JP2023010586A - Polyphenylene ether resin composition - Google Patents

Abstract

To provide a polyphenylene ether-based resin composition which has excellent heat-resistant aging characteristics and molding appearance, and holds a performance balance between heat resistance and impact resistance held by a polyphenylene ether-based resin in itself without impairing the performance balance.SOLUTION: A polyphenylene ether-based resin composition contains polyphenylene ether (A), a condensation type phosphate-based compound (C), a metal oxide and/or metal sulfide (D), a lubricant (E) containing at least one or more selected from the group consisting of higher fatty acid amide, higher fatty acid bisamide, and higher fatty acid metal salt, and optionally a styrenic resin (B), wherein as for contents of each of the components with respect to 100 pts.mass of the total amount of the components (A), (B), (C), (D) and (E), the component (A) is 10 to 95 pts.mass, the component (B) is 0 to 80 pts.mass, the component (C) is 1 to 25 pts.mass, and the total of the component (D) and the component (E) is 0.1 to 3.5 pts.mass, and a content ratio (D)/(E) of the component (D) to the component (E) in the resin composition is within a range of 80/20 to 55/45.SELECTED DRAWING: None

Description

The present invention relates to a polyphenylene ether resin composition.

The polyphenylene ether resin is usually a mixture of polyphenylene ether and a styrenic resin in an arbitrary ratio depending on the level of heat resistance and molding fluidity required, and if necessary, an elastomer component, Additive components such as a flame retardant, an inorganic filler, and a heat stabilizer are blended to form a resin composition. Polyphenylene ether resins have excellent heat resistance, mechanical properties, molding processability, acid and alkali resistance, dimensional stability, electrical properties, etc., and are widely used in the fields of home appliance OA, business machines, information equipment, automobiles, and the like.

In recent years, polyphenylene ether resin compositions have been studied for use in projectors, moldings used in various lighting fixtures, and thin-walled automobile parts. In addition to heat resistance and molding fluidity, there are cases where it is required to have an extremely high level of molded appearance that is different from ordinary molded products, and to maintain sufficient mechanical strength when exposed to high temperatures for a long time. Not a few.

As a technique for improving the high-temperature aging (long-term high-temperature exposure) properties of polyphenylene ether resin compositions, the high-temperature aging properties of polyphenylene ether can be significantly improved by blending polyphenylene ether with a condensed metal phosphate at a specific ratio. Techniques for improvement have been disclosed (see Patent Document 1, for example).

In addition, by combining a specific phosphate ester compound and a metal oxide with a polyphenylene ether resin, components derived from the phosphate ester compound volatilize from the molded product and bleed to the surface of the molded product. A technique related to a resin composition in which is suppressed has also been disclosed (see, for example, Patent Document 2).

WO2018/066530 JP-A-8-12877

However, even with the resin compositions disclosed in Patent Document 1 and Patent Document 2, in terms of aging characteristics under high temperature conditions, a resin composition that retains mechanical properties to some extent can be obtained, but the appearance of the molded product is affected. In particular, it was often seen that the retention of molded appearance during long-term continuous molding was not necessarily sufficient.

The present invention provides a polyphenylene ether-based resin composition that exhibits excellent heat resistance aging properties and molded appearance, and at the same time, maintains the performance balance between heat resistance and impact resistance that polyphenylene ether-based resins inherently possess. for the purpose.

As a result of intensive studies to solve the above problems, the present inventors have found that a polyphenylene ether resin is added with a condensed phosphoric acid ester compound, a metal oxide and / or metal sulfide, and a specific lubricant component in a specific amount. By blending together, it is possible to achieve both heat aging resistance under temperature conditions around 110 to 140 ° C, which is particularly difficult to improve, and maintenance of molded appearance in long-term continuous molding. The present inventors have found that the desired resin composition can be obtained while maintaining or improving the performance balance between fluidity and impact resistance, and have been able to provide the present invention.

（化学式（１）の、Ｒ^１～Ｒ^４は、２，６－キシリル基を表し、ｎは１～３を表す。）
［３］前記（Ｄ）成分が、酸化チタン、酸化亜鉛、硫化亜鉛からなる群から選択される少なくとも一種以上を含むことを特徴とする、［１］又は［２］に記載のポリフェニレンエーテル系樹脂組成物。
［４］前記（Ａ）、（Ｂ）、（Ｃ）、（Ｄ）、及び（Ｅ）成分の合計量１００質量部中における、前記（Ｃ）成分と（Ｄ）成分と（Ｅ）成分の合計含有量が１７質量部以下であることを特徴とする、［１］～［３］のいずれかに記載のポリフェニレンエーテル系樹脂組成物。
［５］前記（Ａ）、（Ｂ）、（Ｃ）、（Ｄ）、及び（Ｅ）成分の合計量１００質量部に対して、更にスチレン系熱可塑性エラストマー（Ｆ）０．１～２５質量部を含有することを特徴とする、［１］～［４］のいずれかに記載のポリフェニレンエーテル系樹脂組成物。
［６］前記（Ａ）、（Ｂ）、（Ｃ）、（Ｄ）、（Ｅ）及び、（Ｆ）成分の合計含有量が、前記ポリフェニレンエーテル系樹脂組成物全体の８５質量％以上を占めることを特徴とする、［１］～［５］のいずれかに記載のポリフェニレンエーテル系樹脂組成物。
［７］前記ポリフェニレンエーテル系樹脂組成物１００質量部中におけるポリオレフィン系樹脂の含有量が５質量部以下であることを特徴とする、［１］～［６］のいずれかに記載のポリフェニレンエーテル系樹脂組成物。
［８］１３０℃、１０００時間エイジング後の引張強度保持率が９０％以上であることを特徴とする、［１］～［７］のいずれかに記載のポリフェニレンエーテル系樹脂組成物。
［９］［１］～［８］のいずれかに記載のポリフェニレンエーテル系樹脂組成物を製造する方法であって、前記（Ａ）、（Ｃ）、（Ｄ）及び（Ｅ）成分、並びに必要に応じて前記（Ｂ）、（Ｆ）成分及びその他の材料を溶融混練する工程を含み、前記（Ｄ）成分と前記（Ｅ）成分とを予め混合したものを原料として用いることを特徴とする、ポリフェニレンエーテル系樹脂組成物の製造方法。 That is, the present invention is as follows.
[1] Selected from the group consisting of polyphenylene ether (A), condensed phosphoric ester compound (C), metal oxide and/or metal sulfide (D), higher fatty acid amide, higher fatty acid bisamide, and higher fatty acid metal salt containing at least one or more lubricants (E), and optionally a styrenic resin (B),
The content of each component with respect to the total amount of 100 parts by mass of components (A), (B), (C), (D) and (E) is 10 to 95 parts by mass for component (A) and 0 for component (B). 80 parts by mass, 1 to 25 parts by mass of component (C), and 0.1 to 3.5 parts by mass of components (D) and (E) in total,
Polyphenylene ether-based, characterized in that the content ratio of the (D) component and the (E) component in the resin composition is within the range of (D) / (E) = 80/20 to 55/45 Resin composition.
[2] The polyphenylene ether resin composition according to [1], wherein the component (C) is a condensed phosphate compound represented by the following formula (1).

(R ¹ to R ⁴ in chemical formula (1) represent a 2,6-xylyl group, and n represents 1 to 3.)
[3] The polyphenylene ether-based resin according to [1] or [2], wherein the component (D) contains at least one selected from the group consisting of titanium oxide, zinc oxide, and zinc sulfide. Composition.
[4] In the total amount of 100 parts by mass of the components (A), (B), (C), (D), and (E), the components (C), (D), and (E) The polyphenylene ether resin composition according to any one of [1] to [3], wherein the total content is 17 parts by mass or less.
[5] 0.1 to 25 parts by mass of a styrenic thermoplastic elastomer (F) in addition to 100 parts by mass of the total amount of components (A), (B), (C), (D), and (E) The polyphenylene ether resin composition according to any one of [1] to [4], characterized by containing a part.
[6] The total content of the components (A), (B), (C), (D), (E) and (F) accounts for 85% by mass or more of the entire polyphenylene ether resin composition. The polyphenylene ether resin composition according to any one of [1] to [5], characterized by:
[7] The polyphenylene ether system according to any one of [1] to [6], wherein the content of the polyolefin resin in 100 parts by mass of the polyphenylene ether resin composition is 5 parts by mass or less. Resin composition.
[8] The polyphenylene ether resin composition according to any one of [1] to [7], which has a tensile strength retention of 90% or more after aging at 130° C. for 1000 hours.
[9] A method for producing the polyphenylene ether-based resin composition according to any one of [1] to [8], comprising the components (A), (C), (D) and (E), and necessary A step of melting and kneading the components (B), (F) and other materials according to the above, and using a mixture of the component (D) and the component (E) in advance as a raw material , a method for producing a polyphenylene ether-based resin composition.

According to the present invention, at the same time as being excellent in both heat aging resistance in the vicinity of 110 to 140 ° C. and maintaining molded appearance in continuous molding for a long time, the heat resistance and impact resistance that the polyphenylene ether resin originally retains. It is possible to provide a polyphenylene ether resin composition that maintains the performance balance with.

EMBODIMENT OF THE INVENTION Hereinafter, the form (henceforth "this embodiment") for implementing this invention is demonstrated in detail. The present invention is not limited to the following description, and various modifications can be made within the scope of the gist thereof.

[Resin composition]
The polyphenylene ether-based resin composition of the present embodiment includes polyphenylene ether (A), condensed phosphoric ester compound (C), metal oxide and/or metal sulfide (D), higher fatty acid amide, higher fatty acid bisamide, Lubricant (E) containing at least one or more selected from the group consisting of higher fatty acid metal salts, and optionally containing styrene resin (B), the above (A), (B), (C), ( The content of each component with respect to 100 parts by mass of the total amount of components D) and (E) is 10 to 95 parts by mass of component (A), 0 to 80 parts by mass of component (B), and 1 to 25 parts by mass of component (C). , a total of 0.1 to 3.5 parts by mass of the component (D) and the component (E), and the content ratio of the component (D) and the component (E) in the resin composition is (D)/ (E) is a polyphenylene ether resin composition in the range of 80/20 to 55/45. The polyphenylene ether-based resin composition of the present embodiment further optionally contains a styrene-based thermoplastic elastomer (F).

但し、上記化学式（２）及び（３）中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５及びＲ^６は、それぞれ独立して、水素原子、炭素数１～４のアルキル基、炭素数６～９のアリール基、又はハロゲン原子から選ばれる一価の残基を表す。但し、Ｒ^５及びＲ^６は同時に水素ではない。 (Polyphenylene ether (A))
Polyphenylene ether (A) contained in the polyphenylene ether-based resin composition of the present embodiment (hereinafter, polyphenylene ether (A) is also simply referred to as "(A) component") is represented by the following chemical formula (1) and/or chemical formula ( It is preferably a single polymer (homopolymer) or a copolymer (copolymer) having a repeating unit (structural unit) represented by 2).

However, in the above chemical formulas (2) and (3), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a carbon It represents a monovalent residue selected from 6 to 9 aryl groups or halogen atoms. However, R5 and ^R6 are not hydrogen at the ^same time.

The alkyl group preferably has 1 to 3 carbon atoms, the aryl group preferably has 6 to 8 carbon atoms, and among the monovalent residues, hydrogen is preferred.
The number of repeating units represented by the above chemical formulas (2) and (3) varies depending on the molecular weight distribution of the polyphenylene ether (A) and is not particularly limited.

Representative examples of polyphenylene ether homopolymers include poly(2,6-dimethyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, poly(2, 6-diethyl-1,4-phenylene) ether, poly(2-ethyl-6-n-propyl-1,4-phenylene) ether, poly(2,6-di-n-propyl-1,4-phenylene) ether, poly(2-methyl-6-n-butyl-1,4-phenylene) ether, poly(2-ethyl-6-isopropyl-1,4-phenylene) ether, poly(2-methyl-6-chloroethyl- 1,4-phenylene) ether, poly(2-methyl-6-hydroxyethyl-1,4-phenylene) ether, poly(2-methyl-6-chloroethyl-1,4-phenylene) ether and the like.

Examples of polyphenylene ether copolymers include, but are not limited to, copolymers of 2,6-dimethylphenol and 2,3,6-trimethylphenol, 2,6-dimethylphenol and o- A polyphenylene ether structure represented by chemical formula (2) and / or chemical formula (3), such as a copolymer with cresol and a copolymer with 2,3,6-trimethylphenol and o-cresol, as a main repeating unit There are things to do.

In the present embodiment, the polyphenylene ether chain preferably contains at least a portion of the structure in which R ¹ and R ² are methyl groups in the chemical formula (2). Among them, poly(2,6-dimethyl-1,4-phenylene) ether is preferred.

The various polyphenylene ethers (A) described above may be used singly or in combination of two or more.

In the above polyphenylene ether (A), from the viewpoint of sufficient affinity with the metal oxides and metal sulfides that are the component (D), the terminal OH group concentration is 0.5 per 100 monomer units constituting the polyphenylene ether. It is preferably 4 to 2.0, more preferably 0.6 to 1.3.
Incidentally, the terminal OH group concentration of the polyphenylene ether (A) can be calculated by NMR measurement.

Polyphenylene ether (A) is a polyphenylene ether containing various phenylene ether units other than those represented by general formulas (2) and (3) as a partial structure as long as the heat resistance of the resin composition is not excessively lowered. may contain.
Various phenylene ether units other than the above chemical formulas (2) and (3) are not limited to the following. 2-(dialkylaminomethyl)-6-methylphenylene ether units, 2-(N-alkyl-N-phenylaminomethyl)-6-methylphenylene ether units, and the like described therein.

The polyphenylene ether (A) may have diphenoquinone or the like bound to the main chain of the polyphenylene ether.

Furthermore, the polyphenylene ether (A) contains a carboxyl group, an acid anhydride group, an acid amide group, an imide group, an amino group, an orthoester group, a hydroxy group, and a carboxylic acid It is possible to have a functionalized polyphenylene ether substituted structure by reacting (modifying) with a functionalizing agent comprising one or more functional groups selected from the group consisting of groups derived from ammonium salts.
In particular, when inorganic fillers are blended, from the viewpoint of improving adhesion with inorganic fillers and improving heat resistance and mechanical properties, polyphenylene ether is added with acid anhydrides such as maleic anhydride, malic acid, citric acid, fumaric acid, etc. is part or all of polyphenylene ether (A).
In the polyphenylene ether (A), from the viewpoint of further improving the affinity with the component (D), the concentration of the functionalized modified terminal is 0.1 to 10 per 100 monomer units constituting the polyphenylene ether. is preferably 0.1 to 3.0, and still more preferably 0.1 to 1.0.
The modified terminal concentration of the polyphenylene ether (A) can be calculated by NMR measurement.

The ratio of the weight average molecular weight Mw to the number average molecular weight Mn (Mw/Mn value) of the polyphenylene ether (A) is preferably 2.0 to 5.5, more preferably 2.5 to 4.5, Still more preferably 3.0 to 4.5.
The Mw/Mn value is preferably 2.0 or more from the viewpoint of moldability of the resin composition, and preferably 5.5 or less from the viewpoint of mechanical properties of the resin composition.
The number average molecular weight Mn of the polyphenylene ether (A) is preferably 8000 to 28000, more preferably 12000 to 24000, still more preferably 14000 to 22000, from the viewpoint of moldability and mechanical properties.
Here, the weight-average molecular weight Mw and the number-average molecular weight Mn are obtained from polystyrene equivalent molecular weights by GPC (gel permeation chromatography) measurement.

The reduced viscosity of the polyphenylene ether (A) is preferably in the range of 0.25-0.65 dL/g. More preferably in the range of 0.30 to 0.55 dL/g, still more preferably in the range of 0.33 to 0.42 dL/g.
The reduced viscosity of the polyphenylene ether is preferably 0.25 dL/g or more from the viewpoint of sufficient mechanical properties, and preferably 0.65 dL/g or less from the viewpoint of moldability.
The reduced viscosity can be measured with a 0.5 g/dL solution at 30° C. in a chloroform solvent using an Ubbelohde viscometer.

Polyphenylene ether (A) is generally available as a powder, and preferably has an average particle size of 1 to 1000 μm, more preferably 10 to 700 μm, particularly preferably 100 to 500 μm. The thickness is preferably 1 μm or more from the viewpoint of handling during processing, and preferably 1000 μm or less in order to suppress the generation of unmelted matter during melt-kneading.

In the resin composition of the present embodiment, a polyphenylene ether (A), a styrene resin (B), a condensed phosphoric ester compound (C), a metal oxide and / or a metal sulfide (D), The content of the polyphenylene ether (A) in 100 parts by mass of the total amount of the lubricant (E) containing at least one selected from the group consisting of higher fatty acid amides, higher fatty acid bisamides, and higher fatty acid metal salts is 10. It is within the range of ∼95 parts by mass. It is preferably in the range of 20 to 90 parts by mass, more preferably in the range of 35 to 80 parts by mass.
The content of polyphenylene ether is preferably 10 parts by mass or more from the viewpoint of imparting sufficient heat resistance, and preferably 95 parts by mass or less from the viewpoint of moldability and maintenance of molded appearance.

(Styrene resin (B))
In the resin composition of the present embodiment, a styrene-based resin (B) can be blended mainly for the purpose of improving molding fluidity.

In the present embodiment, the styrene-based resin (B) is a homopolymer of a styrene-based compound, a copolymer of a styrene-based compound and a compound that can be copolymerized with a styrene-based compound (excluding a conjugated diene compound). Say. This component (B) does not include those included in the category of the component (F) described later.

Specific examples of the styrenic resin (B) include styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert-butylstyrene, ethylstyrene and the like.

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

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

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

In the resin composition of the present embodiment, a polyphenylene ether (A), a styrene resin (B), a condensed phosphoric ester compound (C), a metal oxide and / or a metal sulfide (D), The content of the polystyrene resin (B) in 100 parts by mass of the total amount of the lubricant (E) containing at least one selected from the group consisting of higher fatty acid amides, higher fatty acid bisamides, and higher fatty acid metal salts is It is in the range of 0 to 80 parts by mass. It is preferably in the range of 10 to 60 parts by mass, more preferably in the range of 20 to 50 parts by mass.
The content of the polystyrene resin (B) is preferably more than 0 parts by mass from the viewpoint of imparting sufficient molding fluidity, and preferably 80 parts by mass or less from the viewpoint of maintaining sufficient heat resistance.

（化学式（４）中、Ｒ^１～Ｒ^４は、２，６－キシリル基を表し、ｎは１～３を表す。） (Condensed phosphoric acid ester compound (C))
Examples of the condensed phosphoric ester compound (C) include cresyl diphenyl phosphate, xylenyl diphenyl phosphate, dixylenyl phenyl phosphate, hydroxynon bisphenol phosphate, resorcinol bisphosphate, bisphenol A bisphosphate, bisphenol A bisdiphenyl phosphate, and the like. triphenyl-substituted aromatic phosphate esters, compounds represented by the following chemical formula (4), etc. are preferably used. A compound represented by 4) is more preferably used.

(In chemical formula (4), R ¹ to R ⁴ represent 2,6-xylyl groups, and n represents 1 to 3.)

The condensed phosphate compound (B) may be used alone or in combination of two or more.

In the resin composition of the present embodiment, a polyphenylene ether (A), a styrene resin (B), a condensed phosphoric ester compound (C), a metal oxide and / or a metal sulfide (D), Condensed phosphoric acid ester compound (C) in 100 parts by mass combined with lubricant (E) containing at least one selected from the group consisting of higher fatty acid amides, higher fatty acid bisamides, and higher fatty acid metal salts. The content is within the range of 1 to 25 parts by mass. It is preferably in the range of 2 to 20 parts by mass, more preferably 3 to 15 parts by mass, and even more preferably 4 to 10 parts by mass.
The content of the condensed phosphate ester compound (C) is preferably 1 part by mass or more from the viewpoint of improving heat aging resistance, and is 25 parts by mass or less from the viewpoint of preventing mold contamination and maintaining molding appearance. is preferred.

(Metal oxide, metal sulfide (D))
Metal oxides and/or metal sulfides (D) contained in the polyphenylene ether-based resin composition of the present embodiment include, for example, titanium oxide, zinc oxide, zinc sulfide, magnesium oxide, aluminum oxide, barium oxide, and calcium oxide. , molybdenum oxide and the like.
Titanium oxide, zinc oxide, and zinc sulfide are preferred for the resin composition of the present embodiment.

In the resin composition of the present embodiment, the average primary particle size of metal oxides and metal sulfides is preferably in the range of 0.01 to 1 μm. More preferably 0.05 to 0.5 μm, still more preferably 0.1 to 0.4 μm. From the viewpoint of improving long-term aging properties, it is preferably 0.01 µm or more, and preferably 1 µm or less.
The average primary particle size is calculated by observing 50 arbitrarily selected particles with an electron microscope and measuring the major axis and minor axis of each particle by magnified image analysis. can be done.

In the resin composition of the present embodiment, a polyphenylene ether (A), a styrene resin (B), a condensed phosphoric ester compound (C), a metal oxide and / or a metal sulfide (D), Metal oxide and/or metal sulfide (D ) is in the range of 0.05 to 3 parts by mass. It is preferably in the range of 0.1 to 2 parts by mass, more preferably in the range of 0.2 to 1.5 parts by mass. It is preferably 0.05 parts by mass or more from the viewpoint of improving heat resistance to aging, and preferably 3 parts by mass or less from the viewpoint of maintaining mechanical properties and molded appearance.

(Lubricant (E))
The lubricant (E) contained in the polyphenylene ether-based resin composition of the present embodiment is at least one lubricant selected from the group consisting of higher fatty acid amides, higher fatty acid bisamides, and higher fatty acid metal salts.

The higher fatty acid (bis)amide used in the resin composition of the present embodiment is a higher fatty acid amide or a higher fatty acid bisamide, and is preferably a compound obtained by a dehydration reaction between a higher fatty acid and/or a polybasic acid and a diamine. . As the higher fatty acid, saturated aliphatic monocarboxylic acids having 16 or more carbon atoms, such as 16 to 30 carbon atoms, are preferable from the viewpoint of preventing the occurrence of scorching and die-casting. Specifically, palmitic acid, stearic acid, and oleic acid are preferred. , erucic acid, behenic acid, montanic acid and the like.
Polybasic acids include dibasic or higher carboxylic acids, such as aliphatic dicarboxylic acids such as malonic acid, succinic acid, adipic acid, sebacic acid, pimelic acid and azelaic acid, and aromatic acids such as phthalic acid and terephthalic acid. Dicarboxylic acids and alicyclic dicarboxylic acids such as cyclohexyldicarboxylic acid and cyclohexylsuccinic acid are included.
Examples of diamines include ethylenediamine, 1,3-diaminopropane, 1,4-
Diaminobutane, hexamethylenediamine, metaxylylenediamine, tolylenediamine, paraxylylenediamine, phenylenediamine, isophoronediamine and the like.
Specific examples of higher fatty acid amides include stearic acid amide, behenic acid amide, and montanic acid amide. Examples of higher fatty acid bisamides include higher fatty acid bisamides obtained by reacting the above higher fatty acids with aliphatic diamines having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms. stearylamide, ethylenebisstearylamide, and the like. Among these, stearic acid amide and ethylenebisstearylamide are preferable from the viewpoint of the effect of preventing occurrence of discoloration and die buildup.
These higher fatty acid (bis)amides may be used singly or in combination of two or more. Moreover, it may be used in combination with a higher fatty acid metal salt described later in an arbitrary ratio.

The higher fatty acid metal salt used in the resin composition of the present invention has 10 to 30 carbon atoms, preferably 14 to 24 carbon atoms, and has low volatility and is highly effective in preventing the occurrence of scorch and die buildup. preferred from Specific examples of higher fatty acids include caproic acid, capric acid, lauric acid, palmitic acid, stearic acid, behenic acid, lignoceric acid, montanic acid, oleic acid, and linoleic acid, with stearic acid and behenic acid being preferred. acid, montanic acid and the like.
Examples of metal salts include alkali metal salts such as potassium salts and sodium salts of these higher fatty acids, alkaline earth metal salts such as calcium salts and magnesium salts, and zinc salts.
Specific examples of higher fatty acid alkali metal salts include calcium stearate, sodium stearate, magnesium stearate, zinc stearate, calcium oleate, sodium oleate, calcium palmitate and sodium palmitate.
Among these, zinc stearate, magnesium stearate, and calcium stearate are more preferred.
These higher fatty acid metal salts may be used singly or in combination of two or more. Further, it may be used in combination with the higher fatty acid amides and higher fatty acid bisamides described above.

In the resin composition of the present embodiment, a polyphenylene ether (A), a styrene resin (B), a condensed phosphoric ester compound (C), a metal oxide and / or a metal sulfide (D), The content of the lubricant (E) in 100 parts by mass of the total amount of the lubricant (E) composed of at least one or more selected from the group consisting of higher fatty acid amides, higher fatty acid bisamides, and higher fatty acid metal salts is 0.015. It is preferably in the range of up to 1.75 parts by mass. It is more preferably in the range of 0.02 to 1 part by mass, still more preferably in the range of 0.05 to 0.5 part by mass. It is preferably 0.015 parts by mass or more from the viewpoint of improving heat resistance and aging resistance, and preferably 1.75 parts by mass or less from the viewpoint of preventing mold contamination and maintaining molding appearance.

In the resin composition of the present embodiment, a lubricant consisting of a metal oxide and/or metal sulfide (D) and at least one selected from the group consisting of higher fatty acid amides, higher fatty acid bisamides, and higher fatty acid metal salts ( The total content of E) is 0.1 to 3.5 parts by mass per 100 parts by mass of the total amount of components (A), (B), (C), (D) and (E). Within range. It is preferably 0.15 to 3 parts by mass, more preferably 0.25 to 2 parts by mass. It is preferably 0.1 part by mass or more from the viewpoint of sufficient heat aging resistance improvement, and preferably 3.5 parts by mass or less from the viewpoint of maintaining the mechanical properties of the molded product and the appearance of the molded product.

Furthermore, the content ratio of the component (D) and the component (E) in the resin composition is preferably within the range of (D)/(E) = 85/15 to 55/45. is in the range of 80/20 to 55/45, more preferably in the range of 80/20 to 60/40, still more preferably in the range of 80/20 to 65/35. From the viewpoint of maintaining the appearance and toughness of the molded article and heat aging resistance, it is desirable that the content ratio of (D)/(E) is within the range of 80/20 to 55/45. The component (D) and the component (E) may be added separately to form a composition during melt-kneading of the composition, for example, during melt-kneading using a twin-screw extruder or the like, which will be described later. It is preferable to use a mixture of the component (D) and the component (E) by means of a Henschel mixer or the like as the raw material from the viewpoint of maintaining the appearance and impact resistance of the molded article and heat aging resistance.

Furthermore, in the resin composition of the present embodiment, the condensed phosphoric ester compound (C), the metal oxide and / or metal sulfide (D), the higher fatty acid amide, the higher fatty acid bisamide, the higher fatty acid The total content of the lubricant (E) composed of at least one or more selected from the group consisting of metal salts is 100 mass of the total amount of (A), (B), (C), (D), and (E) It is preferable that the content is 17 parts by mass or less in the part, from the viewpoint of maintaining the appearance of the molded product and maintaining the balance of physical properties, more preferably 15 parts by mass or less, and 13 parts by mass or less. is more preferable.

Furthermore, in the resin composition of the present embodiment, the content ratio of the component (C) and the components (D) + (E) in the resin composition provides sufficient heat aging resistance and impact resistance. from the viewpoint of (C)/((D)+(E))=94/6 to 60/40. More preferably 92/8 to 66/34, still more preferably 90/10 to 70/30.

(Styrene-based thermoplastic elastomer (F))
The styrenic thermoplastic elastomer (F) used in the present embodiment is a block copolymer having a styrene block and a conjugated diene compound block.
From the viewpoint of thermal stability, the conjugated diene compound block is preferably hydrogenated at a hydrogenation rate of at least 50%. The hydrogenation rate is more preferably 80% or higher, still more preferably 95% or higher.
Examples of the conjugated diene compound block include, but are not limited to, polybutadiene, polyisoprene, poly(ethylene-butylene), poly(ethylene-propylene), and vinyl-polyisoprene. The conjugated diene compound blocks may be used singly or in combination of two or more.
The pattern of arrangement of the repeating units constituting the block copolymer may be linear or radial. The block structure composed of polystyrene blocks and rubber intermediate blocks may be of type 2, type 3 or type 4. Among them, from the viewpoint of sufficiently exhibiting the desired effect in the present embodiment, a trimorphic linear type block copolymer composed of a polystyrene-poly(ethylene-butylene)-polystyrene structure is preferable. A butadiene unit may be contained in the conjugated diene compound block within a range not exceeding 30% by mass.
In addition, in the composition of the present embodiment, a functionalized styrene thermoplastic elastomer into which a functional group such as a carbonyl group or an amino group is introduced can be used as the styrene thermoplastic elastomer.

The bound styrene content of the styrene-based thermoplastic elastomer (F) according to the present embodiment is selected from the range of 20 to 90% by mass, preferably 50 to 80% by mass, more preferably 60 to 70% by mass. be. From the viewpoint of miscibility with the (A) component and the (B) component, it is preferably 20% by mass or more, and from the viewpoint of imparting sufficient impact resistance, it is preferably 90% by mass or less.

The number average molecular weight Mn of the styrene-based thermoplastic elastomer (F) according to the present embodiment is preferably 30,000 to 500,000, more preferably 40,000 to 300,000, still more preferably 45,000 to 250,000 range. A range of 30,000 to 500,000 is preferable from the viewpoint of imparting sufficient toughness to molded articles.
The Mw/Mn value obtained from the weight average molecular weight Mw obtained from the polystyrene equivalent molecular weight and the number average molecular weight Mn of the component (F) is preferably 1.0 to 3.0, more preferably 1.0 to 2.0. 0, even more preferably in the range 1.0 to 1.5. From the viewpoint of mechanical properties, it is preferably within the range of 1.0 to 3.0.
Here, the weight-average molecular weight Mw and the number-average molecular weight Mn are obtained from polystyrene equivalent molecular weights by GPC (gel permeation chromatography) measurement.

The content of the styrene-based thermoplastic elastomer (F) according to the present embodiment is The content is preferably 0.1 to 25 parts by mass, more preferably 0.5 to 20 parts by mass, and still more preferably 1 to 15 parts by mass. From the viewpoint of improving toughness, the content is preferably 0.1 parts by mass or more, and from the viewpoint of maintaining the mechanical properties of the molded product, the content is preferably 25 parts by mass or less.

(other materials)
In the polyphenylene ether-based resin composition of the present embodiment, the polyolefin-based resin and / Alternatively, it is possible to blend a styrenic resin.
Polyolefin resins include polyolefin resins such as polyethylene and polypropylene, and polyolefin copolymers such as ethylene-propylene copolymers, ethylene-octene copolymers, ethylene-ethyl acrylate copolymers, and ethylene-ethyl methacrylate copolymers. A coalescence etc. are mentioned.
Only one type of polyolefin resin may be used alone, or two or more types may be mixed and used.
The content of the polyolefin resin in the resin composition of the present embodiment is preferably 5% by mass or less with respect to 100% by mass of the resin composition. It is more preferably 3% by mass or less, and still more preferably 2% by mass or less. The total content of the polyolefin-based resin and the styrene-based resin is preferably 5% by mass or less from the viewpoint of the mechanical properties of the resin composition.

Further, in the resin composition of the present embodiment, an ultraviolet absorber, a colorant, a mold release agent, etc. are added to 100 mass of the resin composition of the present application within a range that does not significantly deteriorate the heat resistance, mechanical properties, and surface appearance of the molded product. %, it can be contained at a rate of 0.001 to 3% by mass. It is preferably in the range of 0.01 to 2% by mass, more preferably in the range of 0.2 to 1% by mass.
From the viewpoint of achieving a sufficient addition effect, the content is desirably 0.001% by mass or more, and from the viewpoint of maintaining physical properties, it is desirably 3% by mass or less.

In the resin composition of the present embodiment, an inorganic filler can be blended for the purpose of reinforcing mechanical properties and imparting special properties.
Examples of inorganic fillers that can be used in the resin composition of the present embodiment include, but are not limited to, glass fiber, carbon fiber, mica, glass flakes, talc, glass milled fiber, chlorite, organic clay and the like.
The content of the inorganic filler in the resin composition of the present embodiment is less than 15% by mass with respect to 100% by mass of the resin composition, from the viewpoint of maintaining the appearance of the molded product and exhibiting a sufficient effect of heat aging resistance. is preferably It is more preferably less than 11% by mass, still more preferably less than 6% by mass, still more preferably 4% by mass or less, and particularly preferably 2% by mass or less.

[Method for producing resin composition]
The resin composition of the present embodiment is produced by melt-kneading components (A), (C), (D), (E) and, if necessary, components (B), (F), and other materials. can do.
The method for preparing the resin composition of the present embodiment is not limited to the following, but in order to stably produce a large amount of the resin composition, a twin-screw extruder is preferably used from the viewpoint of production efficiency. .
The screw diameter of the twin-screw extruder is preferably in the range of 25-90 mm. More preferably, it is within the range of 40-70 mm. For example, ZSK40MC twin-screw extruder (manufactured by Werner & Pfleiderer of Germany, barrel number 13, screw diameter 40 mm, L / D = 50; kneading disk L: 2 pieces, kneading disk R: 6 pieces, and kneading disk N: When using a screw pattern with 4 pieces, a method of melt-kneading under the conditions of a cylinder temperature of 270 to 330 ° C., a screw rotation speed of 150 to 600 rpm, and an extrusion rate of 40 to 300 kg / h, or a TEM58SS twin screw extruder (Toshiba Machine Co., Ltd., 13 barrels, screw diameter 58 mm, L / D = 53; kneading disk L: 2, kneading disk R: 14, and kneading disk N: screw pattern with 2) was used. In some cases, a method of melt-kneading under the conditions of a cylinder temperature of 270 to 330° C., a screw rotation speed of 150 to 600 rpm, and an extrusion rate of 250 to 700 kg/h is suitable.
Here, "L" is the "screw barrel length" of the extruder and "D" is the "screw barrel diameter".

The conditions for producing the resin composition of the present embodiment are not limited to the following. It is also possible to produce a resin composition by collectively melt-kneading the components (B), (F) and other materials.
Further, when the resin composition of the present embodiment is produced using a twin-screw extruder, the components (D) and (E) are mixed in advance with a Henschel mixer or the like as described above, and then this is used as a raw material. Using, (A), (B), (C) components and other raw materials are supplied from the most upstream supply port (top feed) of the extruder and melt-kneaded to produce a resin composition. Also good. In addition, an inorganic filler or the like may be side-fed from an extruder barrel on the way, and when the component (C) is liquid, the resin composition is produced by blending and melt-kneading in a liquid addition facility. is also possible.
Further, from the viewpoint of imparting heat resistance and mechanical properties, the components (A), (D) and (E) are supplied from the most upstream supply port (top feed) of the extruder, and if necessary It is preferable that the components (B) and (F) are supplied from a raw material feed port (side feed) provided in the middle of the extruder and melt-kneaded to form a composition.

[Physical properties of resin composition]
The level of long-term heat aging resistance of the resin composition of the present embodiment is determined from the viewpoint of preventing destruction of the molded product due to thermal deterioration in a use temperature environment of about 110 to 140 ° C., exposure for 1000 hours at a temperature condition of 110 to 140 ° C. The post-exposure tensile strength retention is preferably 90% or more, more preferably 95% or more, than before exposure. Preferably, the tensile strength retention rate after exposure for 1000 hours at a temperature of 130° C. is preferably 90% or more, more preferably 95% or more, of that before exposure.
Specifically, the tensile strength of the resin composition can be measured by the method described in Examples below.

The Charpy impact strength (according to ISO179, measured at 23° C.) of the resin composition of the present embodiment is preferably 2 kJ/m ² or more from the viewpoint of preventing cracks during use. More preferably, it is 3 kJ/m ² or more.
The Charpy impact strength of the resin composition can be specifically measured by the method described in Examples below.

The melt flow rate (MFR) of the resin composition of the present embodiment (measured at 280° C. under a load of 5 kg according to ISO 1133) is preferably 10 g/10 min or more from the viewpoint of molding fluidity. It is more preferably 12 g/10 min or more, still more preferably 14 g/10 min or more.
Specifically, the MFR of the resin composition can be measured by the method described in Examples below.

〔Molding〕
A molded article made of the resin composition of the present embodiment can be obtained by molding the resin composition described above.
Incidentally, the average molding thickness of the molded article made of the polyphenylene ether-based resin composition of the present embodiment is preferably within the range of 0.5 to 2.5 mm. It is more preferably in the range of 0.7 to 2.2 mm, still 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 method for molding the resin composition is not limited to the following, but suitable examples thereof include injection molding, extrusion molding, vacuum molding, and pressure molding. In particular, from the viewpoint of mass production, injection molding is more preferably used. .
The molding temperature during molding of the resin composition is preferably within the range of 280 to 350°C, more preferably 300 to 340°C, and still more preferably 300 to 330°C. . The molding temperature is preferably 280° C. or higher from the viewpoint of sufficient molding processability, and preferably 350° C. or lower from the viewpoint of suppressing thermal deterioration of the resin.
The mold temperature during molding of the resin composition is preferably 40 to 160.degree. C., more preferably 80 to 150.degree. C., still more preferably 80 to 130.degree. The mold temperature is preferably 40° C. or higher and preferably 160° C. or lower from the viewpoint of sufficiently maintaining the appearance of the molded product.

A suitable molded article in the present embodiment is one in which deterioration in mechanical properties (especially tensile strength) of the molded article caused by high temperature aging (long-term heat exposure) under temperature conditions of about 110 to 140° C. is remarkably suppressed, Since it can be used as a molded product with high heat resistance and good appearance, it can be used as home appliance OA equipment parts, internal parts of electrical and electronic equipment, automotive internal parts, decorative molded parts used for various industrial products, and the like.

Hereinafter, the present invention will be described with specific examples and comparative examples.
The present invention is not limited to these.

Methods for measuring physical properties and raw materials used in Examples and Comparative Examples are shown below.

(1. Molding fluidity (MFR))
After drying the pellets of the resin compositions obtained in the following examples and comparative examples in a hot air dryer at 80 ° C. for 2 hours, using a melt indexer (P-111, manufactured by Toyo Seiki Co., Ltd.), ISO1133 , Examples 15 to 19 and Comparative Examples 6 to 8 at a set temperature of 250 ° C. and a load of 10 kg, and Examples 1 to 14, Comparative Examples 1 to 5, and Examples 20 to 22 at a set temperature of 280 ° C. and a load of 5 kg. Flow rate (MFR) (g/10min) was measured.
As an evaluation criterion, it was determined that the higher the MFR value, the better the molding fluidity.

(2. Tensile strength (before aging))
Pellets of the resin compositions produced in Examples and Comparative Examples were dried in a hot air dryer at 90° C. for 1 hour.
Using the resin composition after drying, Comparative Examples 1 to 5, Examples 1 to 14, and Examples 20 to 20 by an injection molding machine (IS-80EPN, manufactured by Toshiba Machine Co., Ltd.) equipped with an ISO physical property test piece mold. 22 has a cylinder temperature of 300°C and a mold temperature of 90°C; Example 19 has a cylinder temperature of 290°C and a mold temperature of 80°C; Comparative Examples 6-8 and Examples 15-18 have a cylinder temperature of 270°C and a mold temperature of 270°C At 60° C., an injection pressure of 50 MPa (gauge pressure), an injection speed of 200 mm/sec, and an injection time/cooling time of 20 sec/20 sec were set. The obtained multi-purpose test piece A dumbbell molded piece was cut to prepare a molded piece of 80 mm x 10 mm x 4 mm. Using the test piece, according to ISO527, after leaving it for 24 hours in an environment with a temperature of 23 ° C. and a humidity of 50%, the tensile strength (MPa) was measured at 23 ° C. and a test speed of 5 mm / min. An average value of 5 pieces was obtained.
As an evaluation criterion, it was judged that the higher the average value of the measured tensile strength, the better the mechanical strength.

(3. Charpy impact strength)
ISO 3167, multi-purpose test piece A-type dumbbell molded piece produced in the above "2. Tensile strength (before aging)" was cut to prepare a molded piece of 80 mm x 10 mm x 4 mm. Using the test piece, according to ISO179, after leaving it for 24 hours in an environment with a temperature of 23 ° C. and a humidity of 50%, the Charpy impact strength (with notch) (kJ / m ² ) was measured at 23 ° C. , the average value of 5 measurements was obtained.
As an evaluation criterion, it was determined that the higher the average value of the measured values, the better the impact resistance.

(4. Tensile strength after aging at 110°C or 130°C for 1000 hours)
The average value of the tensile strength of the five dumbbell molded pieces of the multi-purpose test piece A type obtained in the above "2. Tensile strength (before aging)" was used as the sample before aging (blank, 0 hr).
Separately, 5 tubes, Comparative Examples 1 to 5, Examples 1 to 14, and Examples 20 to 22 at 130 ° C., Comparative Examples 6 to 8, Examples 15 to 17, Examples 18, and 19 at 110 ° C. After 1000 hours, the specimens were placed in a hot air oven set to 20°C, and after 1000 hours, the specimens were left in an environment of 23°C and 50% humidity for 24 hours to obtain post-aging specimens. As described in "2. Tensile strength (before aging)", the tensile strength (MPa) of each test piece was measured according to ISO527.
As an evaluation criterion, the smaller the degree of decrease in the measured value after aging with respect to the measured value of the blank, the better the aging property. In particular, it was determined that a tensile strength retention of 90% or more is desirable for the resin composition of the present embodiment, and a tensile strength retention of 95% or more is particularly desirable.

(5. Molded product appearance evaluation by continuous molding test)
Pellets of the resin compositions produced in Examples and Comparative Examples were dried in a hot air dryer at 90° C. for 2 hours. Using the dried resin composition, an injection molding machine (IS-100GN, manufactured by Toshiba Machine Co., Ltd.) equipped with a 50 mm × 50 mm × 1.2 mm thick mirror surface flat plate mold whose mold surface was polished with #5000. , Comparative Examples 1-5, Examples 1-14, and Examples 20-22 had a cylinder temperature of 320°C and a mold temperature of 90°C. Comparative Examples 6-8 and Examples 15-19 had a cylinder temperature of 280°C and metal Mold temperature was 60° C., injection pressure was 80 MPa (gauge pressure), injection speed (panel set value) was 60%, injection time/cooling time=15 sec/15 sec, and 250 shots of continuous molding were performed. The 250th shot of the mirror surface flat plate molded product was visually observed. Those with good appearance were evaluated as ◯, and those with surface roughness and cloudiness were evaluated as x.

〔raw materials〕
<Polyphenylene ether (PPE) (A)>
(A-1) Poly(2,6-dimethyl-1,4-phenylene) ether powder (A- 1) was prepared by solution polymerization (hereinafter sometimes simply referred to as “A-1”).

<Styrene resin (B)>
(B-1) General purpose polystyrene. Trade name: Polystyrene 680 (registered trademark), manufactured by PS Japan (hereinafter sometimes referred to as "B-1").
(B-2) High impact polystyrene. Trade name: Polystyrene CT60 (registered trademark), manufactured by Petrochemicals (hereinafter sometimes referred to as "B-2").

（Ｃ－２）
下記の化学式（６）で表される化合物（常温（２３℃）で固体性状。商品名：ＰＸ－２０１〔登録商標〕、大八化学社製）（以下、「Ｃ－２」ということもある）。

（Ｃ－３）
ビスフェノールＡビスジフェニルホスフェート（常温（２３℃）で液体性状。商品名：ＣＲ７４１〔登録商標〕、大八化学社製）（以下、「Ｃ－３」ということもある）。 <Condensed phosphoric acid ester compound (C)>
(C-1)
Compound represented by the following chemical formula (5) (solid at normal temperature (23 ° C.); trade name: PX-200 [registered trademark], manufactured by Daihachi Chemical Co., Ltd.) (hereinafter sometimes referred to as "C-1" ).

(C-2)
Compound represented by the following chemical formula (6) (solid at normal temperature (23 ° C.); trade name: PX-201 [registered trademark], manufactured by Daihachi Chemical Co., Ltd.) (hereinafter sometimes referred to as "C-2" ).

(C-3)
Bisphenol A bisdiphenyl phosphate (liquid at normal temperature (23° C.); trade name: CR741 [registered trademark], manufactured by Daihachi Chemical Co., Ltd.) (hereinafter sometimes referred to as “C-3”).

<Metal oxide, metal sulfide (D)>
(D-1) Titanium oxide having an average primary particle size of 0.2 μm. Trade name: R-TC30 (registered trademark) manufactured by Huntsman (hereinafter sometimes referred to as "D-1").
(D-2) Zinc oxide having an average primary particle size of 0.3 μm. Trade name: Ginrei A (registered trademark), manufactured by Mitsui Kinzoku Mining Co., Ltd. (hereinafter sometimes referred to as "D-2").
(D-3) Zinc sulfide having an average primary particle size of 0.3 μm. Trade name: Sactris HD (registered trademark), manufactured by Sacttriben (hereinafter sometimes referred to as "D-3").
(D-4) Magnesium oxide having an average primary particle size of 0.6 μm. Trade name: Starmag PSF-150 (registered trademark), manufactured by Kojima Chemical Co., Ltd. (hereinafter sometimes referred to as "D-4").

<Lubricant (E)>
(E-1) Zinc stearate. Trade name: Daiwax Z (registered trademark), manufactured by Dainichi Chemical Industry Co., Ltd. (hereinafter sometimes referred to as "E-1").
(E-2) Calcium stearate. Trade name: Calcium Stearate S (registered trademark) manufactured by NOF Corporation (hereinafter sometimes referred to as "E-2").
(E-3) Ethylene bis stearamide. Trade name: Kaowax EB-FF (registered trademark), manufactured by Kao Corporation (hereinafter sometimes referred to as "E-3").

<Styrene-based thermoplastic elastomer (F)>
(F-1) A copolymer having a styrene block and a hydrogenated butadiene block. Trade name: Tuftec H1043 (registered trademark), manufactured by Asahi Kasei Corporation (hereinafter sometimes referred to as "F-1").

<Other materials>
(TAFMER) ethylene-propylene copolymer. Trade name: TAFMER P0680J (registered trademark), manufactured by Mitsui Chemicals.

[Comparative Example 1]
(A-1) 68 parts by mass, (B-1) 19 parts by mass, (F-1) 12 parts by mass, and (TAFMER) 1 part by mass, manufactured by Werner & Pfleiderer in Germany, barrel number 13, screw ZSK40MC twin screw extruder with a diameter of 40 mm (kneading disk L: 2, kneading disk R: 6, kneading disk N: screw pattern with 4) supplied from the most upstream part (top feed), cylinder A resin composition was obtained by melt-kneading at a temperature of 300° C., a screw rotation speed of 450 rpm, and an extrusion rate of 150 kg/h. Table 1 shows the physical property test results of the resin composition.

[Comparative Example 2]
(A-1) 68 parts by mass, (B-1) 13.5 parts by mass, (C-1) 5 parts by mass, (E-1) 0.5 parts by mass, and (F-1) 12 A part by mass and 1 part by mass of (TAFMER) are mixed with a ZSK40MC twin-screw extruder with a barrel number of 13 and a screw diameter of 40 mm (kneading disc L: 2, kneading disc R: 6, knee A resin composition was obtained by feeding from the most upstream part (top feed) of a screw pattern having 4 Ding discs N, and melt-kneading at a cylinder temperature of 300° C., a screw rotation speed of 450 rpm, and an extrusion rate of 150 kg/h. Table 1 shows the physical property test results of the resin composition.

[Comparative Example 3]
(A-1) 68 parts by mass, (B-1) 16.5 parts by mass, (D-1) 80% by mass and (E-1) 20% by mass were mixed in advance with a Henschel mixer 2.5 raw materials Part by mass, (F-1) 12 parts by mass, and (TAFMER) 1 part by mass, ZSK40MC twin screw extruder with 13 barrels and a screw diameter of 40 mm manufactured by Werner & Pfleiderer in Germany (kneading disc L: 2 pieces , kneading disk R: 6, kneading disk N: screw pattern with 4), supplied from the most upstream part (top feed), and melted at a cylinder temperature of 300 ° C., a screw rotation speed of 450 rpm, and an extrusion rate of 150 kg / h. A resin composition was obtained by kneading. Table 1 shows the physical property test results of the resin composition.

[Example 1]
(A-1) 68 parts by mass, (B-1) 13.8 parts by mass, (C-1) 5 parts by mass, (D-1) 80% by mass / (E-1) 20% by mass 0.2 parts by mass of the raw material premixed in a Henschel mixer, 12 parts by mass of (F-1), and 1 part by mass of (TAFMER) were mixed in a ZSK40MC biaxial with a barrel number of 13 and a screw diameter of 40 mm manufactured by Werner & Pfleiderer of Germany. Supplied from the most upstream part (top feed) of the extruder (kneading disc L: 2, kneading disc R: 6, kneading disc N: screw pattern with 4), cylinder temperature 300 ° C., screw rotation A resin composition was obtained by melt kneading at several 450 rpm and an extrusion rate of 150 kg/h. Table 1 shows the physical property test results of the resin composition.

[Example 2]
(B-1) is 13.8 parts by mass to 13.4 parts by mass, and 80% by mass of (D-1) / 20% by mass of (E-1) are mixed in advance with a Henschel mixer, and 0.2 parts by mass of the raw material A resin composition was obtained by melt-kneading under the same conditions as in Example 1, except that the content was changed from to 0.6 parts by mass. Table 1 shows the physical property test results of the resin composition.

[Example 3]
(B-1) is 13.8 parts by mass to 12.8 parts by mass, and 80% by mass of (D-1) / 20% by mass of (E-1) are mixed in advance with a Henschel mixer, and 0.2 parts by mass of the raw material A resin composition was obtained by melt-kneading under the same conditions as in Example 1, except that the content was changed from to 1.2 parts by mass. Table 1 shows the physical property test results of the resin composition.

[Example 4]
(B-1) is 13.8 parts by mass to 11.5 parts by mass, and 80% by mass of (D-1) / 20% by mass of (E-1) are mixed in advance with a Henschel mixer, and 0.2 parts by mass of the raw material A resin composition was obtained by melt-kneading under the same conditions as in Example 1, except that the content was changed from to 2.5 parts by mass. Table 1 shows the physical property test results of the resin composition.

[Example 5]
(D-1) 80% by mass / (E-1) 20% by mass were mixed in advance with a Henschel mixer, and 2.5 parts by mass of the raw material was mixed with 1.5 parts by mass of (D-1) and 1 part by mass of (E-1). A resin composition was obtained by melt-kneading under the same conditions as in Example 4, except that the components were changed to . Table 1 shows the physical property test results of the resin composition.

[Comparative Example 4]
(D-1) 80% by mass / (E-1) 20% by mass were mixed in advance with a Henschel mixer, and 2.5 parts by mass of the raw material was mixed with 1 part by mass of (D-1) and 1.5 parts by mass of (E-1). A resin composition was obtained by melt-kneading under the same conditions as in Example 4, except that the components were changed to . Table 1 shows the physical property test results of the resin composition.

[Comparative Example 5]
(D-1) 80% by mass/(E-1) 20% by mass were mixed in advance with a Henschel mixer, and 2.5 parts by mass of the raw material was mixed with 2.2 parts by mass of (D-1) and 0.2 parts by mass of (E-1). A resin composition was obtained by melt-kneading under the same conditions as in Example 4, except that the content was changed to 3 parts by mass. Table 1 shows the physical property test results of the resin composition.

[Example 6]
(A-1) 84 parts by mass, (B-2) 4.8 parts by mass, (C-1) 5 parts by mass, (D-1) 80% by mass / (E-1) 20% by mass 1.2 parts by mass of the raw material previously mixed with a Henschel mixer and 5 parts by mass of (F-1) were mixed with a ZSK40MC twin-screw extruder (kneading disk L: 2, kneading disk R: 6, kneading disk N: screw pattern having 4), supplied from the most upstream part (top feed), cylinder temperature 300 ° C., screw rotation speed 450 rpm, extrusion rate 150 kg / h to obtain a resin composition. Table 1 shows the physical property test results of the resin composition.

[Example 7]
(A-1) 68 parts by mass, (B-1) 6.5 parts by mass, (C-3) 10 parts by mass, (D-1) 2 parts by mass, and (E-1) 0.5 Part by mass, (F-1) 12 parts by mass, and (TAFMER) 1 part by mass, ZSK40MC twin screw extruder with 13 barrels and a screw diameter of 40 mm manufactured by Werner & Pfleiderer in Germany (kneading disc L: 2 pieces , kneading disk R: 6, kneading disk N: screw pattern with 4), supplied from the most upstream part (top feed), and melted at a cylinder temperature of 300 ° C., a screw rotation speed of 450 rpm, and an extrusion rate of 150 kg / h. A resin composition was obtained by kneading. Table 2 shows the physical property test results of the resin composition.

[Example 8]
A resin composition was obtained by melt-kneading under the same conditions as in Example 7, except that (C-3) was replaced with (C-1). Table 2 shows the physical property test results of the resin composition.

[Example 9]
A resin composition was obtained by melt-kneading under the same conditions as in Example 7, except that (C-3) was replaced with (C-2). Table 2 shows the physical property test results of the resin composition.

[Example 10]
A resin composition was obtained by melt-kneading under the same conditions as in Example 7, except that (D-1) was replaced with (D-2). Table 2 shows the physical property test results of the resin composition.

[Example 11]
A resin composition was obtained by melt-kneading under the same conditions as in Example 7, except that (D-1) was replaced with (D-3). Table 2 shows the physical property test results of the resin composition.

[Example 12]
A resin composition was obtained by melt-kneading under the same conditions as in Example 7, except that (D-1) was replaced with (D-4). Table 2 shows the physical property test results of the resin composition.

[Example 13]
A resin composition was obtained by melt-kneading under the same conditions as in Example 7, except that (E-1) was replaced with (E-2). Table 2 shows the physical property test results of the resin composition.

[Example 14]
A resin composition was obtained by melt-kneading under the same conditions as in Example 7, except that (E-1) was replaced with (E-3). Table 2 shows the physical property test results of the resin composition.

[Example 15]
(A-1) 20 parts by mass, (B-1) 30 parts by mass, (C-1) 3 parts by mass, (D-1) 80% by mass / (E-1) 20% by mass in advance Henschel 1.2 parts by mass of the raw material mixed with a mixer, ZSK40MC twin-screw extruder with 13 barrels and a screw diameter of 40 mm manufactured by Werner & Pfleiderer in Germany (kneading disc L: 2, kneading disc R: 6, knee (B-2) 45.8 parts by mass of (B-2) is supplied by side feed from the barrel 5 on the way, and the cylinder temperature is 300 ° C. , and melt-kneaded at a screw rotation speed of 450 rpm and an extrusion rate of 150 kg/h to obtain a resin composition. Table 3 shows the physical property test results of the resin composition.

[Example 16]
(B-2) Of 45.8 parts by mass, 12 parts by mass were replaced with (F-1) and melt-kneaded under the same conditions as in Example 15, except that it was supplied from the most upstream part (top feed). to obtain a resin composition. Table 3 shows the physical property test results of the resin composition.

[Example 17]
(A-1) 20 parts by mass, (B-1) 25.5 parts by mass, (C-1) 3 parts by mass, (D-1) 2.1 parts by mass, and (E-1) 1 .4 parts by mass, manufactured by Werner & Pfleiderer of Germany, ZSK40MC twin-screw extruder with 13 barrels and a screw diameter of 40 mm (kneading disc L: 2, kneading disc R: 6, kneading disc N: 4 (B-2) is supplied from the most upstream part (top feed) of the screw pattern), and 48 parts by mass of (B-2) is supplied by side feed from the barrel 5 on the way, the cylinder temperature is 300 ° C., the screw rotation speed is 450 rpm, and the extrusion rate is A resin composition was obtained by melt-kneading at 150 kg/h. Table 3 shows the physical property test results of the resin composition.

[Comparative Example 6]
(D-1) was changed from 2.1 parts by mass to 1.4 parts by mass, and (E-1) was changed from 1.4 parts by mass to 2.1 parts by mass. A resin composition was obtained by melt-kneading under the conditions. Table 3 shows the physical property test results of the resin composition.

[Comparative Example 7]
(B-1) was changed from 25.5 parts by mass to 24.8 parts by mass, and (E-1) was changed from 1.4 parts by mass to 2.1 parts by mass. A resin composition was obtained by melt-kneading under the conditions. Table 3 shows the physical property test results of the resin composition.

[Comparative Example 8]
(B-1) was changed from 25.5 parts by mass to 24.8 parts by mass, (D-1) was changed from 2.1 parts by mass to 3.6 parts by mass, and (E-1) was changed to 1. A resin composition was obtained by melt-kneading under the same conditions as in Example 17, except that the content was changed from 4 parts by mass to 0.6 parts by mass. Table 3 shows the physical property test results of the resin composition.

[Example 18]
Under the same conditions as in Example 15, except that (A-1) was changed from 20 parts by mass to 35 parts by mass and (B-2) was changed from 45.8 parts by mass to 30.8 parts by mass. A resin composition was obtained by melt-kneading. Table 3 shows the physical property test results of the resin composition.

[Example 19]
(A-1) was changed from 20 parts by mass to 45 parts by mass, (B-1) was changed from 30 parts by mass to 25 parts by mass, and (B-2) was changed from 45.8 parts by mass to 25.8 parts by mass. A resin composition was obtained by melt-kneading under the same conditions as in Example 15, except that the components were changed to parts. Table 3 shows the physical property test results of the resin composition.

[Example 20]
(A-1) 68 parts by mass, (B-1) 8.4 parts by mass, (D-1) 80% by mass / (E-1) 20% by mass 0.6 raw material mixed in advance with a Henschel mixer Part by mass, (F-1) 12 parts by mass, and (TAFMER) 1 part by mass, ZSK40MC twin screw extruder with 13 barrels and a screw diameter of 40 mm manufactured by Werner & Pfleiderer in Germany (kneading disc L: 2 pieces , kneading disk R: 6, kneading disk N: screw pattern with 4) supplied from the most upstream part (top feed), and 10 parts by mass of (C-3) from the barrel 8 on the way, liquid addition They were added using a nozzle and melt-kneaded at a cylinder temperature of 300° C., a screw rotation speed of 450 rpm and an extrusion rate of 150 kg/h to obtain a resin composition. Table 4 shows the physical property test results of the resin composition.

[Example 21]
(F-1) was changed from 12 parts by mass to 7 parts by mass, and (C-3) was changed from 10 parts by mass to 15 parts by mass. got stuff Table 4 shows the physical property test results of the resin composition.

[Example 22]
(F-1) was changed from 12 parts by mass to 2 parts by mass, and (C-3) was changed from 10 parts by mass to 20 parts by mass. got stuff Table 4 shows the physical property test results of the resin composition.

From Table 1, the resin compositions of Comparative Examples 1 and 3 do not have sufficient heat aging resistance because the component (C) of the present application is not blended.
Since the resin composition of Comparative Example 2 does not contain the component (D) of the present application, the appearance of the molded product after continuous molding is not sufficient. Adhesion of MD (mold deposit), which is considered to be derived from component (C), was observed.
In the resin compositions of Comparative Examples 4 and 5, the ratio of the components (D)/(E) of the present application deviates from the ratio stipulated in the present application. In Comparative Example 4, cloudiness was observed in the flat plate molded product at the 250th shot, and MD adhesion was observed on the mold, which was considered to be derived from components (C) and (E). In Comparative Example 5, the flat plate molded product after 250 shots was found to have a poor appearance, probably due to poor dispersion of the component (D). It is presumed that the component (D) was not sufficiently dispersed due to the small amount of the component (E) used in combination, causing the poor appearance.
On the other hand, in the resin compositions of Examples 1 to 6, the blending amounts and blending ratios of the components (C), (D), and (E) of the present application are all within the ranges specified in the present application, and thus are excellent in heat resistance aging. In addition, the appearance and Charpy impact strength of the flat plate molded product after continuous molding were both good.

From Table 2, the resin compositions of Examples 7 to 14 are excellent because the blending amounts and blending ratios of the components (C), (D), and (E) of the present application are within the ranges specified in the present application. In addition to exhibiting heat aging resistance, the appearance and Charpy impact strength of flat plate molded articles after continuous molding were both good.
In particular, in Examples 7 to 9, Example 8 using PX-200 as the component (C) tended to be excellent in heat aging resistance and Charpy impact strength.

From Table 3, the resin compositions of Examples 15 to 19 are excellent because the blending amounts and blending ratios of the components (C), (D), and (E) of the present application are within the ranges specified in the present application. It showed heat aging resistance, and the appearance of the flat plate molded products after continuous molding was also good.
On the other hand, in the resin compositions of Comparative Examples 6 to 8, since the ratio of the components (D)/(E) of the present application deviates from the ratio specified in the present application, the heat aging resistance and the appearance of the molded product after continuous molding are not sufficient. None. In Comparative Examples 6 and 7, the blending ratio of the component (E) to the component (D) is outside the specified range of the present application, and in Comparative Example 7, the blending ratio of the component (D) and the component (E) is also within the range specified in the present application. Since the specified upper limit was exceeded, haze was observed in all flat plate molded products at the 250th shot. On the other hand, in Comparative Example 8, the blending ratio of the component (D) to the component (E) is out of the range specified in the present application, and the blending amounts of the components (D) and (E) also exceed the upper limit specified in the present application. In the flat plate molded product with shot marks, poor appearance was observed, which was considered to be due to poor dispersion of the component (D).

From Table 4, the resin compositions of Examples 20 to 22 are excellent because the blending amounts and blending ratios of the components (C), (D), and (E) of the present application are within the ranges specified in the present application. It showed heat aging resistance, and the appearance of the flat plate molded products after continuous molding was also good. In Example 20, since the amount of component (C) was slightly large, the MFR was difficult to measure, and the Charpy impact strength tended to decrease slightly.

The polyphenylene ether-based resin composition of the present invention is particularly excellent in compatibility with heat aging resistance near 110 to 140 ° C. and retention of molded appearance in long-term continuous molding. It is a polyphenylene ether resin composition that maintains a balance between performance and impact resistance without impairing the performance balance, and is therefore used for home appliance OA equipment parts, internal parts of electrical and electronic equipment, internal parts of automobiles, and various industrial products. It can be effectively used for decorative molded parts.

Claims (9)

At least selected from the group consisting of polyphenylene ether (A), condensed phosphoric ester compound (C), metal oxide and/or metal sulfide (D), higher fatty acid amide, higher fatty acid bisamide, and higher fatty acid metal salt A lubricant (E) containing one or more, and optionally a styrenic resin (B),
The content of each component with respect to the total amount of 100 parts by mass of components (A), (B), (C), (D) and (E) is 10 to 95 parts by mass for component (A) and 0 for component (B). 80 parts by mass, 1 to 25 parts by mass of component (C), and 0.1 to 3.5 parts by mass of components (D) and (E) in total,
Polyphenylene ether-based, characterized in that the content ratio of the (D) component and the (E) component in the resin composition is within the range of (D) / (E) = 80/20 to 55/45 Resin composition. 2. The polyphenylene ether resin composition according to claim 1, wherein the component (C) is a condensed phosphoric acid ester compound represented by the following formula (1).

(R ¹ to R ⁴ in chemical formula (1) represent a 2,6-xylyl group, and n represents 1 to 3.) 3. The polyphenylene ether resin composition according to claim 1, wherein the component (D) contains at least one selected from the group consisting of titanium oxide, zinc oxide and zinc sulfide. Total content of component (C), component (D) and component (E) in 100 parts by mass of the total amount of components (A), (B), (C), (D) and (E) is 17 parts by mass or less, the polyphenylene ether resin composition according to claim 1 or 2. 0.1 to 25 parts by mass of a styrenic thermoplastic elastomer (F) is added to the total amount of 100 parts by mass of components (A), (B), (C), (D), and (E). The polyphenylene ether-based resin composition according to claim 1 or 2, characterized by: The total content of the components (A), (B), (C), (D), (E) and (F) accounts for 85% by mass or more of the entire polyphenylene ether resin composition. The polyphenylene ether-based resin composition according to claim 1 or 2, wherein 3. The polyphenylene ether-based resin composition according to claim 1, wherein the content of the polyolefin-based resin in 100 parts by mass of the polyphenylene ether-based resin composition is 5 parts by mass or less. 3. The polyphenylene ether resin composition according to claim 1, wherein the tensile strength retention after aging at 130[deg.] C. for 1000 hours is 90% or more. 3. A method for producing the polyphenylene ether-based resin composition according to claim 1 or 2, comprising the components (A), (C), (D) and (E), and optionally the (B) A polyphenylene ether-based resin composition comprising a step of melt-kneading the (F) component and other materials, and using a premix of the (D) component and the (E) component as raw materials. manufacturing method.