viewpoint of exhibiting a sufficient addition effect, the above-mentioned other additives are preferably contained in an amount of 0.001% by mass or more, and preferably 3% by mass or less from the viewpoint of sufficient appearance and maintenance of physical properties of the molded product.

Further, the resin composition of the present embodiment may contain a polyamide-based resin as long as it is in a small amount.
The polyamide-based resin is not particularly limited, but for example, polyamide 6, polyamide 6, 6, polyamide 4, 6, polyamide 11, polyamide 12, polyamide 6, 10, polyamide 6, 12, polyamide 6/6, 6, polyamide. 6/6, 12, Polyamide MXD (m-xylylene diamine), 6, Polyamide 6, T, Polyamide 9, T, Polyamide 6, I, Polyamide 6 / 6, T, Polyamide 6/6, I, Polyamide 6, 6/6, T, Polyamide 6,6 / 6, I, Polyamide 6/6, T / 6, I, Polyamide 6, 6/6, T / 6, I, Polyamide 6/12 / 6, T, Polyamide 6 , 6/12/6 T, Polyamide 6/12/6, I, Polyamide 6, 6/12/6, I and the like.
When the resin composition of the present embodiment contains a polyamide-based resin and / or a polyolefin-based resin (F), the polyamide-based resin and the polyolefin in 100% by mass of the resin composition from the viewpoint of sufficient appearance of the molded product and retention of physical properties. The total content with the based resin (F) (when containing only one of the polyamide resin or the polyolefin resin (F), the content of only one of them) is preferably 8% by mass or less. It is more preferably 5% by mass or less, further preferably 3% by mass or less, and particularly preferably 1% by mass or less.

In the resin composition of the present embodiment, from the viewpoint of sufficient appearance of the molded product and maintenance of physical properties, the total content of the components (A), (B), (C), and (D) is the entire resin composition. It is preferably 90% by mass or more. It is more preferably 92% by mass or more, further preferably 95% by mass or more, and particularly preferably 97% by mass or more.

[Manufacturing method of resin composition]
The resin composition of the present embodiment melts the above-mentioned (A), (B), (C), and (D) components, and if necessary, raw materials such as (E) component and / or other additives. It can be produced by melt-kneading by appropriately adjusting the kneading conditions.
Regarding the conditions for melt-kneading the components (A), (B), (C), and (D) for producing the resin composition, and the component (E) and / or other additives, the resin composition. Although not particularly limited in the material, from the viewpoint of stably obtaining a large amount of a resin composition capable of sufficiently exerting the desired effect of the present embodiment, biaxial extrusion with a screw diameter of 25 to 90 mm is performed. It is preferable to use a machine. As an example, TEM58SS twin-screw extruder (manufactured by Toshiba Machine Co., Ltd., number of barrels 13, screw diameter 58 mm, L / D = 53); kneading disc L: 2, kneading disc R: 14, and kneading disc N. : When using a screw pattern with two pieces), the conditions are a cylinder temperature of 270 to 330 ° C., a screw rotation speed of 150 to 700 rpm, an extrusion rate of 150 to 700 kg / h, and a vent vacuum degree of 11.0 to 1.0 kPa. A method of melt-kneading can be mentioned.

The extruded resin temperature is preferably in the range of 280 to 360 ° C. from the viewpoint of sufficient expression of the effects required for the present application and extrudability. A more preferable range of the extruded resin temperature is 290 to 350 ° C, and a more preferable range is 300 to 340 ° C. The temperature is preferably 280 ° C. or higher from the viewpoint of sufficient miscibility of the resin composition, and is preferably 360 ° C. or lower from the viewpoint of preventing thermal deterioration of the resin.

When the polyphenylene ether-based resin composition of the present embodiment is produced using a large-sized (screw diameter 40 to 90 mm) twin-screw extruder, it should be noted that the above-mentioned ( A) The mixing of gels and carbides generated from the components may cause deterioration of the surface appearance, impact resistance, and toughness of the molded product. Therefore, it is preferable to charge the component (A) from the most upstream raw material inlet (top feed) and set the oxygen concentration inside the shooter at the most upstream inlet to 8% by volume or less, more preferably. It is 5% by volume or less, and even more preferably 1% by volume or less.
To adjust the oxygen concentration, sufficiently replace the inside of the raw material storage hopper with nitrogen, seal the feed line from the raw material storage hopper to the raw material input port of the extruder so that air does not enter and exit, and then the amount of nitrogen feed. It is possible by adjusting the opening of the gas vent.

[Molding]
The molded product made of the resin composition of the present embodiment can be obtained by molding the above-mentioned resin composition.
The average molding thickness of the molded product made of the polyphenylene ether-based resin composition of the present embodiment is preferably in the range of 0.5 to 2.5 mm. It is more preferably in the range of 0.7 to 2.2 mm, and even more preferably in the range of 1.0 to 2.0 mm.
From the viewpoint of maintaining sufficient strength of the molded product, it is preferably 0.5 mm or more, and from the viewpoint of maintaining the lightness of the molded product, it is preferably 2.5 mm or less.

The molding method of the resin composition is not limited to the following, and examples thereof include injection molding, extrusion molding, vacuum forming and pressure molding, and injection molding is more preferably used from the viewpoint of mass productivity. ..
The molding temperature at the time of molding the resin composition is preferably in the range of the barrel set maximum temperature of 280 to 340 ° C, more preferably 300 to 330 ° C, and even more preferably 300 to 320 ° C. .. From the viewpoint of sufficient molding processability, the molding temperature is preferably 280 ° C. or higher, and from the viewpoint of suppressing thermal deterioration of the resin, it is preferably 340 ° C. or lower.
The mold temperature at the time of molding the resin composition is preferably in the range of 40 to 160 ° C., more preferably 80 to 150 ° C., and even more preferably 80, from the viewpoint of sufficiently maintaining the appearance of the molded product. It is in the range of ~ 130 ° C.

As a suitable molded product in the present embodiment, deterioration of the molded appearance due to the generation of silver streak caused by molding under high temperature and high shear conditions is remarkably suppressed, and the molded product can be used as a molded product having a high appearance without painting. Therefore, examples thereof include home appliance OA equipment parts, electric and electronic equipment, automobile applications, decorative molded parts used in various industrial products, and the like.

Hereinafter, the present embodiment will be described in more detail with reference to Examples and Comparative Examples, but the present embodiment is not limited to these Examples. The methods for measuring physical properties and raw materials used in Examples and Comparative Examples are shown below.

[Method for producing molded pieces and measuring physical properties]
1. 1. Preparation of Molded Piece The pellets of the resin composition obtained in the following Examples and Comparative Examples were dried in a hot air dryer at 100 ° C. for 2 hours, and then an injection molding machine equipped with an ISO physical property test piece mold (IS). -100EPN, manufactured by Toshiba Machinery Co., Ltd.), set the cylinder temperature to 300 ° C, the mold temperature to 80 ° C, the injection pressure to 50 MPa (gauge pressure), the injection speed to 200 mm / sec, and the injection time / cooling time to 20 sec / 20 sec, and set it to ISO3167. , Multipurpose test piece A type dumbbell molded piece was molded.

2. 2. Heat distortion (DTUL)
Above 1. The multipurpose test piece A type dumbbell molded piece obtained in 1 was cut to prepare three 80 mm × 10 mm × 4 mm molded pieces. Using the test piece, the deflection temperature under load (DTUL) (° C.) was measured at 1.82 MPa by the flatwise method in accordance with ISO75.
As an evaluation standard, it was determined that the higher the measured value (the average value of three measured pieces), the better the heat resistance.

3. 3. Molding fluidity (MFR)
The pellets of the resin composition obtained in the following Examples and Comparative Examples are dried in a hot air dryer at 100 ° C. for 2 hours, and then conformed to ISO1133 using a melt indexer (P-111, manufactured by Toyo Seiki Co., Ltd.). Examples 5 to 9 and Comparative Examples 2 to 8 have a set temperature of 250 ° C. and a load of 10 kg, and Examples 1 to 4, Comparative Example 1 and Comparative Example 9 have a set temperature of 280 ° C. and a load of 10 kg and a melt flow rate (MFR). ) (G / 10min) was measured.
As an evaluation standard, it was determined that the higher the MFR value, the better the molding fluidity.
Further, it was determined that the higher the value of DTUL and the higher the value of MFR described above, the better the balance between heat resistance and molding fluidity, which is advantageous in terms of material design.

4. Rigidity (bending strength, flexural modulus)
Above 1. The multipurpose test piece A type dumbbell molded piece obtained in 1 was cut to prepare three 80 mm × 10 mm × 4 mm molded pieces. Using the test piece, the bending strength (MPa) and the bending elastic modulus (MPa) were measured at 23 ° C. in accordance with ISO178.
As an evaluation standard, it was determined that the higher the measured values of bending strength and flexural modulus (average value of three measured lines), the better the rigidity.

5. Impact resistance (Charpy impact strength)
Above 1. The multipurpose test piece A type dumbbell molded piece obtained in 1 was cut to prepare 5 molded pieces having a size of 80 mm × 10 mm × 4 mm. Using the test piece, the Charpy impact strength (with notch) (kJ / m ² ) was measured at 23 ° C. in accordance with ISO179.
As an evaluation standard, it was determined that the higher the measured value (the average value of 5 measured pieces), the better the impact resistance.

6. Stagnant molding stability (visual judgment of silver streak)
The pellets of the resin composition obtained in the following Examples and Comparative Examples were dried in a hot air dryer at 100 ° C. for 2 hours, and then an injection molding machine (IS-100EPN, Toshiba) equipped with an ISO physical characteristic test piece mold was provided. Using (manufactured by Machine Co., Ltd.), the resin composition was filled in the cylinder at a cylinder set temperature of 300 ° C. and retained for 30 minutes. Then, after injecting one shot of the resin composition inside the cylinder, the above 1. Under the conditions of ISO3167, continuous molding (30 shots) of a dumbbell molded piece of ISO3167, multipurpose test piece A type was performed.
“◎” indicates that no silver streak was observed from the molded pieces on the 1st and 2nd shots, and “〇”, 6 to 10 indicate that no silver streak was observed from the molded pieces after the 3rd to 5th shots. Those in which silver streak was no longer observed in the molded pieces after the 10th shot were evaluated as "Δ", and those in which silver streak was observed in the molded pieces after the 10th shot were evaluated as "x". As evaluation criteria, ⊚ and 〇 were judged to be excellent in retention molding stability, and ⊚ was judged to be particularly preferable as the resin composition of the present invention.

[raw materials]
<Polyphenylene ether (A)>
(A-1)
Poly (2,6-dimethyl-1,4-phenylene ether) having a reduced viscosity of 0.40 dL / g (0.5 g / dL chloroform solution, 30 ° C., measured with an Ubbelohde viscometer) (hereinafter, "(A-1)). ") Was used.
(A-2)
Poly (2,6-dimethyl-1,4-phenylene ether) having a reduced viscosity of 0.30 dL / g (0.5 g / dL chloroform solution, 30 ° C., measured with an Ubbelohde viscometer) (hereinafter, "(A-2)). ") Was used.

<Styrene resin (B)>
(B-1)
General Purpose Polystyrene (GPPS) (trade name: Polystyrene 680 [registered trademark], manufactured by PS Japan Corporation. Hereinafter, it may be referred to as "(B-1)") was used.
(B-2)
High-impact polystyrene (HIPS) (trade name: polystyrene H9405 [registered trademark], manufactured by PS Japan Corporation. Hereinafter, it may be referred to as "(B-2)") was used.

<Styrene block-hydrogenated conjugated diene compound block copolymer (C)>
(C-1)
Oil exhibition SEBS (trade name: Tough Tech H1272 [registered trademark], manufactured by Asahi Kasei Corporation. Hereinafter, it may be referred to as "(C-1)") was used.
(C-a)
A three-type hydrogenated block copolymer having a polystyrene block-hydrogenated polybutadiene block-polystyrene block structure with an amount of bound styrene of 67% by mass and a hydrogenation rate of the polybutadiene block portion of 98% (hereinafter, "(. C-a) ”) was used.

<Terpene / phenolic resin (D)>
(D-1)
A terpene-phenol resin (trade name: YS Polystar T160 [registered trademark], manufactured by Yasuhara Chemical Co., Ltd., hereinafter sometimes referred to as "(D-1)") having a softening point (measured by the ring and ball method) at 160 ° C. was used.

<Terpen / phenolic resin>
(D'-1)
A terpene phenolic resin (trade name: YS Polystar T145 [registered trademark], manufactured by Yasuhara Chemical Co., Ltd., hereinafter sometimes referred to as "(D'-1)") having a softening point (measured by the ring and ball method) at 145 ° C. was used. ..
(D'-2)
A terpene phenolic resin (trade name: YS Polystar T130 [registered trademark], manufactured by Yasuhara Chemical Co., Ltd., hereinafter sometimes referred to as "(D'-2)") having a softening point (measured by the ring and ball method) at 130 ° C. was used. ..

<Aromatic petroleum resin>
Aromatic petroleum resin with a softening point (measured by the ring and ball method) at 165 ° C (trade name: Nisseki Neopolymer 160 [registered trademark], manufactured by JXTG Energy Co., Ltd. Hereinafter, it may be simply referred to as "aromatic petroleum resin". ) Was used.

<Heat stabilizer (E)>
(E-1)
Hindered phenolic heat stabilizer with a melting point of 242 ° C (chemical names: 3,3', 3'', 5,5', 5''-hexa-tert-butyl-a, a'', a''-( Mesitylene-2,4,6-triyl) tri-p-cresol, trade name: Irganox1330 [registered trademark], manufactured by BASF, Inc., hereinafter sometimes referred to as "(E-1)") was used.
(E-2)
Phosphorus-based heat stabilizer having a melting point of 225 ° C. (chemical name: bis (2,4-dicumylphenyl) pentaerythritol diphosphite, trade name: DoverPhos S-9228 [registered trademark], manufactured by Dover Chemical Co., Ltd. E-2) ”) was used.

<Polyolefin resin (F)>
(F-1)
An ethylene-octene copolymer (trade name: Engage 8180 [registered trademark], manufactured by DuPont Dow Elastomer, Inc., hereinafter sometimes referred to as "(F-1)") was used.
(F-2)
LDPE (trade name: Suntech LD M2004 [registered trademark], manufactured by Asahi Kasei Corporation. Hereinafter, it may be referred to as "(F-2)") was used.

[Comparative Example 1]
(A-1) 74 parts by mass, (B-1) 21 parts by mass, (C-a) 5 parts by mass, and (F-1) 2 parts by mass, TEM58SS twin-screw extruder (Toshiba Machine Co., Ltd.) The most upstream part of (screw pattern having 13 barrels, 58 mm screw diameter, L / D = 53) (kneading disc L: 2, kneading disc R: 14, and kneading disc N: 2). It was supplied from (top feed) and melt-kneaded under the conditions of a cylinder temperature of 300 ° C., a screw rotation speed of 450 rpm, an extrusion rate of 400 kg / hr, and a vent vacuum degree of 7.998 kPa (60 Torr) to obtain pellets of a resin composition.
The evaluation results of the obtained resin composition are shown in Table 1 below.

[Example 1]
Pellets of the resin composition were obtained by melt-kneading under the same conditions as the extrusion of Comparative Example 1 except that 10 parts by mass of the 21 parts by mass of (B-1) was replaced with (D-1). ..
The evaluation results of the obtained resin composition are shown in Table 1 below.

[Example 2]
(A-1) 74 parts by mass, (B-1) 11 parts by mass, (C-a) 5 parts by mass, (D-1) 10 parts by mass, (E-1) 0.5 parts by mass. And (F-1) 2 parts by mass, TEM58SS twin-screw extruder (manufactured by Toshiba Machine Co., Ltd., number of barrels 13, screw diameter 58 mm, L / D = 53) (kneading disc L: 2, kneading disc) Supply from the most upstream part (top feed) of R: 14 pieces and kneading disk N: 2 pieces), cylinder temperature 300 ° C, screw rotation speed 450 rpm, extrusion rate 400 kg / hr, vent vacuum degree 7 Pellets of the resin composition were obtained by melt-kneading under the condition of .998 kPa (60 Torr).
The evaluation results of the obtained resin composition are shown in Table 1 below.

[Example 3]
(A-1) 74 parts by mass, (B-1) 11 parts by mass, (B-2) 5 parts by mass, (C-a) 5 parts by mass, (D-1) 5 parts by mass, (E-1) 0.5 parts by mass and (F-1) 2 parts by mass are TEM58SS twin-screw extruder (manufactured by Toshiba Machine Co., Ltd., number of barrels 13, screw diameter 58 mm, L / D = 53) (knee). Supply from the most upstream part (top feed) of the screw pattern (screw pattern having 2 ding discs L: 2, 14 kneading discs R, and 2 kneading discs), the cylinder temperature is 300 ° C., the screw rotation speed is 450 rpm, and the screw rotation speed is 450 rpm. Pellets of the resin composition were obtained by melt-kneading under the conditions of an extrusion rate of 400 kg / hr and a vent vacuum degree of 7.998 kPa (60 Torr).
The evaluation results of the obtained resin composition are shown in Table 1 below.
[Example 4]
Pellets of the resin composition were obtained by melt-kneading under the same conditions as in the extrusion of Example 3 except that 0.5 part by mass of (E-1) was changed to (E-2).
The evaluation results of the obtained resin composition are shown in Table 1 below.

[Comparative Example 2]
(A-1) 29 parts by mass, (A-2) 29 parts by mass, (B-1) 15 parts by mass, (B-2) 20 parts by mass, and (C-1) 7 parts by mass. , TEM58SS twin-screw extruder (manufactured by Toshiba Machine Co., Ltd., number of barrels 13, screw diameter 58 mm, L / D = 53) (kneading disc L: 2, kneading disc R: 14, and kneading disc N: 2) It is supplied from the most upstream part (top feed) of a screw pattern (with a screw pattern) and melt-kneaded under the conditions of a cylinder temperature of 300 ° C., a screw rotation speed of 450 rpm, an extrusion rate of 400 kg / hr, and a vent vacuum degree of 7.998 kPa (60 Torr). Pellets of the resin composition were obtained.
The evaluation results of the obtained resin composition are shown in Table 1 below.

[Comparative Example 3]
(A-1) 29 parts by mass, (A-2) 29 parts by mass, (B-2) 28 parts by mass, and (D-1) 14 parts by mass, TEM58SS twin-screw extruder (Toshiba Machine Co., Ltd.) The most upstream part of (screw pattern having 13 barrels, 58 mm screw diameter, L / D = 53) (kneading disc L: 2, kneading disc R: 14, and kneading disc N: 2). It was supplied from (top feed) and melt-kneaded under the conditions of a cylinder temperature of 300 ° C., a screw rotation speed of 450 rpm, an extrusion rate of 400 kg / hr, and a vent vacuum degree of 7.998 kPa (60 Torr) to obtain pellets of a resin composition.
The evaluation results of the obtained resin composition are shown in Table 1 below.

[Example 5]
(A-1) 29 parts by mass, (A-2) 29 parts by mass, (B-2) 21 parts by mass, (C-1) 7 parts by mass, and (D-1) 14 parts by mass. , TEM58SS twin-screw extruder (manufactured by Toshiba Machine Co., Ltd., number of barrels 13, screw diameter 58 mm, L / D = 53) (kneading disc L: 2, kneading disc R: 14, and kneading disc N: 2) It is supplied from the most upstream part (top feed) of a screw pattern (with a screw pattern) and melt-kneaded under the conditions of a cylinder temperature of 300 ° C., a screw rotation speed of 450 rpm, an extrusion rate of 400 kg / hr, and a vent vacuum degree of 7.998 kPa (60 Torr). Pellets of the resin composition were obtained.
The evaluation results of the obtained resin composition are shown in Table 1 below.

[Example 6]
(A-1) 29 parts by mass, (A-2) 29 parts by mass, (B-2) 21 parts by mass, (C-1) 7 parts by mass, (D-1) 14 parts by mass, (E-2) 1 part by mass is a TEM58SS twin-screw extruder (manufactured by Toshiba Machine Co., Ltd., number of barrels 13, screw diameter 58 mm, L / D = 53) (kneading disc L: 2, kneading disc R: Supplied from the most upstream part (top feed) of 14 pieces and kneading disk N: 2 pieces, cylinder temperature 300 ° C., screw rotation speed 450 rpm, extrusion rate 400 kg / hr, vent vacuum degree 7.998 kPa. Pellets of the resin composition were obtained by melt-kneading under the condition of (60 Torr).
The evaluation results of the obtained resin composition are shown in Table 1 below.

[Comparative Example 4]
The resin composition pellets were obtained by melt-kneading under the same conditions as in the extrusion of Example 6 except that 14 parts by mass of (D-1) was changed to (D'-1).
The evaluation results of the obtained resin composition are shown in Table 1 below.

[Comparative Example 5]
The resin composition pellets were obtained by melt-kneading under the same conditions as in the extrusion of Example 6 except that 14 parts by mass of (D-1) was changed to (D'-2).
The evaluation results of the obtained resin composition are shown in Table 1 below.

[Comparative Example 6]
The resin composition pellets were obtained by melt-kneading under the same conditions as in the extrusion of Example 6 except that 14 parts by mass of (D-1) was changed to an aromatic petroleum resin.
The evaluation results of the obtained resin composition are shown in Table 1 below.

[Example 7]
Melting and kneading under the same conditions as in the extrusion of Example 6 except that 7 parts by mass of (C-1) was changed to 7 parts by mass of (C-a) and 1 part by mass of (F-1) was further added. Then, pellets of the resin composition were obtained.
The evaluation results of the obtained resin composition are shown in Table 1 below.

[Example 8]
Pellets of the resin composition were obtained by melt-kneading under the same conditions as in the extrusion of Example 7 except that 1 part by mass of (F-1) was changed to 1 part by mass of (F-2).
The evaluation results of the obtained resin composition are shown in Table 1 below.

[Comparative Example 7]
(A-1) 40 parts by mass, (B-1) 12 parts by mass, (B-2) 36 parts by mass, (C-a) 12 parts by mass, (E-1) 2 parts by mass, (F-1) 2 parts by mass and (F-2) 1 part by mass are TEM58SS twin-screw extruder (manufactured by Toshiba Machine Co., Ltd., number of barrels 13, screw diameter 58 mm, L / D = 53) (kneading disc). It is supplied from the most upstream part (top feed) of a screw pattern having L: 2, kneading disc R: 14, and kneading disc N: 2, and has a cylinder temperature of 300 ° C., a screw rotation speed of 450 rpm, and an extrusion rate. Pellets of the resin composition were obtained by melt-kneading under the conditions of 400 kg / hr and a vent vacuum degree of 7.998 kPa (60 Torr).
The evaluation results of the obtained resin composition are shown in Table 1 below.

[Example 9]
Pellets of the resin composition were obtained by melt-kneading under the same conditions as the extrusion of Comparative Example 7 except that 12 parts by mass of (B-1) was changed to (D-1).
The evaluation results of the obtained resin composition are shown in Table 1 below.

[Comparative Example 8]
(A-1) 40 parts by mass, (B-2) 28 parts by mass, (C-a) 12 parts by mass, (D-1) 20 parts by mass, (E-1) 2 parts by mass, (F-1) 2 parts by mass and (F-2) 1 part by mass are TEM58SS twin-screw extruder (manufactured by Toshiba Machine Co., Ltd., number of barrels 13, screw diameter 58 mm, L / D = 53) (kneading disc). It is supplied from the most upstream part (top feed) of a screw pattern having L: 2, kneading disc R: 14, and kneading disc N: 2, and has a cylinder temperature of 300 ° C., a screw rotation speed of 450 rpm, and an extrusion rate. Pellets of the resin composition were obtained by melt-kneading under the conditions of 400 kg / hr and a vent vacuum degree of 7.998 kPa (60 Torr).
The evaluation results of the obtained resin composition are shown in Table 1 below.

[Comparative Example 9]
(A-1) 80 parts by mass, (B-2) 5 parts by mass, (C-1) 5 parts by mass, (D-1) 10 parts by mass, and (E-1) 2 parts by mass. , TEM58SS twin-screw extruder (manufactured by Toshiba Machine Co., Ltd., number of barrels 13, screw diameter 58 mm, L / D = 53) (kneading disc L: 2, kneading disc R: 14, and kneading disc N: 2) It is supplied from the most upstream part (top feed) of a screw pattern (with a screw pattern) and melt-kneaded under the conditions of a cylinder temperature of 300 ° C., a screw rotation speed of 450 rpm, an extrusion rate of 400 kg / hr, and a vent vacuum degree of 7.998 kPa (60 Torr). Pellets of the resin composition were obtained.
The evaluation results of the obtained resin composition are shown in Table 1 below.

As shown in Table 1, since the resin compositions of Comparative Examples 1, 2, and 7 do not contain the component (D), they have rigidity (bending strength, flexural modulus) and impact resistance (charpy impact strength). Although the retention molding stability was good, the balance between heat resistance (DTUL) and molding fluidity (MFR) was not sufficient.
The resin compositions of Examples 1 to 9 had an excellent balance between heat resistance and molding fluidity, and also had good rigidity, impact resistance, and retention molding stability. In particular, Examples 2 to 4 and 6 to 9 showed a particularly good tendency in retention molding stability by containing the heat stabilizer (E).
Since the resin composition of Comparative Example 3 did not contain the component (C), the impact resistance was not sufficient.
Since the resin compositions of Comparative Examples 4 to 6 contained a molding fluidity modifier other than the component (D), none of them had sufficient retention molding stability, and other physical properties were not always sufficient.
In the resin composition of Comparative Example 8, since the content of the component (D) exceeded the upper limit of the claims of the present application, the retention molding stability tended to decrease, which was not sufficient.
In the resin composition of Comparative Example 9, since the content of the component (A) exceeded the upper limit of the claims of the present application, deterioration in retention molding stability and impact resistance was observed, which was not sufficient.

The resin composition of the present invention has an excellent balance between molding fluidity and heat resistance, and the generation of silver streaks is remarkably suppressed during molding, so that it can be used as a thin-walled molded product having a high appearance without painting. Since it is a polyphenylene ether-based resin composition capable of obtaining various molded products, it can be satisfactorily used for home appliance OA equipment parts, electrical and electronic equipment, automobile applications, decorative molded parts such as various industrial products.

Claims (6)

A block copolymer (C) containing a polyphenylene ether (A), a styrene resin (B), a styrene block and a hydrogenated conjugated diene compound block, and a softening point (measured by the ring ball method) at 155 ° C. Including the above-mentioned terpene-phenol resin (D)
The content of the component (A) is 35 to 75 parts by mass with respect to the total amount of the components (A), (B), (C), and (D) of 100 parts by mass, and the content of the component (B) is contained. The polyphenylene ether system is characterized in that the amount is 5 to 50 parts by mass, the content of the component (C) is 1 to 20 parts by mass, and the content of the component (D) is 0.5 to 15 parts by mass. Resin composition. The heat stabilizer (E) having a melting point of 200 ° C. or higher is contained in an amount of 0.05 to 3 parts by mass with respect to 100 parts by mass of the total amount of the components (A), (B), (C) and (D). , The polyphenylene ether-based resin composition according to claim 1. The invention according to claim 1 or 2, wherein the component (C) contains a copolymer (C-a) of a styrene block having a bound styrene content of 55% by mass or more and a hydrogenated conjugated diene compound block. Polyphenylene ether-based resin composition. Further, it contains a polyolefin resin (F), and the mass ratio ((C-a) / (F)) of the component (C-a) to the component (F) is within the range of 9/1 to 6/4. The polyphenylene ether-based resin composition according to claim 3. Any one of claims 1 to 4, wherein the total content of the components (A), (B), (C), and (D) is 90% by mass or more of the total content of the polyphenylene ether-based resin composition. The polyphenylene ether-based resin composition according to the above. When the polyamide resin and / or the polyolefin resin (F) is contained, the total content of the polyamide resin and the polyolefin resin (F) in the polyphenylene ether resin composition is 8% by mass or less. , The polyphenylene ether-based resin composition according to any one of claims 1 to 5.