JP2023001874A - Polyphenylene ether-based resin composition - Google Patents

Abstract

To provide a polyphenylene ether-based resin composition which has excellent heat aging resistance at around 110-140°C and, at the same time, has a performance balance between stiffness and toughness and has good molding appearance.SOLUTION: There is provided, a polyphenylene ether-based resin composition, comprising polyphenylene ether (A), an antioxidant (C), a metal oxide and/or a metal sulfide (D), a lubricant (E) and, further, optionally a styrene-based resin (B). Relative to 100 pts.mass the (A) component, the (B) component, the (C) component, the (D) component and the (E) component, a mass ratio of each component is 10-95 pts.mass of (A) component, 0-80 pts.mass of (B) component, 0.05-3 pts.mass of (C) component, and 0.1-3.5 pts.mass of the total of (D) component and (E) component, where a mass ratio of the (D) component and the (E) component is (D) component/(E) component=80/20-55/45.SELECTED DRAWING: None

Description

The present invention relates to a polyphenylene ether resin composition.

Many polyphenylene ether-based resins are made by combining polyphenylene ether and styrene-based resin in an arbitrary ratio according to the level of heat resistance and molding fluidity required, and if necessary, an elastomer component, Additive components such as flame retardants, inorganic fillers, and heat stabilizers may be 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 investigated for molded products used in projectors and various lighting fixtures, thin-walled automobile parts, etc., but the parts used in such applications are exposed to high temperatures for long periods of time. In many cases, it is required that the mechanical strength of the molded article is sufficiently maintained even when it is exposed.

As a technology for improving the high-temperature aging (long-term high-temperature exposure) characteristics of polyphenylene ether-based resin compositions, by blending a specific aromatic vinyl resin, the generation of unmelted substances due to oxidative deterioration after high-temperature aging of polyphenylene ether is suppressed. Techniques have been disclosed (see Patent Document 1, for example).

Also, the side chain and terminal methyl group and/or terminal OH group of polyphenylene ether are reacted with a compound such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to modify the terminal. discloses a technique relating to a resin composition with improved high-temperature aging properties (see, for example, Patent Document 2).

JP-A-8-199060 WO2017/119017

However, when a molded article made of conventional polyphenylene ether resin is subjected to a high-temperature aging (long-term heat exposure) test under temperature conditions of about 110 to 140 ° C, mechanical properties such as tensile strength are significantly reduced, so it is not always sufficient. may not be.
Even in the resin composition as disclosed in Patent Document 1 and Patent Document 2, although sufficient mechanical properties are maintained in aging tests under temperature conditions of 150 ° C. or higher, test temperature conditions are less than 150 ° C., especially Under the test temperature conditions of 110 to 140° C., there were cases where the retention of mechanical properties was not necessarily sufficient.

The reason for this is that when the aging test is performed at a temperature of 150°C or higher, the oxidative heat deterioration of the surface layer of the molded product rapidly progresses, forming a barrier layer on the surface layer that prevents the progress of oxidation to the inside. Therefore, it is presumed that the subsequent oxidation into the inside of the molded article becomes difficult for oxygen to permeate, and the oxidation deterioration of the inside progresses relatively slowly. On the other hand, under conditions of temperatures lower than 150°C, particularly at temperatures of about 110 to 140°C, oxidative heat deterioration of the surface layer of the molded product does not progress rapidly, and an oxidation barrier layer is difficult to form on the surface of the molded product. It is conceivable that oxygen permeates to the inside and oxidation deterioration progresses, and as a result, deterioration of mechanical properties progresses relatively rapidly in a short period of time.

It is extremely difficult to improve the heat aging resistance of polyphenylene ether resins under temperature conditions of 110 to 140 ° C., and improving the heat aging resistance in this temperature range is necessary for internal parts such as home appliance OA and office machines. This was an important issue for internal parts around automobile engines and for materials used at relatively high temperatures.

Therefore, the present invention provides a polyphenylene ether-based resin that is excellent in heat aging resistance around 110 to 140 ° C., and at the same time, maintains the performance balance between rigidity and toughness inherent in polyphenylene ether-based resins, and maintains good molded appearance. An object of the present invention is to provide a resin composition.

The present inventors have made intensive studies to solve the above problems. By adjusting the mass ratio of the metal oxide and/or metal sulfide and the lubricant to a specific range, it is possible to improve heat aging resistance under temperature conditions around 110 to 140 ° C. The inventors have found that a resin composition can be obtained, and have been able to provide the present invention.

That is, the present invention is as follows.
[1]
Polyphenylene ether (A), antioxidant (C), metal oxide and/or metal sulfide (D), and at least one lubricant selected from the group consisting of higher fatty acid amides, higher fatty acid bisamides and higher fatty acid metal salts (E) containing
Further optionally contains a styrene resin (B),
The mass ratio of each component to a total of 100 parts by mass of the component (A), the component (B), the component (C), the component (D) and the component (E) is 10 to 95 mass parts of the component (A). parts, 0 to 80 parts by mass of component (B), 0.05 to 3 parts by mass of component (C), and 0.1 to 3.5 parts by mass of components (D) and (E) in total,
A polyphenylene ether-based resin composition characterized in that the mass ratio of the component (D) and the component (E) is component (D)/component (E) = 80/20 to 55/45.
[2]
The polyphenylene ether-based resin composition according to [1], wherein the inorganic filler has a mass ratio of less than 15% by mass with respect to 100% by mass of the polyphenylene ether-based resin composition.
[3]
The polyphenylene ether resin composition according to [2], wherein the inorganic filler has a mass ratio of 4% by mass or less.
[4]
The polyphenylene ether resin composition according to any one of [1] to [3], wherein the component (C) is an antioxidant having a melting point of 180° C. or higher.
[5]
The content of the aromatic phosphate ester flame retardant and/or the phosphazene flame retardant in 100% by mass of the polyphenylene ether resin composition is 5% by mass or less, [1] to [4]. A polyphenylene ether resin composition.
[6]
The polyphenylene ether resin composition according to any one of [1] to [5], wherein the component (C) is a phosphorus antioxidant.
[7]
The polyphenylene ether resin composition according to any one of [1] to [6], wherein the component (D) contains at least one selected from the group consisting of titanium oxide, zinc oxide and zinc sulfide.
[8]
The (C) component, the (D) component and the ( E) The polyphenylene ether resin composition according to any one of [1] to [7], wherein the total mass ratio of components is 4 parts by mass or less.
[9]
Furthermore, it contains a styrene-based thermoplastic elastomer (F),
The mass ratio of the component (F) with respect to a total of 100 parts by mass of the component (A), the component (B), the component (C), the component (D) and the component (E) is 0.1 to The polyphenylene ether resin composition according to any one of [1] to [8], which is 25 parts by mass.
[10]
Total mass of the (A) component, the (B) component, the (C) component, the (D) component, the (E) component and the (F) component with respect to 100% by mass of the polyphenylene ether resin composition The polyphenylene ether-based resin composition according to [9], wherein the proportion is 85% by mass or more.
[11]
The polyphenylene ether-based resin composition according to any one of [1] to [10], wherein the polyolefin-based resin has a mass ratio of 5% by mass or less with respect to 100% by mass of the polyphenylene ether-based resin composition.
[12]
The polyphenylene ether resin composition according to any one of [1] to [11], which has a tensile strength retention of 90% or more after aging for 500 hours at 130°C.
[13]
[1] A method for producing a polyphenylene ether-based resin composition according to any one of [1] to [12],
A step of melt-kneading the (A) component, the (C) component, the (D) component and the (E) component, and optionally the (B) component, the (F) component and/or other materials including
A method for producing a polyphenylene ether-based resin composition, wherein in the melt-kneading step, a mixture of the component (D) and the component (E) is used as a raw material.

According to the present invention, there is provided a polyphenylene ether-based resin composition which is excellent in heat aging resistance around 110 to 140° C. and which maintains the performance balance between rigidity and toughness inherent in polyphenylene ether-based resins. be able to.

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 comprises polyphenylene ether (A), antioxidant (C), metal oxide and/or metal sulfide (D), higher fatty acid amide, higher fatty acid bisamide and higher fatty acid metal Containing at least one lubricant (E) selected from the group consisting of salts, optionally containing a styrenic resin (B), the component (A), the component (B), and the component (C) , The mass ratio of each component to a total of 100 parts by mass of the above component (D) and the above component (E) is 10 to 95 parts by mass of component (A), 0 to 80 parts by mass of component (B), and 0 part by mass of component (C). .05 to 3 parts by mass, total 0.1 to 3.5 parts by mass of component (D) and component (E), in the polyphenylene ether resin composition of component (D) and component (E) is in the range of component (D)/component (E) = 85/15 to 55/45.
In addition, in this specification, the said polyphenylene-ether-type resin composition may only be called a "resin composition." Further, polyphenylene ether (A) is "(A) component", styrene resin (B) is "(B) component", antioxidant (C) is "(C) component", metal oxide and / or metal When the sulfide (D) is referred to as "(D) component" and the lubricant (E), which is at least one selected from the group consisting of higher fatty acid amides, higher fatty acid bisamides and higher fatty acid metal salts, is referred to as "(E) component" There is

但し、上記化学式（１）及び（２）中、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５及びＲ６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、又はハロゲン原子を表す。但しＲ５及びＲ６は同時に水素ではない。また、上記アルキル基の好ましい炭素数は１～３であり、上記アリール基の好ましい炭素数は６～８である。中でも、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５及びＲ６は、それぞれ独立して、水素原子、炭素数１～４のアルキル基（好ましくは炭素数１～３のアルキル基）が好ましく、より好ましくは炭素数１～４のアルキル基（好ましくは炭素数１～３のアルキル基）である。
尚、上記化学式（１）、（２）で表され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))
Polyphenylene ether (A) contained in the polyphenylene ether-based resin composition of the present embodiment is a repeating unit represented by the following chemical formula (1) and / or a repeating unit (structural unit) represented by the chemical formula (2) It is preferably a homopolymer (homopolymer) or a copolymer (copolymer) having

However, in the above chemical formulas (1) and (2), R1, R2, R3, R4, R5 and R6 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 9 carbon atoms. represents a group or a halogen atom. However, R5 and R6 are not hydrogen at the same time. The alkyl group preferably has 1 to 3 carbon atoms, and the aryl group preferably has 6 to 8 carbon atoms. Among them, R1, R2, R3, R4, R5 and R6 are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (preferably an alkyl group having 1 to 3 carbon atoms), more preferably carbon It is an alkyl group having 1 to 4 numbers (preferably an alkyl group having 1 to 3 carbon atoms).
The number of repeating units represented by the above chemical formulas (1) and (2) 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 the chemical formula (1) and / or chemical formula (2), 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 contains at least a portion of a structure in which each of R1 and R2 in the chemical formula (1) is a methyl group (and, as described later, a structure derived from the structure). preferably. 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.

The polyphenylene ether (A) is a polyphenylene ether containing various phenylene ether units other than those represented by the general formulas (1) and (2) 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 (1) and (2) 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 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 acid 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. It is 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 (A) 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, polyphenylene ether (A), styrene resin (B), antioxidant (C), metal oxide and/or metal sulfide (D), higher fatty acid amide, The mass ratio of the polyphenylene ether (A) to the total 100 parts by mass of the lubricant (E), which is at least one selected from the group consisting of higher fatty acid bisamides and higher fatty acid metal salts, is within the range of 10 to 95 parts by mass. , preferably 10 to 90 parts by mass, more preferably 40 to 90 parts by mass, still more preferably 40 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 from the viewpoint of further imparting heat resistance (for example, imparting heat resistance at a temperature of 130 ° C. or higher) and expressing mechanical properties. 40 parts by mass or more is more preferable, and 95 parts by mass or less is preferable 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 resin (B) is a homopolymer of a styrene compound, a copolymer of a styrene compound and a compound copolymerizable with a styrene compound (excluding a conjugated diene compound) ( preferably a random copolymer). This component (B) does not include those included in the category of the component (F) described later.
The above component (B) may be used alone or in combination of multiple types.

Specific examples of the styrene compounds 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 or hydrogenated products thereof, copolymers of conjugated dienes and aromatic vinyl compounds or 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, polyphenylene ether (A), styrene resin (B), antioxidant (C), metal oxide and/or metal sulfide (D), higher fatty acid amide, The mass ratio of the styrene resin (B) to the total 100 parts by mass of the lubricant (E), which is at least one selected from the group consisting of higher fatty acid bisamides and higher fatty acid metal salts, is in the range of 0 to 80 parts by mass. is. 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 mass ratio of the styrene resin (B) is preferably more than 0 parts by mass from the viewpoint of imparting sufficient molding fluidity, and is preferably 80 parts by mass or less from the viewpoint of maintaining sufficient heat resistance. preferable.

(Antioxidant (C))
Antioxidants (C) may be used singly or in combination of two or more.
As the antioxidant (C), both primary antioxidants that act as radical chain inhibitors and secondary antioxidants that are effective in decomposing peroxides can be used. That is, by using an antioxidant, when the polyphenylene ether is exposed to high temperature for a long time, it is possible to capture radicals that may be generated in the terminal methyl group or the side chain methyl group (primary antioxidant), or The radicals can decompose peroxides formed on terminal methyl groups or side-chain methyl groups (secondary antioxidants), thus preventing oxidative cross-linking of polyphenylene ether.

As the primary antioxidant, mainly hindered phenol-based antioxidants can be used, and specific examples include 2,6-di-t-butyl-4-methylphenol, pentaerythritol tetrakis[3-(3 ,5-di-t-butyl-4-hydroxyphenyl)propionate], n-octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,2′-methylenebis(4- methyl-6-t-butylphenol), 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenylacrylate, 2-[1-(2-hydroxy- 3,5-di-t-pentylphenyl)ethyl]-4,6-di-t-pentylphenyl acrylate, 4,4′-butylidenebis(3-methyl-6-t-butylphenol), alkylated bisphenol, tetrakis [methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methyl phenyl)-propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxyspiro[5,5]undecane and the like.

Phosphorus-based antioxidants can be mainly used as secondary antioxidants. Specific examples of phosphorus antioxidants include trisnonylphenyl phosphite, triphenyl phosphite, tris(2,4-di-t-butylphenyl)phosphite, bis(2,4-di-t-butylphenyl) Pentaerythritol-di-phosphite, bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol-di-phosphite, 3,9-bis(2,6-di-tert-butyl-4 -methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane and other phosphite antioxidants.

The melting point of the antioxidant (C) used in the present embodiment is preferably 180° C. or higher, more preferably 200 to 310° C., more preferably 220 to 270° C., from the viewpoint of improving long-term heat aging resistance. It is even more preferred to have
The above melting point can be determined as the melting end point temperature using a melting point measuring instrument model: B-545 (manufactured by Shibata Kagaku Co., Ltd.) in accordance with JISK 0064 light transmission measurement.

In addition, from the viewpoint of further improving aging properties after long-term high-temperature exposure, phosphorus-based antioxidants, which are secondary antioxidants, are preferred, and phosphite-based antioxidants are more preferred.

In the resin composition of the present embodiment, polyphenylene ether (A), styrene resin (B), antioxidant (C), metal oxide and/or metal sulfide (D), higher fatty acid amide, The mass ratio of the antioxidant (C) to the total 100 parts by mass of the lubricant (E), which is at least one selected from the group consisting of higher fatty acid bisamides and higher fatty acid metal salts, is 0.05 to 3 parts by mass. Within range. It is preferably in the range of 0.1 to 2 parts by mass, more preferably in the range of 0.2 to 1 part by mass.
The mass ratio of the antioxidant (C) is preferably 0.05 parts by mass or more from the viewpoint of improving heat aging resistance, and is 3 parts by mass or less from the viewpoint of preventing mold contamination and maintaining the appearance of molding. 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.
The component (D) may be used singly or in combination of multiple types.

In the resin composition of the present embodiment, the average primary particle size of component (D) 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.

In the resin composition of the present embodiment, polyphenylene ether (A), styrene resin (B), antioxidant (C), metal oxide and/or metal sulfide (D), higher fatty acid amide, The mass ratio of the metal oxide and/or metal sulfide (D) to 100 parts by mass in total with the lubricant (E), which is at least one selected from the group consisting of higher fatty acid bisamides and higher fatty acid metal salts, is 0. It is preferably in the range of 05 to 3 parts by mass, more preferably in the range of 0.1 to 2 parts by mass, still more preferably in the range of 0.2 to 1.5 parts by mass. From the viewpoint of improving heat-resistant aging resistance, the amount is preferably 0.05 parts by mass or more, and from the viewpoints of mechanical properties and maintenance of molding appearance, it is preferably 3 parts by mass or less.

(Lubricant (E))
The lubricant (E) contained in the polyphenylene ether-based resin composition of the present embodiment is at least one 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 (for example, 16 to 30 carbon atoms) are preferred from the viewpoint of the effect of preventing the occurrence of scorch and dandruff. Specifically, palmitic acid, stearic acid, and olein are preferred. acid, erucic acid, behenic acid, montanic acid and the like.
Examples of 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; aromatic acids such as phthalic acid and terephthalic acid. dicarboxylic acids; alicyclic dicarboxylic acids such as cyclohexyldicarboxylic acid and cyclohexylsuccinic acid; and the like.
Examples of diamines include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, hexamethylenediamine, metaxylylenediamine, tolylenediamine, paraxylylenediamine, phenylenediamine, and isophoronediamine.

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), specifically methylene. bisstearylamide, ethylene bisstearylamide, 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 embodiment has a carbon number of 10 to 30 (preferably 14 to 24) as the higher fatty acid, has low volatility, and is highly effective in preventing the occurrence of discoloration and build-up. Therefore, it is preferable.
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. It may also 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, polyphenylene ether (A), styrene resin (B), antioxidant (C), metal oxide and/or metal sulfide (D), higher fatty acid amide, The mass ratio of the lubricant (E) to the total 100 parts by mass of the lubricant (E), which is at least one or more selected from the group consisting of higher fatty acid bisamides and higher fatty acid metal salts, is 0.015 to 1.60 parts by mass. is preferably within the range of 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. From the viewpoint of improving resistance to heat aging, the amount is preferably 0.015 parts by mass or more, and from the viewpoints of preventing mold contamination and maintaining molding appearance, it is preferably 1.60 parts by mass or less.

In the resin composition of the present embodiment, at least one lubricant (E ) with respect to a total of 100 parts by mass of the component (A), the component (B), the component (C), the component (D) and the component (E), from 0.1 to It is within the range of 3.5 parts by mass. It is preferably 0.15 to 3 parts by mass, more preferably 0.25 to 2 parts by mass. From the viewpoint of sufficient heat aging resistance improvement, it is preferably 0.1 parts by mass or more, and from the viewpoint of the mechanical properties of the molded product and the maintenance of molded appearance, it is desirable to mix it at 3.5 parts by mass or less.
The ratio of the total mass of the component (A), the component (B), the component (C), the component (D) and the component (E) in the resin composition of the present embodiment is 80 parts by mass or more. More preferably, it is 85 parts by mass or more, and may be 100 parts by mass or less, or may be 98 parts by mass or less.

The mass ratio of the component (D) and the component (E) in the resin composition of the present embodiment is within the range of component (D)/component (E)=80/20 to 55/45. It is preferably in the range of 80/20 to 60/40, more preferably in the range of 80/20 to 65/35. From the viewpoint of maintenance of the appearance and toughness of the molded article and resistance to heat aging, the content ratio of (D)/(E) is desirably within the range of 80/20 to 55/45.

The (D) component and the (E) component are used during melt kneading of the composition (for example, the (A) component, the (C) component, the (D) component and the (E) component, and optionally During the step of melt-kneading the component (B), the component (F) and/or other materials described later), for example, during melt-kneading with a twin-screw extruder or the like described later, each may be added separately. It is preferable to use a material obtained by mixing the component (D) and the component (E) in advance using a Henschel mixer or the like, from the viewpoint of maintaining the appearance and toughness of the molded product and heat aging resistance.

Furthermore, the group consisting of antioxidant (C), metal oxide and/or metal sulfide (D), higher fatty acid amide, higher fatty acid bisamide and higher fatty acid metal salt in the resin composition of the present embodiment The total mass ratio with the lubricant (E), which is at least one selected from It is preferably 4 parts by mass or less with respect to 100 parts by mass from the viewpoint of maintaining the appearance of the molded product and maintaining the balance of physical properties.

(Styrene-based thermoplastic elastomer (F))
The styrenic thermoplastic elastomer (F) used in this 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 block 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 preferred. A butadiene unit may be contained in the conjugated diene compound block within a range not exceeding 30% by mass.

In addition, in the resin composition of the present embodiment, the styrene thermoplastic elastomer may be a functionalized styrene thermoplastic elastomer into which a functional group such as a carbonyl group or an amino group is introduced.

The bound styrene content of the styrenic thermoplastic elastomer (F) is preferably in the range of 20 to 90% by mass, more preferably 50 to 80% by mass, still more preferably 60 to 70% by mass. From the viewpoint of miscibility with the component (A) and the component (B), 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) is preferably from 30,000 to 500,000, more preferably from 40,000 to 300,000, still more preferably from 45,000 to 250,000. be. 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.

The mass ratio of the styrene-based thermoplastic elastomer (F) is based on a total of 100 parts by mass of the component (A), the component (B), the component (C), the component (D), and the component (E). , 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, it is preferably 0.1 parts by mass or more, and from the viewpoint of maintaining the mechanical properties of the molded product, it is preferably 25 parts by mass or less.

(other materials)
In the polyphenylene ether-based resin composition of the present embodiment, it is possible to further blend a polyolefin-based 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 mass ratio 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.

The resin composition of the present embodiment may further contain a flame retardant.
Flame retardants include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, dixylenyl phenyl phosphate, hydroxynon bisphenol phosphate, resorcinol bisphosphate, bisphenol A bisphosphate, and the like. triphenyl-substituted aromatic phosphate compounds, phosphazene-based flame retardants such as cyclic phenoxyphosphazene compounds and chain phosphazene compounds.
A flame retardant may be used individually by 1 type, and may be used in combination of 2 or more types.

The mass ratio of the flame retardant 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, still more preferably 2% by mass or less, and particularly preferably 1% by mass or less. The mass ratio of the flame retardant is preferably 5% by mass or less from the viewpoint of maintaining heat resistance and molding appearance of the resin composition. Among them, from the viewpoint of molding retention stability of the resin composition, the content of the aromatic phosphoric acid ester flame retardant and/or the phosphazene flame retardant in 100% by mass of the resin composition is preferably 5% by mass or less. , is more preferably 3% by mass or less, still more preferably 2% by mass or less, and particularly preferably 1% by mass or less. Among them, from the viewpoint of further improving the molding retention stability of the resin composition, the flame retardant is an aromatic phosphoric acid ester flame retardant and/or a phosphazene flame retardant, and the aromatic phosphorus in 100% by mass of the resin composition The content of the acid ester flame retardant and/or the phosphazene flame retardant is preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less, and 1% by mass. % or less is particularly preferred.

Further, in the resin composition of the present embodiment, an ultraviolet absorber, a colorant, a release agent, etc. are added to 100% by mass of the resin composition within a range that does not significantly deteriorate the heat resistance, mechanical properties, and surface appearance of the molded product. It can be contained in a proportion 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 mass ratio 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, even 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 includes the above component (A), the above component (C), the above component (D) and the above component (E), and optionally the above component (B), the above component (F) and/or Alternatively, it can be manufactured by melt-kneading other materials.

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, the above "L" is the "screw barrel length" of the extruder, and the above "D" is the "screw barrel diameter".

The conditions for producing the resin composition of the present embodiment are not limited to the following, but for example, the above component (A), the above component (C), the above component (D), and the above (E ) component and, if necessary, the above component (B), the above component (F), and the above other materials are all melt-kneaded together to produce a resin composition.

Further, when the resin composition of the present embodiment is produced using a twin-screw extruder, the component (D) and the component (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) component, (B) component, (C) component, other raw materials, etc. are supplied from the supply port (top feed) at the most upstream part of the extruder and melt-kneaded to form a resin composition. You can manufacture it. Inorganic fillers and the like may be side-fed from an extruder barrel on the way, or a resin composition may be produced by blending components such as a flame retardant in a liquid addition facility and melt-kneading them. It is possible.

Further, from the viewpoint of imparting heat resistance and mechanical properties, components (A), (C), (D) and (E) are supplied from the most upstream supply port (top feed) of the extruder, 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 as necessary, melt-kneaded, and formed into 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 usage temperature environment of about 110 to 140 ° C. (for example, 110 ° C. or 130 ° C.). It is preferable that the tensile strength retention rate after exposure for 500 hours at 110 to 140° C. (eg, 110° C. or 130° C.) is 90% or more of that before exposure. More preferably, the tensile strength retention after exposure to temperature conditions of 130° C. for 500 hours is 90% 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 tensile elongation (according to ISO527, measured at 23° C.) of the resin composition of the present embodiment is preferably 10% or more from the viewpoint of shape retention and crack prevention during use of the molded product. It is more preferably 14% or more, and still more preferably 20% or more. Within the above range, the resin composition can be more preferably used for home appliance OA and business machine internal parts. Moreover, it may be 60% or less.
The tensile elongation (nominal tensile strain) of the resin composition can be specifically 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. Also, it may be 20 kJ/m ² or less.
The Charpy impact strength of the resin composition can be specifically measured by the method described in Examples below.

The deflection temperature under load (DTUL) of the resin composition of the present embodiment (based on ISO75, measured by the flatwise method under a load of 0.45 MPa) is 110° C. or higher from the viewpoint of preventing thermal deformation of thin-walled molded products when used at high temperatures. is preferably It is more preferably 125° C. or higher, and still more preferably 140° C. or higher. Moreover, it may be 180° C. or lower.
The DTUL 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. Moreover, it may be 60 g/10 min or less.
Specifically, the MFR of the resin composition can be measured by the method described in Examples below.

〔Molding〕
A molded product can be obtained by molding the resin composition of the present embodiment.
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.

Examples of suitable methods for molding the resin composition include injection molding, extrusion molding, vacuum molding, 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 within the range of 260 to 340° C. (preferably 280 to 340° C.), more preferably 300 to 330° C., and still more. It is preferably 300 to 320°C. The molding temperature is preferably 280° C. or higher from the viewpoint of sufficient molding workability, and preferably 340° 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., and 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.

Suitable molded articles in the present embodiment include mechanical properties (especially tensile strength ) is remarkably suppressed, and it can be used as a molded product with high heat resistance and good appearance. decorative molded parts 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. Deflection temperature under load (DTUL))
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, an injection molding machine (IS-80EPN, manufactured by Toshiba Machine Co., Ltd.) equipped with an ISO physical property test piece mold was used. ℃, mold temperature 90 ℃, Comparative Examples 7 to 9 and Examples 15 to 18, cylinder temperature 270 ℃, mold temperature 60 ℃, Example 19, cylinder temperature 290 ℃, mold temperature 80 ℃, respectively. 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 to mold an ISO 3167, multi-purpose specimen A-type dumbbell molded piece. 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, the deflection temperature under load (DTUL) (° C.) was measured by the flatwise method at 0.45 MPa according to ISO75, and the average value of three measured pieces was obtained.
As an evaluation criterion, it was determined that the higher the average value of the measured values, the better the heat resistance.

(2. Charpy impact strength)
1 above. ISO 3167, Multi-Purpose Specimen A-type dumbbell molded pieces were cut to produce 80 mm x 10 mm x 4 mm molded pieces. Using the test piece, Charpy impact strength (with notch) (kJ/m ² ) was measured at 23° C. in accordance with ISO179, and the average value of five measured pieces was obtained.
As an evaluation criterion, it was determined that the higher the average value of the measured values, the better the impact resistance.

(3. Tensile strength, tensile elongation)
1 above. Using the ISO3167 multi-purpose test piece A type dumbbell molded piece manufactured in ISO527, the tensile strength (MPa) and tensile elongation (tensile nominal strain) (%) are measured at 23 ° C. at a test speed of 5 mm / min. Then, the average value of 5 measurements was obtained.
As evaluation criteria, the higher the average value of the measured values of tensile strength, the better the mechanical strength, and the higher the average value of the measured values of tensile elongation (nominal tensile strain), the better the toughness. judged to be excellent.

(4. Tensile strength after aging at 110°C or 130°C for 500 hours)
3. above. The average value of the tensile strength of five dumbbell molded pieces of the multi-purpose test piece A type obtained in 1 was used as a sample before aging (blank, 0 hr). Separately, five tubes were placed in a hot air oven set to 130°C for Comparative Examples 1 to 6 and Examples 1 to 14, and 110°C for Comparative Examples 7 to 9 and Examples 15 to 19, and 500 hours passed. Afterwards, they were taken out and left for 24 hours in an environment of 23° C. temperature and 50% humidity to obtain test pieces after 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.
The tensile strength retention rate was calculated from the following formula.
(Tensile strength retention rate) (%) = (tensile strength after aging for 500 hours (MPa)) / (tensile strength before aging (MPa)) x 100

(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 to 6 and Examples 1 to 14 had a cylinder temperature of 300°C and a mold temperature of 90°C. Comparative Examples 7 to 9 and Examples 15 to 18 had a cylinder temperature of 270°C and a mold temperature of 60°C. In Example 19, the cylinder temperature is 290°C, the mold temperature is 80°C, the injection pressure is 80 MPa (gauge pressure), the injection speed (panel set value) is 60%, and the injection time/cooling time is set to 15 sec/15 sec. Continuous molding of shots was carried out. The 200th shot mirror surface flat plate molded product was visually observed. Those with good appearance were evaluated as "◯", and those with surface roughness or cloudiness were evaluated as "x". It was judged.

(6. MFR)
After drying the pellets of the resin compositions produced in Examples and Comparative Examples in a hot air dryer at 100 ° C. for 2 hours, a melt indexer (P-111, manufactured by Toyo Seiki Co., Ltd.) is used to set according to ISO 1133. A melt flow rate (MFR) (g/10 min) was measured at a temperature of 280° C. and a load of 5 kg.
As an evaluation criterion, it was determined that the higher the MFR value, the better the molding fluidity.
Moreover, it was determined that the higher the DTUL value and the higher the MFR value, the better the balance between heat resistance and molding fluidity, and the more advantageous in terms of material design.

〔raw materials〕
<Polyphenylene ether (PPE) (A)>
(A-1)
Solution polymerization of poly(2,6-dimethyl-1,4-phenylene) ether powder (A-1) with a reduced viscosity of 0.40 dl/g (0.5 g/dl chloroform solution, 30°C, measured with an Ubbelohde viscometer) (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").

<Antioxidant (C)>
(C-1)
Hindered phenol heat stabilizer with a melting point of 242° C. Chemical name: 3,3′,3″,5,5′,5″-hexa-tert-butyl-a,a′,a″-(mesitylene-2,4 ,6-triyl)tri-p-cresol Trade name: Irganox 1330 (registered trademark), manufactured by BASF (hereinafter sometimes referred to as "C-1").
(C-2)
Phosphorus-based heat stabilizer with a melting point of 184° C. Chemical name: tris(2,4-di-tert-butylphenyl)phosphite. Trade name: Irgafos 168 (registered trademark), manufactured by BASF (hereinafter sometimes referred to as "C-2").
(C-3)
Phosphorus-based heat stabilizer with a melting point of 235°C Chemical name: 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[ 5,5]undecane. Trade name: Adekastab PEP-36 (registered trademark), manufactured by Adeka Corporation (hereinafter sometimes referred to as "C-3").
The melting point of the heat stabilizer was measured with a melting point measuring instrument model: B-545 (manufactured by Shibata Kagaku Co., Ltd.).

<Metal oxide, metal sulfide (D)>
(D-1)
Titanium oxide with an average primary particle size of 0.2 μm. _TiO2 . Trade name: R-TC30 (registered trademark) manufactured by Huntsman (hereinafter sometimes referred to as "D-1").
(D-2)
Zinc oxide with an average primary particle size of 0.3 μm. ZnO. Trade name: Ginrei A (registered trademark), manufactured by Mitsui Kinzoku Mining Co., Ltd. (hereinafter sometimes referred to as "D-2").
(D-3)
Zinc sulfide with an average primary particle size of 0.3 μm. ZnS. Trade name: Sactris HD (registered trademark), manufactured by Sacttriben (hereinafter sometimes referred to as "D-3").
(D-4)
Magnesium oxide with an average primary particle size of 0.6 μm. MgO. 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. EBS. 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.
(HCA)
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. Heat resistant aging improver. Product name: HCA (registered trademark), manufactured by Sanko.

[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) 17.5 parts by mass, (C-3) 1 part 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) 17 parts by mass, (C-3) 1 part by mass, (HCA) 1 part by mass, (F-1) 12 parts by mass, (TAFMER ) 1 part by mass, manufactured by Werner & Pfleiderer, 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 A resin composition was obtained by supplying from the most upstream part (top feed) of the screw pattern) 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 4]
(A-1) 68 parts by mass, (B-1) 16.5 parts by mass, (D-1) 80% by mass / (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) 18.7 parts by mass, (C-3) 0.1 parts by mass, (D-1) 80 mass% / (E-1) 20 mass 0.2 parts by mass of raw materials previously mixed with a Henschel mixer, 12 parts by mass of (F-1), and 1 part by mass of (TAFMER), manufactured by Werner & Pfleiderer in Germany, ZSK40MC with a barrel number of 13 and a screw diameter of 40 mm. Twin-screw extruder (kneading disk L: 2, kneading disk R: 6, kneading disk N: screw pattern with 4) supplied from the most upstream part (top feed), cylinder temperature 300 ° C., A resin composition was obtained by melt-kneading at 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.

[Example 2]
(B-1) from 18.7 parts by mass to 17.9 parts by mass, (C-3) from 0.1 parts by mass to 0.5 parts by mass, (D-1) 80% by mass / (E- 1) A resin composition was obtained by melt-kneading under the same conditions as in Example 1, except that 0.2 parts by mass of raw materials previously mixed with a Henschel mixer at 20% by mass was changed from 0.2 parts by mass to 0.6 parts by mass. Table 1 shows the physical property test results of the resin composition.

[Example 3]
(B-1) is 18.7 parts by mass to 16.8 parts by mass, (C-3) is 0.1 part by mass to 1 part by mass, and (D-1) is 80% by mass/(E-1) A resin composition was obtained by melt-kneading under the same conditions as in Example 1, except that 0.2 parts by mass of the raw materials previously mixed with a Henschel mixer was changed from 0.2 parts by mass to 1.2 parts by mass. Table 1 shows the physical property test results of the resin composition.

[Example 4]
(B-1) is 18.7 parts by mass to 15.5 parts by mass, (C-3) is 0.1 part by mass to 1 part by mass, and (D-1) is 80% by mass/(E-1) A resin composition was obtained by melt-kneading under the same conditions as in Example 1, except that 0.2 parts by mass of the raw material previously mixed with a Henschel mixer was changed from 0.2 parts by mass 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 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 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 6]
(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) 85 parts by mass, (B-2) 7.8 parts by mass, (C-3) 1 part 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) 15.5 parts by mass, (C-3) 1 part 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 weight, (B-1) 30 parts by weight, (C-3) 1 part by weight, (D-1) 80% by weight / (E-1) 20% by weight 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) 47.8 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 the 47.8 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) 26.5 parts by mass, (C-3) 2 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 7]
(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 8]
(E-1) was changed from 1.4 parts by mass to 2.1 parts by mass, and (B-1) was changed from 26.5 parts by mass to 25.8 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 9]
(D-1) was changed from 2.1 parts by mass to 3.6 parts by mass, and (E-1) was changed from 2.1 parts by mass to 0.6 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.

[Example 18]
Melt-kneading 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 47.8 parts by mass to 32.8 parts by mass. Then, a resin composition was obtained. Table 3 shows the physical property test results of the resin composition.

[Example 19]
(A-1) was changed from 35 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 32.8 parts by mass to 27.8 parts by mass. A resin composition was obtained by melt-kneading under the same conditions as in Example 18, except that the components were changed to parts. Table 3 shows the physical property test results of the resin composition.

From Table 1, the resin compositions of Comparative Examples 1 to 4 do not contain any or all of the above components (C), (D), and (E), so none of them have sufficient heat aging resistance. None.
The resin compositions of Comparative Examples 5 and 6 do not have sufficient heat aging resistance because the ratio of the components (D)/(E) deviates from the ratio specified above. In addition, in Comparative Examples 5 and 6, fogging was observed in both flat plate molded products at the 200th shot. In Comparative Example 5, there was MD adhesion to the mold after 200 shots, which was considered to be derived from component (E). ) component was used in a small amount, the component (D) was not sufficiently dispersed, which is presumed to be the cause of the poor appearance.
On the other hand, in the resin compositions of Examples 1 to 5, the blending amounts and blending ratios of the components (C), (D), and (E) are all within the ranges specified above, so excellent heat aging is achieved. showed sex. The appearance of the flat plate molded product at the 200th shot was also 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) are all within the ranges specified above. It showed heat aging resistance. The appearance of the flat plate molded product at the 200th shot was also good.

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) are all within the ranges specified above. The heat aging resistance was exhibited, and the appearance of the flat plate molded product at the 200th shot was also good. On the other hand, the resin composition of Comparative Example 7 does not have sufficient heat aging resistance because the ratio of the components (D)/(E) deviates from the ratio specified above.
Further, in Example 17 and Comparative Examples 7 to 9, haze was observed in the flat plate molded products at the 200th shot. In Example 17, the ratio of component (D)/(E) was within the range specified above. On the other hand, in Comparative Examples 7 to 9, the blending ratio of the (D)/(E) component is outside the range of the ratio specified above, and in Comparative Examples 8 and 9, the blending ratio of the (D)/(E) component Since the amount is outside the upper limit range specified above, the heat aging resistance is not sufficient. In Comparative Examples 7 and 8, after 200 shots, MD adhesion was also observed on the mold, which was considered to be derived from the component (E). In Comparative Example 9, the blending amount of component (D) was too large with respect to the blending amount of component (E), so component (D) was not sufficiently dispersed, presumably causing the poor appearance.

The polyphenylene ether-based resin composition of the present invention is excellent in heat aging resistance around 110 to 140 ° C. (for example, 110 ° C. or 130 ° C.), and at the same time, the performance balance between the rigidity and toughness that the polyphenylene ether-based resin originally retains. It is a polyphenylene ether-based resin composition that is retained without being damaged, and therefore can be effectively used for home appliance OA equipment parts, internal parts of electrical and electronic equipment, internal parts of automobiles, and decorative molded parts used for various industrial products. is possible.

Claims (13)

Polyphenylene ether (A), antioxidant (C), metal oxide and/or metal sulfide (D), and at least one lubricant selected from the group consisting of higher fatty acid amides, higher fatty acid bisamides and higher fatty acid metal salts (E) containing
Further optionally contains a styrene resin (B),
The mass ratio of each component to a total of 100 parts by mass of the component (A), the component (B), the component (C), the component (D) and the component (E) is 10 to 95 mass parts of the component (A). parts, 0 to 80 parts by mass of component (B), 0.05 to 3 parts by mass of component (C), and 0.1 to 3.5 parts by mass of components (D) and (E) in total,
A polyphenylene ether-based resin composition characterized in that the mass ratio of the component (D) and the component (E) is component (D)/component (E) = 80/20 to 55/45. 2. The polyphenylene ether-based resin composition according to claim 1, wherein the inorganic filler has a mass ratio of less than 15% by mass with respect to 100% by mass of the polyphenylene ether-based resin composition. 3. The polyphenylene ether resin composition according to claim 2, wherein the inorganic filler has a mass ratio of 4% by mass or less. The polyphenylene ether resin composition according to claim 1 or 3, wherein the component (C) is an antioxidant having a melting point of 180°C or higher. The polyphenylene ether resin composition according to claim 1 or 3, wherein the content of the aromatic phosphate ester flame retardant and/or the phosphazene flame retardant in 100% by mass of the polyphenylene ether resin composition is 5% by mass or less. thing. The polyphenylene ether resin composition according to claim 1 or 3, wherein the component (C) is a phosphorus antioxidant. The polyphenylene ether resin composition according to claim 1 or 3, wherein the component (D) contains at least one selected from the group consisting of titanium oxide, zinc oxide and zinc sulfide. The (C) component, the (D) component and the ( E) The polyphenylene ether-based resin composition according to claim 1 or 3, wherein the total mass ratio of component is 4 parts by mass or less. Furthermore, it contains a styrene-based thermoplastic elastomer (F),
The mass ratio of the component (F) with respect to a total of 100 parts by mass of the component (A), the component (B), the component (C), the component (D) and the component (E) is 0.1 to The polyphenylene ether resin composition according to claim 1 or 3, which is 25 parts by mass. Total mass of the (A) component, the (B) component, the (C) component, the (D) component, the (E) component and the (F) component with respect to 100% by mass of the polyphenylene ether resin composition The polyphenylene ether-based resin composition according to claim 9, wherein the proportion is 85% by mass or more. The polyphenylene ether-based resin composition according to claim 1 or 3, wherein the polyolefin-based resin has a mass ratio of 5% by mass or less with respect to 100% by mass of the polyphenylene ether-based resin composition. 4. The polyphenylene ether resin composition according to claim 1, which has a tensile strength retention of 90% or more after aging at 130° C. for 500 hours. A method for producing the polyphenylene ether-based resin composition according to claim 1 or 3,
A step of melt-kneading the (A) component, the (C) component, the (D) component and the (E) component, and optionally the (B) component, the (F) component and/or other materials including
A method for producing a polyphenylene ether-based resin composition, wherein in the melt-kneading step, a mixture of the component (D) and the component (E) is used as a raw material.